GRAND RAPIDS

COMMUNITY
COLLEGE: CHM 120
SURVEY OF GENERAL
CHEMISTRY

Thomas Neils
Grand Rapids Community College
 Grand Rapids Community College
Grand Rapids Community College: CHM 120
Survey of General Chemistry

Thomas Neils
This text is disseminated via the Open Education Resource (OER) LibreTexts Project ([Link] and like the hundreds
of other texts available within this powerful platform, it is freely available for reading, printing and "consuming." Most, but not all,
pages in the library have licenses that may allow individuals to make changes, save, and print this book. Carefully
consult the applicable license(s) before pursuing such effects.
Instructors can adopt existing LibreTexts texts or Remix them to quickly build course-specific resources to meet the needs of their
students. Unlike traditional textbooks, LibreTexts’ web based origins allow powerful integration of advanced features and new
technologies to support learning.

The LibreTexts mission is to unite students, faculty and scholars in a cooperative effort to develop an easy-to-use online platform
for the construction, customization, and dissemination of OER content to reduce the burdens of unreasonable textbook costs to our
students and society. The LibreTexts project is a multi-institutional collaborative venture to develop the next generation of open-
access texts to improve postsecondary education at all levels of higher learning by developing an Open Access Resource
environment. The project currently consists of 14 independently operating and interconnected libraries that are constantly being
optimized by students, faculty, and outside experts to supplant conventional paper-based books. These free textbook alternatives are
organized within a central environment that is both vertically (from advance to basic level) and horizontally (across different fields)
integrated.
The LibreTexts libraries are Powered by NICE CXOne and are supported by the Department of Education Open Textbook Pilot
Project, the UC Davis Office of the Provost, the UC Davis Library, the California State University Affordable Learning Solutions
Program, and Merlot. This material is based upon work supported by the National Science Foundation under Grant No. 1246120,
1525057, and 1413739.
Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not
necessarily reflect the views of the National Science Foundation nor the US Department of Education.
Have questions or comments? For information about adoptions or adaptions contact info@[Link]. More information on our
activities can be found via Facebook ([Link] Twitter ([Link] or our blog
([Link]
This text was compiled on 09/11/2023
TABLE OF CONTENTS
Licensing

1: Matter and Energy

1.1 The Terms of Science
1.2: A First Look at the Periodic Table
1.3: The Classification of Matter
1.4: A First Look at Energy
1.5: Making Measurements
1.6: Limits on Measurements
1.7: Dimensional Analysis
1.8: Matter, Measurement, and Problem Solving (Exercises)

2: Atomic Structure
2.1: Modern Atomic Theory and the Laws That Led to It
2.2 The Structure of the Atom
2.3 Molar Mass - Counting Atoms by Weighing Them
2.4 Nuclear Reactions
2.5 The Belt of Stability - Predicting the Type of Radioactivity
2.6 Half-lives and the Rate of Radioactive Decay
2.7 Mass Defect - The Source of Nuclear Energy
2.8 Nuclear Energy - Fission and Fusion
2.9 The Nature of Light
2.10 Quantum Mechanics and The Atom
2.11 Trends of the Periodic Table
2.12 Example Problems

3: Chemical Formulas and Bonding

3.1 An Atomic-Level Perspective of Ionic and Covalent Compounds
3.2 Composition of Compounds
3.3 Chemical Bonds
3.4 Ionic Compounds: Formulas and Names
3.5 Covalently-Bonded Species: Formulas and Names
3.6 Electronegativity and Bond Polarity
3.7 Lewis Structures
3.8 Resonance and Formal Charge Revisited
3.9 Exceptions to the Octet Rule
3.10 Shapes of Molecules - VSEPR Theory and Valence Bond Theory
3.11 Practice Problems

4: Intermolecular Forces, Phases, and Solutions

4.1 Water in Zero Gravity - an Introduction to Intermolecular Forces
4.2 Intermolecular Forces
4.3 Application of IMFs: Evaporation, Vapor Pressure, and Boiling Points
4.4: Intermolecular Forces in Action: Surface Tension, Viscosity, and Capillary Action
4.5: Solids, Liquids, and Gases: A Molecular Comparison
4.6 Phase Changes

1 [Link]
 4.7: Pressure: The Result of Particle Collisions
4.8: Gases
4.9 Solutions - What Mixes Together and Why
4.10 Factors Affecting Solubility
4.11 Suspensions and Colloids
4.12 Practice Problems
Intermolecular Forces

5: The Numbers Game - Solutions and Stoichiometry

5.1 Expressing Solution Concentration
5.2 Types of Aqueous Solutions and Solubility
5.3 Colligative Properties and Freezing Point Depression and Boiling Point Elevation and Osmosis
5.4 Writing and Balancing Chemical Equations
5.5 Limiting Reactant and Theoretical Yield and Percent Yield
5.6 Representing Aqueous Reactions Molecular and Ionic and Complete Ionic Equations
5.7 Chemical Reactions and Aqueous Reactions (Exercises)

6: Reaction Kinetics
6.1: Chemical Kinetics
6.2 The Effect of Concentration on Reaction Rate
6.3: Reaction Mechanisms
6.4: The Effect of Temperature on Reaction Rate
6.5 Catalysts

7: Equilibrium and Thermodynamics

7.1: The Concept of Dynamic Equilibrium
7.2 The Equilibrium Constant
7.3: Calculating the Equilibrium Constant From Measured Equilibrium Concentrations
7.4 Predicting the Direction of a Reaction
7.5 Le Châtelier’s Principle: How a System at Equilibrium Responds to Disturbances
7.6: The First Law of Thermodynamics
7.7: Enthalpy: The Heat Evolved in a Chemical Reaction at Constant Pressure
7.8 Quantifying Heat
7.9: Entropy and the Second Law of Thermodynamics
7.10: Gibbs Free Energy
7.11 Gibbs Free Energy and Equilibrium
What we are studying

8: Acids and Bases

8.1: An Introduction to Acids and Bases
8.2: Brønsted-Lowry Acids and Bases
8.3 Lewis Acids and Bases
8.4: Acid Strength and the Acid Dissociation Constant (Ka)
8.5: Autoionization of Water and pH
8.6 - Finding the Hydronium Ion Concentration and pH of Strong and Weak Acid Solutions
8.7: The Acid-Base Properties of Ions and Salts
8.8: Buffers: Solutions That Resist pH Change
8.9 Buffer Capacity and Buffer Range
8.10: Lewis Acids and Bases
8.11: Acid/Base (Exercises)

2 [Link]
9: Electrochemistry
9.1: Oxidation-Reduction Reactions
9.2: Standard Reduction Potentials
9.3 Cell Potential, Gibbs Free Energy, and Equilibrium
9.4: Batteries: Using Chemistry to Generate Electricity
9.5 Driving Reactant-Favored Reactions Using Electricity
9.6 Undesirable Redox Reactions

Index
Glossary

Detailed Licensing

3 [Link]
Licensing
A detailed breakdown of this resource's licensing can be found in Back Matter/Detailed Licensing.

1 [Link]
 CHAPTER OVERVIEW

1: Matter and Energy

1.1 The Terms of Science
1.2: A First Look at the Periodic Table
1.3: The Classification of Matter
1.4: A First Look at Energy
1.5: Making Measurements
1.6: Limits on Measurements
1.7: Dimensional Analysis
1.8: Matter, Measurement, and Problem Solving (Exercises)

1: Matter and Energy is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
1.1 The Terms of Science
1.1 The Terms of Science is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1 [Link]
1.2: A First Look at the Periodic Table
Building Blocks
Chemistry involves studying the interaction of the basic building blocks of nature. These building blocks are the atoms of the 118
known elements. People often get confused about atoms and elements. Atoms are the smallest particle of an element that exhibit
the properties of that element. An analogy for elements and atoms is LegosTM. Each Lego piece is an atom, and each shape
represents an element. Thus, all cube-shaped Lego pieces with one "peg" on top, regardless of color, could represent H atoms, and
all rectangular box pieces with two pegs on top, regardless of color, could represent He atoms. In nature, the defining feature of
each element is the number of protons in the nucleus, which is called the atomic number of that element. Chemists created an
organized chart of the elements called the Periodic Table of the Elements. In the most common format of the table, the elements are
arranged in order of increasing atomic numbers.
The periodic table is not simply a grid of elements arranged numerically. In the periodic table, the elements are arranged in
horizontal rows called periods, and into vertical columns called groups. These groups are numbered by two, somewhat conflicting,
schemes. In the simplest presentation, favored by the International Union of Pure and Applied Chemistry (IUPAC), the groups are
simply numbered 1-18. The convention in much of the world, however, is to number the first two groups IA and IIA, the last six
groups IIIA-VIIIA; the middle ten groups are then numbered IB-VIIIB (but not in that order!). While the IUPAC numbering
appears much simpler, in this class we will use the "old-fashioned" nomenclature (IA-VIIIA). The reason for this choice will
become more apparent in later chapters when we discuss “valence" electrons and bonding. The actual layout of the periodic table is
based on the grouping of the elements according to chemical properties. For example, elements in each group of the periodic table
(each vertical column) will share many of the same chemical properties. As we discuss the properties of elements and the ways
they combine with other elements, the reasons for this particular arrangement of the periodic table will become more obvious.

As you can see, each element in the periodic table is represented by a box containing the chemical symbol, the atomic number (the
number of protons in the nucleus) and the atomic mass of the element. As we will discover, the atomic mass is the weighted

1.2.1 [Link]
average of the masses of all of the natural isotopes of the particular element.
The elements can be classified in many ways. For instance, elements in Groups IA – VIIIA are called the representative, or main
group, elements, and the elements in Groups IB - VIIIB are called the transition metals. The broadest classification of elements is
into metals, metalloids (or semi-metals) and nonmetals. The metallic elements are shown in green on the table here. Metals are
solids at room temperature (except for mercury), can conduct electricity, and are usually malleable (can be rolled into sheets) and
ductile (can be drawn into wires). Metals are usually separated into the main group metals in Groups IA - VA and the transition
metals in Groups IB - VIIIB. Nonmetals (red in the figure) do not conduct electricity well or at all, and have a variety of physical
states (some are solids, some liquids and some gases). At the border between metals and nonmetals lie the elements boron, silicon,
germanium, arsenic, antimony and tellurium. These elements share physical properties of metals and nonmetals and are called
metalloids, or semi-metals. The common semiconductors silicon and germanium are in this group, and it is their unique electrical
properties that make transistors and other solid-state devices possible. The elements Po, At, Lv, Ts, and Og are all fairly rare
elements, and there is some discussion about how they should be classified. We will not concern ourselves with them.

Named Families
Group IA: The Alkali Metals
The alkali metals are lithium, sodium, potassium, rubidium, cesium, and francium. The name "alkali" comes from an Arabic term
related to ashes from burned plants. These ashes contain large amounts of potassium and sodium compounds that form basic
aqueous solutions. The compounds of the alkali metals are common in nature and daily life. One example is table salt (sodium
chloride); lithium compounds are used in greases, in batteries, and as drugs to treat patients who exhibit manic-depressive, or
bipolar, behavior. Although lithium, rubidium, and cesium are relatively rare in nature, and francium is so unstable and highly
radioactive that it exists in only trace amounts, sodium and potassium are the seventh and eighth most abundant elements in Earth’s
crust, respectively. Note: Hydrogen is generally placed in Group 1, but it is not an alkali metal.

Group IIA: The Alkaline Earth Metals

The alkaline earth metals are beryllium, magnesium, calcium, strontium, barium, and radium. The name "alkaline earth" comes
from the fact that the oxides of the metals in this family were called "earths", and when these compounds are placed in water, the
solution becomes basic. Beryllium, strontium, and barium are rare, and radium is unstable and highly radioactive. In contrast,
calcium and magnesium are the fifth and sixth most abundant elements on Earth, respectively; they are found in huge deposits of
limestone and other minerals.

Group VIIA: The Halogens

The halogens are fluorine, chlorine, bromine, iodine, astatine, and tennessine. The name halogen is derived from the Greek words
for “salt forming,” which reflects that all the halogens react readily with metals to form compounds, such as sodium chloride and
calcium chloride (used in some areas as road salt).
Compounds that contain the fluoride ion are added to toothpaste and the water supply to prevent dental cavities. Fluorine is also
found in Teflon coatings on kitchen utensils. Although chlorofluorocarbon propellants and refrigerants are believed to lead to the
depletion of Earth’s ozone layer and contain both fluorine and chlorine, the latter is responsible for the adverse effect on the ozone
layer. Bromine and iodine are less abundant than chlorine, and astatine is so radioactive that it exists in only negligible amounts in
nature.

Group VIIIA: The Noble Gases

The noble gases are helium, neon, argon, krypton, xenon, radon, and oganesson. Because the noble gases are composed of only
single atoms, they are called monatomic elements. At room temperature and pressure, they are unreactive gases. This lack of
reactivity led to their name, in that "noble" elements would not interact with the rest of the elements. Because of their lack of
reactivity, for many years they were also called inert gases or rare gases. However, the first chemical compounds containing the
noble gases were prepared in 1962. Although the noble gases are relatively minor constituents of the atmosphere, natural gas
contains substantial amounts of helium. Because of its low reactivity, argon is often used as an unreactive (inert) atmosphere for
welding and in light bulbs. The red light emitted by neon in a gas discharge tube is used in neon lights.

1.2.2 [Link]
Contributors
Paul R. Young, Professor of Chemistry, University of Illinois at Chicago, Wiki: AskTheNerd; PRY [Link] - pyoung
[Link]; [Link]
Tom Neils (Grand Rapids Community College)

1.2: A First Look at the Periodic Table is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1.2.3 [Link]
1.3: The Classification of Matter
Skills to Develop
To classify matter.

Chemists study the structures, physical properties, and chemical properties of material substances. These consist of matter, which
is anything that occupies space and has mass. Gold and iridium are matter, as are peanuts, people, and postage stamps. Smoke,
smog, and laughing gas are matter. Energy, light, and sound, however, are not matter; ideas and emotions are also not matter.
The mass of an object is the quantity of matter it contains. Do not confuse an object’s mass with its weight, which is a force caused
by the gravitational attraction that operates on the object. Mass is a fundamental property of an object that does not depend on its
[Link] physical terms, the mass of an object is directly proportional to the force required to change its speed or direction. A
more detailed discussion of the differences between weight and mass and the units used to measure them is included in Essential
Skills 1 (Section 1.9). Weight, on the other hand, depends on the location of an object. An astronaut whose mass is 95 kg weighs
about 210 lb on Earth but only about 35 lb on the moon because the gravitational force he or she experiences on the moon is
approximately one-sixth the force experienced on Earth. For practical purposes, weight and mass are often used interchangeably in
laboratories. Because the force of gravity is considered to be the same everywhere on Earth’s surface, 2.2 lb (a weight) equals 1.0
kg (a mass), regardless of the location of the laboratory on Earth.
Under normal conditions, there are three distinct states of matter: solids, liquids, and gases. Solids are relatively rigid and have
fixed shapes and volumes. A rock, for example, is a solid. In contrast, liquids have fixed volumes but flow to assume the shape of
their containers, such as a beverage in a can. Gases, such as air in an automobile tire, have neither fixed shapes nor fixed volumes
and expand to completely fill their containers. Whereas the volume of gases strongly depends on their temperature and pressure
(the amount of force exerted on a given area), the volumes of liquids and solids are virtually independent of temperature and
pressure. Matter can often change from one physical state to another in a process called a physical change. For example, liquid
water can be heated to form a gas called steam, or steam can be cooled to form liquid water. However, such changes of state do not
affect the chemical composition of the substance.

Figure 1.3.1 : The Three States of Matter. Solids have a defined shape and volume. Liquids have a fixed volume but flow to assume
the shape of their containers. Gases completely fill their containers, regardless of volume. Figure used with permission from
Wikipedia

Pure Substances and Mixtures

A pure chemical substance is any matter that has a fixed chemical composition and characteristic properties. Oxygen, for example,
is a pure chemical substance that is a colorless, odorless gas at 25°C. Very few samples of matter consist of pure substances;
instead, most are mixtures, which are combinations of two or more pure substances in variable proportions in which the individual
substances retain their identity. Air, tap water, milk, blue cheese, bread, and dirt are all mixtures. If all portions of a material are in
the same state, have no visible boundaries, and are uniform throughout, then the material is homogeneous. Examples of
homogeneous mixtures are the air we breathe and the tap water we drink. One type of homogeneous mixture is called a solution.
Thus air is a solution of nitrogen, oxygen, water vapor, carbon dioxide, and several other gases; tap water is a solution of small
amounts of several substances in water. The specific compositions of both of these solutions are not fixed, however, but depend on
both source and location; for example, the composition of tap water in Boise, Idaho, is not the same as the composition of tap water
in Buffalo, New York. Although most solutions we encounter are liquid, solutions can also be solid. The gray substance still used
by some dentists to fill tooth cavities is a complex solid solution that contains 50% mercury and 50% of a powder that contains
mostly silver, tin, and copper, with small amounts of zinc and mercury. Solid solutions of two or more metals are commonly called
alloys.

1.3.1 [Link]
If the composition of a material is not completely uniform, then it is heterogeneous (e.g., chocolate chip cookie dough, blue
cheese, and dirt). Mixtures that appear to be homogeneous are often found to be heterogeneous after microscopic examination.
Milk, for example, appears to be homogeneous, but when examined under a microscope, it clearly consists of tiny globules of fat
and protein dispersed in water. The components of heterogeneous mixtures can usually be separated by simple means. Solid-liquid
mixtures such as sand in water or tea leaves in tea are readily separated by filtration, which consists of passing the mixture through
a barrier, such as a strainer, with holes or pores that are smaller than the solid particles. In principle, mixtures of two or more solids,
such as sugar and salt, can be separated by microscopic inspection and sorting. More complex operations are usually necessary,
though, such as when separating gold nuggets from river gravel by panning. First solid material is filtered from river water; then
the solids are separated by inspection. If gold is embedded in rock, it may have to be isolated using chemical methods.

Figure 1.3.2 : A Heterogeneous Mixture. Under a microscope, whole milk is actually a heterogeneous mixture composed of
globules of fat and protein dispersed in water. Figure used with permission from Wikipedia
Homogeneous mixtures (solutions) can be separated into their component substances by physical processes that rely on differences
in some physical property, such as differences in their boiling points. Two of these separation methods are distillation and
crystallization. Distillation makes use of differences in volatility, a measure of how easily a substance is converted to a gas at a
given temperature. A simple distillation apparatus for separating a mixture of substances, at least one of which is a liquid. The most
volatile component boils first and is condensed back to a liquid in the water-cooled condenser, from which it flows into the
receiving flask. If a solution of salt and water is distilled, for example, the more volatile component, pure water, collects in the
receiving flask, while the salt remains in the distillation flask.

Figure 1.3.3 : The Distillation of a Solution of Table Salt in Water. The solution of salt in water is heated in the distilling flask
until it boils. The resulting vapor is enriched in the more volatile component (water), which condenses to a liquid in the cold
condenser and is then collected in the receiving flask.
Mixtures of two or more liquids with different boiling points can be separated with a more complex distillation apparatus. One
example is the refining of crude petroleum into a range of useful products: aviation fuel, gasoline, kerosene, diesel fuel, and
lubricating oil (in the approximate order of decreasing volatility). Another example is the distillation of alcoholic spirits such as

1.3.2 [Link]
brandy or whiskey. (This relatively simple procedure caused more than a few headaches for federal authorities in the 1920s during
the era of Prohibition, when illegal stills proliferated in remote regions of the United States!)
Crystallization separates mixtures based on differences in solubility, a measure of how much solid substance remains dissolved in
a given amount of a specified liquid. Most substances are more soluble at higher temperatures, so a mixture of two or more
substances can be dissolved at an elevated temperature and then allowed to cool slowly. Alternatively, the liquid, called the solvent,
may be allowed to evaporate. In either case, the least soluble of the dissolved substances, the one that is least likely to remain in
solution, usually forms crystals first, and these crystals can be removed from the remaining solution by filtration.

Figure 1.3.4 : The Crystallization of Sodium Acetate from a Concentrated Solution of Sodium Acetate in Water. The addition of a
small “seed” crystal (a) causes the compound to form white crystals, which grow and eventually occupy most of the flask. Video
can be found here: [Link]
Most mixtures can be separated into pure substances, which may be either elements or compounds. An element, such as gray,
metallic sodium, is a substance that cannot be broken down into simpler ones by chemical changes; a compound, such as white,
crystalline sodium chloride, contains atoms of two or more elements that have been chemically combined, and has chemical and
physical properties that are usually different from those of the elements of which it is composed. With only a few exceptions, a
particular compound has the same elemental composition (the same elements in the same proportions) regardless of its source or
history. The chemical composition of a substance is altered in a process called a chemical change. The conversion of two or more
elements, such as sodium and chlorine, to a chemical compound, sodium chloride, is an example of a chemical change, often called
a chemical reaction. Currently, about 118 elements are known, but millions of chemical compounds have been prepared from these
118 elements. The known elements are listed in the periodic table.

Figure 1.3.5 : The Decomposition of Water to Hydrogen and Oxygen by Electrolysis. Water is a chemical compound; hydrogen
and oxygen are elements.
In general, a reverse chemical process breaks down compounds into their elements. For example, water (a compound) can be
decomposed into hydrogen and oxygen (both elements) by a process called electrolysis. In electrolysis, electricity provides the
energy needed to separate a compound into its constituent elements (Figure 1.3.5). A similar technique is used on a vast scale to
obtain pure aluminum, an element, from its ores, which are mixtures of compounds. Because a great deal of energy is required for

1.3.3 [Link]
electrolysis, the cost of electricity is by far the greatest expense incurred in manufacturing pure aluminum. Thus recycling
aluminum is both cost-effective and ecologically sound.
The overall organization of matter and the methods used to separate mixtures are summarized in Figure 1.3.6.

Figure 1.3.6 : Relationships between the Types of Matter and the Methods Used to Separate Mixtures

Example 1.3.1
Identify each substance as a compound, an element, a heterogeneous mixture, or a homogeneous mixture (solution).
a. filtered tea
b. freshly squeezed orange juice
c. a compact disc
d. aluminum oxide, a white powder that contains a 2:3 ratio of aluminum and oxygen atoms
e. selenium
Given: a chemical substance
Asked for: its classification
Strategy:
A. Decide whether a substance is chemically pure. If it is pure, the substance is either an element or a compound. If a substance
can be separated into its elements, it is a compound.
B. If a substance is not chemically pure, it is either a heterogeneous mixture or a homogeneous mixture. If its composition is
uniform throughout, it is a homogeneous mixture.
Solution:
a. A Tea is a solution of compounds in water, so it is not chemically pure. It is usually separated from tea leaves by filtration. B
Because the composition of the solution is uniform throughout, it is a homogeneous mixture.
b. A Orange juice contains particles of solid (pulp) as well as liquid; it is not chemically pure. B Because its composition is not
uniform throughout, orange juice is a heterogeneous mixture.
c. A A compact disc is a solid material that contains more than one element, with regions of different compositions visible
along its edge. Hence a compact disc is not chemically pure. B The regions of different composition indicate that a compact
disc is a heterogeneous mixture.
d. A Aluminum oxide is a single, chemically pure compound.
e. A Selenium is one of the known elements.

Exercise 1.3.1
Identify each substance as a compound, an element, a heterogeneous mixture, or a homogeneous mixture (solution).

1.3.4 [Link]
 a. white wine
b. mercury
c. ranch-style salad dressing
d. table sugar (sucrose)

Answer A
solution
Answer B
element
Answer C
heterogeneous mixture
Answer D
compound

Physical versus Chemical Properties

The characteristics that enable us to distinguish one substance from another are called properties. A physical property is a
characteristic of matter that is not associated with a change in its chemical composition. Familiar examples of physical properties
include density, color, hardness, melting and boiling points, and electrical conductivity. We can observe some physical properties,
such as density and color, without changing the physical state of the matter observed. Other physical properties, such as the melting
temperature of iron or the freezing temperature of water, can only be observed as matter undergoes a physical change. A physical
change is a change in the state or properties of matter without any accompanying change in its chemical composition (the identities
of the substances contained in the matter). We observe a physical change when wax melts, when sugar dissolves in coffee, and
when steam condenses into liquid water Figure 1.3.7 . Other examples of physical changes include magnetizing and
demagnetizing metals (as is done with common antitheft security tags) and grinding solids into powders (which can sometimes
yield noticeable changes in color). In each of these examples, there is a change in the physical state, form, or properties of the
substance, but no change in its chemical composition.

Figure 1.3.7 : (a) Wax undergoes a physical change when solid wax is heated and forms liquid wax. (b) Steam condensing inside a
cooking pot is a physical change, as water vapor is changed into liquid water. (credit a: modification of work by
“95jb14”/Wikimedia Commons; credit b: modification of work by “mjneuby”/Flickr).
The change of one type of matter into another type (or the inability to change) is a chemical property. Examples of chemical
properties include flammability, toxicity, acidity, reactivity (many types), and heat of combustion. Iron, for example, combines with
oxygen in the presence of water to form rust; chromium does not oxidize Figure 1.3.8 . Nitroglycerin is very dangerous because it
explodes easily; neon poses almost no hazard because it is very unreactive.

1.3.5 [Link]
Figure Figure 1.3.8 : (a) One of the chemical properties of iron is that it rusts; (b) one of the chemical properties of chromium is
that it does not. (credit a: modification of work by Tony Hisgett; credit b: modification of work by “Atoma”/Wikimedia Commons)
To identify a chemical property, we look for a chemical change. A chemical change always produces one or more types of matter
that differ from the matter present before the change. The formation of rust is a chemical change because rust is a different kind of
matter than the iron, oxygen, and water present before the rust formed. The explosion of nitroglycerin is a chemical change because
the gases produced are very different kinds of matter from the original substance. Other examples of chemical changes include
reactions that are performed in a lab (such as copper reacting with nitric acid), all forms of combustion (burning), and food being
cooked, digested, or rotting Figure 1.3.9 .

Figure 1.3.9 : (a) Copper and nitric acid undergo a chemical change to form copper nitrate and brown, gaseous nitrogen dioxide.
(b) During the combustion of a match, cellulose in the match and oxygen from the air undergo a chemical change to form carbon
dioxide and water vapor. (c) Cooking red meat causes a number of chemical changes, including the oxidation of iron in myoglobin
that results in the familiar red-to-brown color change. (d) A banana turning brown is a chemical change as new, darker (and less
tasty) substances form. (credit b: modification of work by Jeff Turner; credit c: modification of work by Gloria Cabada-Leman;
credit d: modification of work by Roberto Verzo)
Physical properties of matter fall into one of two categories. If the property depends on the amount of matter present, it is an
extensive property. The mass and volume of a substance are examples of extensive properties; for instance, a gallon of milk has a
larger mass and volume than a cup of milk. The value of an extensive property is directly proportional to the amount of matter in
question. If the property of a sample of matter does not depend on the amount of matter present, it is an intensive property.
Temperature is an example of an intensive property. If the gallon and cup of milk are each at 20 °C (room temperature), when they
are combined, the temperature remains at 20 °C. As another example, consider the distinct but related properties of heat and
temperature. A drop of hot cooking oil spattered on your arm causes brief, minor discomfort, whereas a pot of hot oil yields severe

1.3.6 [Link]
burns. Both the drop and the pot of oil are at the same temperature (an intensive property), but the pot clearly contains much more
heat (extensive property).

Summary
Matter can be classified according to physical and chemical properties. Matter is anything that occupies space and has mass. The
three states of matter are solid, liquid, and gas. A physical change involves the conversion of a substance from one state of matter
to another, without changing its chemical composition. Most matter consists of mixtures of pure substances, which can be
homogeneous (uniform in composition) or heterogeneous (different regions possess different compositions and properties). Pure
substances can be either chemical compounds or elements. Compounds can be broken down into elements by chemical reactions,
but elements cannot be separated into simpler substances by chemical means. The properties of substances can be classified as
either physical or chemical. Scientists can observe physical properties without changing the composition of the substance, whereas
chemical properties describe the tendency of a substance to undergo chemical changes (chemical reactions) that change its
chemical composition. Physical properties can be intensive or extensive. Intensive properties are the same for all samples; do not
depend on sample size; and include, for example, color, physical state, and melting and boiling points. Extensive properties depend
on the amount of material and include mass and volume. The ratio of two extensive properties, mass and volume, is an important
intensive property called density.

Contributors
Modified by Joshua Halpern (Howard University)
Tom Neils (Grand Rapids Community College)

1.3: The Classification of Matter is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1.3.7 [Link]
1.4: A First Look at Energy
Skills to Develop
To understand the concept of energy and its various forms.
To know the relationship between energy, work, and heat.

Because energy takes many forms, only some of which can be seen or felt, it is defined by its effect on matter. For example, microwave
ovens produce energy to cook food, but we cannot see that energy. In contrast, we can see the energy produced by a light bulb when we
switch on a lamp. In this section, we describe the forms of energy and discuss the relationship between energy, heat, and work.

Forms of Energy
The forms of energy include thermal energy, radiant energy, electrical energy, nuclear energy, and chemical energy (Figure 1.4.1).
Thermal energy results from atomic and molecular motion; the faster the motion, the greater the thermal energy. The temperature of an
object is a measure of its thermal energy content. Radiant energy is the energy carried by light, microwaves, and radio waves. Objects
left in bright sunshine or exposed to microwaves become warm because much of the radiant energy they absorb is converted to thermal
energy. Electrical energy results from the flow of electrically charged particles. When the ground and a cloud develop a separation of
charge, for example, the resulting flow of electrons from one to the other produces lightning, a natural form of electrical energy.
Nuclear energy is stored in the nucleus of an atom, and chemical energy is stored within a chemical compound because of a particular
arrangement of atoms.

Figure 1.4.1 : Forms of Energy. (a) Thermal energy results from atomic and molecular motion; molten steel at 2000°C has a very high
thermal energy content. (b) Radiant energy (e.g., from the sun) is the energy in light, microwaves, and radio waves. (c) Lightning is an
example of electrical energy, which is due to the flow of electrically charged particles. (d) Nuclear energy is released when particles in
the nucleus of the atom are rearranged. (e) Chemical energy results from the particular arrangement of atoms in a chemical compound;
the heat and light produced in this reaction are due to energy released during the breaking and reforming of chemical bonds.
Electrical energy, nuclear energy, and chemical energy are different forms of potential energy (PE), which is energy of an object
because of the relative positions or orientations of its components. A brick lying on the windowsill of a 10th-floor office has a great
deal of potential energy, but until its position changes by falling, the energy is contained. In contrast, kinetic energy (KE) is energy due
to the motion of an object. When the brick falls, its potential energy is transformed to kinetic energy, which is then transferred to the
object on the ground that it strikes. The electrostatic attraction between oppositely charged particles is a form of potential energy, which
is converted to kinetic energy when the charged particles move toward each other.
Energy can be converted from one form to another (Figure 1.4.2) or, as we saw with the brick, transferred from one object to another.
For example, when you climb a ladder to a high diving board, your body uses chemical energy produced by the combustion of organic
molecules. As you climb, the chemical energy is converted to mechanical work to overcome the force of gravity. When you stand on the

1.4.1 [Link]
end of the diving board, your potential energy is greater than it was before you climbed the ladder: the greater the distance from the
water, the greater the potential energy. When you then dive into the water, your potential energy is converted to kinetic energy as you
fall, and when you hit the surface, some of that energy is transferred to the water, causing it to splash into the air. Chemical energy can
also be converted to radiant energy; one common example is the light emitted by fireflies, which is produced from a chemical reaction.

Figure 1.4.2 : Interconversion of Forms of Energy. When a swimmer steps off the platform to dive into the water, potential energy is
converted to kinetic energy. As the swimmer climbs back up to the top of the diving platform, chemical energy is converted to
mechanical work.
Although energy can be converted from one form to another, the total amount of energy in the universe remains constant. This is known
as the law of conservation of energy: Energy cannot be created or destroyed.

Energy, Heat, and Work

One definition of energy is the capacity to do work. The easiest form of work to visualize is mechanical work (Figure 1.4.3), which is
the energy required to move an object a distance d when opposed by a force F, such as gravity:
work = force x distance
w =F d (1.4.1)

Because the force (F) that opposes the action is equal to the mass (m) of the object times its acceleration (a), we can also write Equation
1.4.1 as follows:

work= mass x acceleration x distance

w =mad (1.4.2)

Recall from that weight is a force caused by the gravitational attraction between two masses, such as you and Earth.
Consider the mechanical work required for you to travel from the first floor of a building to the second. Whether you take an elevator or
an escalator, trudge upstairs, or leap up the stairs two at a time, energy is expended to overcome the force of gravity. The amount of
work done (w) and thus the energy required depends on three things:
1. the height of the second floor (the distance d);
2. your mass, which must be raised that distance against the downward acceleration due to gravity; and
3. your path.

1.4.2 [Link]
 Figure 1.4.2 : An Example of Mechanical Work. One form of energy is mechanical work, the energy required to move an object of
mass m a distance d when opposed by a force F, such as gravity.
In contrast, heat (q) is thermal energy that can be transferred from an object at one temperature to an object at another temperature. The
net transfer of thermal energy stops when the two objects reach the same temperature.
Energy is an extensive property of matter—for example, the amount of thermal energy in an object is proportional to both its mass and
its temperature. A water heater that holds 150 L of water at 50°C contains much more thermal energy than does a 1 L pan of water at
50°C. Similarly, a bomb contains much more chemical energy than does a firecracker.

A Mathematical Description of Kinetic Energy and Potential Energy

A Mathematical Description of Kinetic Energy and Potential Energy
1
2
KE = mv (1.4.3)
2

The potential energy of an object is related to its position relative to another object or to a standard baseline (usually, the ground). As
noted above, the energy required to move an object when opposed by a force (such as gravity), is:

work = mass x acceleration x distance = force x distance

An Example
The kinetic energy of a 1360 kg (approximately 3000 lb) automobile traveling at a velocity of 26.8 m/s (approximately 60 mi/h) i
1
2 5 2
KE = (1360kg)(26.8ms) = 4.88 × 10 g ⋅ m (1.4.4)
2

Because all forms of energy can be interconverted, energy in any form can be expressed using the same units as kinetic energy. The SI
unit of energy, the joule (J), is named after the British physicist James Joule (1818–1889), an early worker in the field of energy. is
defined as 1 kilogram·meter2/second2 (kg·m2/s2). Because a joule is such a small quantity of energy, chemists usually express energy in
kilojoules (1 kJ = 103 J). For example, the kinetic energy of the 1360 kg car traveling at 26.8 m/s is 4.88 × 105 J or 4.88 × 102 kJ. It is
important to remember that the units of energy are the same regardless of the form of energy, whether thermal, radiant, chemical, or any
other form. Because heat and work result in changes in energy, their units must also be the same.

To demonstrate, let’s calculate the potential energy of the same 1360 kg automobile if it were parked on the top level of a parking
garage 36.6 m (120 ft) high. Its potential energy is equivalent to the amount of work required to raise the vehicle from street level to the

1.4.3 [Link]
top level of the parking garage, which is w = Fd. According to Equation 1.4.2, the force (F) exerted by gravity on any object is equal to
its mass (m, in this case, 1360 kg) times the acceleration (a) due to gravity (g, 9.81 m/s2 at Earth’s surface). The distance (d) is the
height (h) above street level (in this case, 36.6 m). Thus the potential energy of the car is as follows:
PE = F d = m a d = m gh (1.4.5)

9.81 m 5
Kg ⋅ m
P E = (1360, Kg) ( ) (36.6 m) = 4.88 × 10 (1.4.6)
2 2
s s

5
= 4.88 × 10 J = 488 kJ (1.4.7)

The units of potential energy are the same as the units of kinetic energy. Notice that in this case the potential energy of the stationary
automobile at the top of a 36.6 m high parking garage is the same as its kinetic energy at 60 mi/h.

If the vehicle fell from the roof of the parking garage, its potential energy would be converted to kinetic energy, and it is reasonable to
infer that the vehicle would be traveling at 60 mi/h just before it hit the ground, neglecting air resistance. After the car hit the ground, its
potential and kinetic energy would both be zero.
Potential energy is usually defined relative to an arbitrary standard position (in this case, the street was assigned an elevation of zero).
As a result, we usually calculate only differences in potential energy: in this case, the difference between the potential energy of the car
on the top level of the parking garage and the potential energy of the same car on the street at the base of the garage.

Units of Energy
The units of energy are the same for all forms of energy. Energy can also be expressed in the non-SI units of calories (cal), where 1 cal
was originally defined as the amount of energy needed to raise the temperature of exactly 1 g of water from 14.5°C to 15.5°[Link]
specify the exact temperatures because the amount of energy needed to raise the temperature of 1 g of water 1°C varies slightly with
elevation. To three significant figures, however, this amount is 1.00 cal over the temperature range 0°C–100°C. The name is derived
from the Latin calor, meaning “heat.” Although energy may be expressed as either calories or joules, calories were defined in terms of
heat, whereas joules were defined in terms of motion. Because calories and joules are both units of energy, however, the calorie is now
defined in terms of the joule:
1 cal = 4.184 J exactly (1.4.8)

1 J = 0.2390 cal (1.4.9)

In this text, we will use the SI units—joules (J) and kilojoules (kJ)—exclusively, except when we deal with nutritional information.

1.4.4 [Link]
 Example 1.4.1
a. If the mass of a baseball is 149 g, what is the kinetic energy of a fastball clocked at 100 mi/h?
b. A batter hits a pop fly, and the baseball (with a mass of 149 g) reaches an altitude of 250 ft. If we assume that the ball was 3 ft
above home plate when hit by the batter, what is the increase in its potential energy?
Given: mass and velocity or height
Asked for: kinetic and potential energy
Strategy:
Use Equation 5.1.4 to calculate the kinetic energy and Equation 5.1.6 to calculate the potential energy, as appropriate.
Solution:
a. The kinetic energy of an object is given by 1

2
mv
2
In this case, we know both the mass and the velocity, but we must convert the
velocity to SI units:

100 mi 1 h 1 min 1.61 km 1000 m

v=( ) ( ) ( )( ) ( ) = 44.7 m/s (1.4.10)
1 h 60 min 60 s 1 mi 1 km

The kinetic energy of the baseball is therefore

2 2
1 1 kg 44.7 m kg ⋅ m
2 2
KE = ( ) × 149 g ( )( ) = 1.49 × 10 = 1.49 × 10 J (1.4.11)
2
2 1000 g s s

b. The increase in potential energy is the same as the amount of work required to raise the ball to its new altitude, which is (250 − 3)
= 247 feet above its initial position. Thus

2
1 kg 9.81 m ⎛ 0.3048 m ⎞ kg ⋅ m
2 2
P E = 149 g ( )( ) (247 ft ) = 1.10 × 10 = 1.10 × 10 J (1.4.12)
2 2
1000 g s ⎝ 1 ft ⎠ s

Exercise 1.4.1
a. In a bowling alley, the distance from the foul line to the head pin is 59 ft, 10 13/16 in. (18.26 m). If a 16 lb (7.3 kg) bowling ball
takes 2.0 s to reach the head pin, what is its kinetic energy at impact? (Assume its speed is constant.)
b. What is the potential energy of a 16 lb bowling ball held 3.0 ft above your foot?

Answer a
3.10 × 102 J
Answer b
65 J

Summary
All forms of energy can be interconverted. Three things can change the energy of an object: the transfer of heat, work performed on or
by an object, or some combination of heat and work. Thermochemistry is a branch of chemistry that qualitatively and quantitatively
describes the energy changes that occur during chemical reactions. Energy is the capacity to do work. Mechanical work is the amount
of energy required to move an object a given distance when opposed by a force. Thermal energy is due to the random motions of
atoms, molecules, or ions in a substance. The temperature of an object is a measure of the amount of thermal energy it contains. Heat
(q) is the transfer of thermal energy from a hotter object to a cooler one. Energy can take many forms; most are different varieties of
potential energy (PE), energy caused by the relative position or orientation of an object. Kinetic energy (KE) is the energy an object
possesses due to its motion. The most common units of energy are the joule (J), defined as 1 (kg·m2)/s2, and the calorie, defined as the
amount of energy needed to raise the temperature of 1 g of water by 1°C (1 cal = 4.184 J).

Modified by Tom Neils (Grand Rapids Community College)

1.4: A First Look at Energy is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1.4.5 [Link]
1.5: Making Measurements
Skills to Develop
Explain the process of measurement
Identify the three basic parts of a quantity
Describe the properties and units of length, mass, volume, density, temperature, and time
Perform basic unit calculations and conversions in the metric and other unit systems

Measurements provide the macroscopic information that is the basis of most of the hypotheses, theories, and laws that describe the
behavior of matter and energy in both the macroscopic and microscopic domains of chemistry. Every measurement provides three
kinds of information: the size or magnitude of the measurement (a number); a standard of comparison for the measurement (a unit);
and an indication of the uncertainty of the measurement. While the number and unit are explicitly represented when a quantity is
written, the uncertainty is an aspect of the measurement result that is more implicitly represented and will be discussed later.
The number in the measurement can be represented in different ways, including decimal form and scientific notation. For example,
the maximum takeoff weight of a Boeing 777-200ER airliner is 298,000 kilograms, which can also be written as 2.98 × 105 kg.
The mass of the average mosquito is about 0.0000025 kilograms, which can be written as 2.5 × 10−6 kg.
Units, such as liters, pounds, and centimeters, are standards of comparison for measurements. When we buy a 2-liter bottle of a soft
drink, we expect that the volume of the drink was measured, so it is two times larger than the volume that everyone agrees to be 1
liter. The meat used to prepare a 0.25-pound hamburger is measured so it weighs one-fourth as much as 1 pound. Without units, a
number can be meaningless, confusing, or possibly life threatening. Suppose a doctor prescribes phenobarbital to control a patient’s
seizures and states a dosage of “100” without specifying units. Not only will this be confusing to the medical professional giving
the dose, but the consequences can be dire: 100 mg given three times per day can be effective as an anticonvulsant, but a single
dose of 100 g is more than 10 times the lethal amount.
We usually report the results of scientific measurements in SI units, an updated version of the metric system, using the units listed
in Table 1.5.1. Other units can be derived from these base units. The standards for these units are fixed by international agreement,
and they are called the International System of Units or SI Units (from the French, Le Système International d’Unités). SI units
have been used by the United States National Institute of Standards and Technology (NIST) since 1964.
Table 1.5.1: Base Units of the SI System
Property Measured Name of Unit Symbol of Unit

length meter m

mass kilogram kg

time second s

temperature kelvin K

electric current ampere A

amount of substance mole mol

luminous intensity candela cd

Sometimes we use units that are fractions or multiples of a base unit. Ice cream is sold in quarts (a familiar, non-SI base unit), pints
(0.5 quart), or gallons (4 quarts). We also use fractions or multiples of units in the SI system, but these fractions or multiples are
always powers of 10. Fractional or multiple SI units are named using a prefix and the name of the base unit. For example, a length
of 1000 meters is also called a kilometer because the prefix kilo means “one thousand,” which in scientific notation is 103 (1
kilometer = 1000 m = 103 m). The prefixes used and the powers to which 10 are raised are listed in Table 1.5.2.
Table 1.5.2: Common Unit Prefixes
Prefix Symbol Factor Example

1 femtosecond (fs) = 1 × 10−15 s

femto f 10−15
(0.000000000000001 s)
1 picometer (pm) = 1 × 10−12 m
pico p 10−12
(0.000000000001 m)

Access for free at OpenStax 1.5.1 [Link]

 Prefix Symbol Factor Example

4 nanograms (ng) = 4 × 10−9 g

nano n 10−9
(0.000000004 g)
1 microliter (μL) = 1 × 10−6 L
micro µ 10−6
(0.000001 L)
2 millimoles (mmol) = 2 × 10−3
milli m 10−3
mol (0.002 mol)
7 centimeters (cm) = 7 × 10−2 m
centi c 10−2
(0.07 m)
1 deciliter (dL) = 1 × 10−1 L (0.1
deci d 10−1
L)
1 kilometer (km) = 1 × 103 m
kilo k 103
(1000 m)
3 megahertz (MHz) = 3 × 106 Hz
mega M 106
(3,000,000 Hz)
8 gigayears (Gyr) = 8 × 109 yr
giga G 109
(8,000,000,000 Gyr)
5 terawatts (TW) = 5 × 1012 W
tera T 1012
(5,000,000,000,000 W)

SI Base Units
The initial units of the metric system, which eventually evolved into the SI system, were established in France during the French
Revolution. The original standards for the meter and the kilogram were adopted there in 1799 and eventually by other countries.
This section introduces four of the SI base units commonly used in chemistry. Other SI units will be introduced in subsequent
chapters.

Length
The standard unit of length in both the SI and original metric systems is the meter (m). A meter was originally specified as
1/10,000,000 of the distance from the North Pole to the equator. It is now defined as the distance light in a vacuum travels in
1/299,792,458 of a second. A meter is about 3 inches longer than a yard (Figure 1.5.1); one meter is about 39.37 inches or 1.094
yards. Longer distances are often reported in kilometers (1 km = 1000 m = 103 m), whereas shorter distances can be reported in
centimeters (1 cm = 0.01 m = 10−2 m) or millimeters (1 mm = 0.001 m = 10−3 m).

Figure 1.5.1 : The relative lengths of 1 m, 1 yd, 1 cm, and 1 in. are shown (not actual size), as well as comparisons of 2.54 cm and 1
in., and of 1 m and 1.094 yd.

Mass
The standard unit of mass in the SI system is the kilogram (kg). A kilogram was originally defined as the mass of a liter of water (a
cube of water with an edge length of exactly 0.1 meter). It is now defined by a certain cylinder of platinum-iridium alloy, which is

Access for free at OpenStax 1.5.2 [Link]

kept in France (Figure 1.4.2). Any object with the same mass as this cylinder is said to have a mass of 1 kilogram. One kilogram is
about 2.2 pounds. The gram (g) is exactly equal to 1/1000 of the mass of the kilogram (10−3 kg).

Figure 1.5.2 : This replica prototype kilogram is housed at the National Institute of Standards and Technology (NIST) in Maryland.
(credit: National Institutes of Standards and Technology).

Temperature
Temperature is an intensive property. The SI unit of temperature is the kelvin (K). The IUPAC convention is to use kelvin (all
lowercase) for the word, K (uppercase) for the unit symbol, and neither the word “degree” nor the degree symbol (°). The degree
Celsius (°C) is also allowed in the SI system, with both the word “degree” and the degree symbol used for Celsius measurements.
Celsius degrees are the same magnitude as those of kelvin, but the two scales place their zeros in different places. Water freezes at
273.15 K (0 °C) and boils at 373.15 K (100 °C) by definition, and normal human body temperature is approximately 310 K (37
°C). The conversion between these two units and the Fahrenheit scale will be discussed later in this chapter.

Time
The SI base unit of time is the second (s). Small and large time intervals can be expressed with the appropriate prefixes; for
example, 3 microseconds = 0.000003 s = 3 × 10−6 and 5 megaseconds = 5,000,000 s = 5 × 106 s. Alternatively, hours, days, and
years can be used.

Derived SI Units
We can derive many units from the seven SI base units. For example, we can use the base unit of length to define a unit of volume,
and the base units of mass and length to define a unit of density.

Volume
Volume is the measure of the amount of space occupied by an object. The standard SI unit of volume is defined by the base unit of
length (Figure 1.5.3). The standard volume is a cubic meter (m3), a cube with an edge length of exactly one meter. To dispense a
cubic meter of water, we could build a cubic box with edge lengths of exactly one meter. This box would hold a cubic meter of
water or any other substance.
A more commonly used unit of volume is derived from the decimeter (0.1 m, or 10 cm). A cube with edge lengths of exactly one
decimeter contains a volume of one cubic decimeter (dm3). A liter (L) is the more common name for the cubic decimeter. One liter
is about 1.06 quarts. A cubic centimeter (cm3) is the volume of a cube with an edge length of exactly one centimeter. The
abbreviation cc (for cubic centimeter) is often used by health professionals. A cubic centimeter is also called a milliliter (mL) and is
1/1000 of a liter.

Access for free at OpenStax 1.5.3 [Link]

 <
Figure 1.5.3 : (a) The relative volumes are shown for cubes of 1 m3, 1 dm3 (1 L), and 1 cm3 (1 mL) (not to scale). (b) The diameter
of a dime is compared relative to the edge length of a 1-cm3 (1-mL) cube.

Density
We use the mass and volume of a substance to determine its density. Thus, the units of density are defined by the base units of mass
and length.
The density of a substance is the ratio of the mass of a sample of the substance to its volume. The SI unit for density is the kilogram
per cubic meter (kg/m3). For many situations, however, this as an inconvenient unit, and we often use grams per cubic centimeter
(g/cm3) for the densities of solids and liquids, and grams per liter (g/L) for gases. Although there are exceptions, most liquids and
solids have densities that range from about 0.7 g/cm3 (the density of gasoline) to 19 g/cm3 (the density of gold). The density of air
is about 1.2 g/L. Table 1.5.3 shows the densities of some common substances.
Table 1.5.3: Densities of Common Substances
Solids Liquids Gases (at 25 °C and 1 atm)

ice (at 0 °C) 0.92 g/cm3 water 1.0 g/cm3 dry air 1.20 g/L

oak (wood) 0.60–0.90 g/cm3 ethanol 0.79 g/cm3 oxygen 1.31 g/L

iron 7.9 g/cm3 acetone 0.79 g/cm3 nitrogen 1.14 g/L

copper 9.0 g/cm3 glycerin 1.26 g/cm3 carbon dioxide 1.80 g/L

lead 11.3 g/cm3 olive oil 0.92 g/cm3 helium 0.16 g/L

silver 10.5 g/cm3 gasoline 0.70–0.77 g/cm3 neon 0.83 g/L

gold 19.3 g/cm3 mercury 13.6 g/cm3 radon 9.1 g/L

While there are many ways to determine the density of an object, perhaps the most straightforward method involves separately
finding the mass and volume of the object, and then dividing the mass of the sample by its volume. In the following example, the
mass is found directly by weighing, but the volume is found indirectly through length measurements.
mass
density = (1.5.1)
volume

Example 1.5.1
Calculation of Density Gold—in bricks, bars, and coins—has been a form of currency for centuries. In order to swindle people
into paying for a brick of gold without actually investing in a brick of gold, people have considered filling the centers of hollow
gold bricks with lead to fool buyers into thinking that the entire brick is gold. It does not work: Lead is a dense substance, but its
density is not as great as that of gold, 19.3 g/cm3. What is the density of lead if a cube of lead has an edge length of 2.00 cm and
a mass of 90.7 g?
Solution

Access for free at OpenStax 1.5.4 [Link]

 The density of a substance can be calculated by dividing its mass by its volume. The volume of a cube is calculated by cubing
the edge length.
3
volume of lead cube = 2.00 cm × 2.00 cm × 2.00 cm = 8.00 cm onumber (1.5.2)

mass 90.7 g 11.3 g 3

density = = = = 11.3 g/cm onumber (1.5.3)
3 3
volume 8.00 cm 1.00 cm

(We will discuss the reason for rounding to the first decimal place in the next section.)

Exercise 1.5.1
a. To three decimal places, what is the volume of a cube (cm3) with an edge length of 0.843 cm?
b. If the cube in part (a) is copper and has a mass of 5.34 g, what is the density of copper to two decimal places?

Answer a
0.599 cm3;
Answer b
8.91 g/cm3

Example 1.5.2 : Using Displacement of Water to Determine Density

This PhET simulation illustrates another way to determine density, using displacement of water. Determine the density of the
red and yellow blocks.
Solution
When you open the density simulation and select Same Mass, you can choose from several 5.00-kg colored blocks that you can
drop into a tank containing 100.00 L water. The yellow block floats (it is less dense than water), and the water level rises to
105.00 L. While floating, the yellow block displaces 5.00 L water, an amount equal to the weight of the block. The red block
sinks (it is more dense than water, which has density = 1.00 kg/L), and the water level rises to 101.25 L.
The red block therefore displaces 1.25 L water, an amount equal to the volume of the block. The density of the red block is:
mass 5.00 kg
density = = = 4.00 kg/L (1.5.4)
volume 1.25 L

Note that since the yellow block is not completely submerged, you cannot determine its density from this information. But if
you hold the yellow block on the bottom of the tank, the water level rises to 110.00 L, which means that it now displaces 10.00
L water, and its density can be found:
mass 5.00 kg
density = = = 0.500 kg/L (1.5.5)
volume 10.00 L

Exercise 1.5.1
Remove all of the blocks from the water and add the green block to the tank of water, placing it approximately in the middle of
the tank. Determine the density of the green block.

Answer
2.00 kg/L

Summary
Measurements provide quantitative information that is critical in studying and practicing chemistry. Each measurement has an
amount, a unit for comparison, and an uncertainty. Measurements can be represented in either decimal or scientific notation.
Scientists primarily use the SI (International System) or metric systems. We use base SI units such as meters, seconds, and
kilograms, as well as derived units, such as liters (for volume) and g/cm3 (for density). In many cases, we find it convenient to use
unit prefixes that yield fractional and multiple units, such as microseconds (10−6 seconds) and megahertz (106 hertz), respectively.

Access for free at OpenStax 1.5.5 [Link]

Key Equations
mass
density =
volume

Glossary
Celsius (°C)
unit of temperature; water freezes at 0 °C and boils at 100 °C on this scale

cubic centimeter (cm3 or cc)

volume of a cube with an edge length of exactly 1 cm

cubic meter (m3)

SI unit of volume

density
ratio of mass to volume for a substance or object

kelvin (K)
SI unit of temperature; 273.15 K = 0 ºC

kilogram (kg)
standard SI unit of mass; 1 kg = approximately 2.2 pounds

length
measure of one dimension of an object

liter (L)
(also, cubic decimeter) unit of volume; 1 L = 1,000 cm3

meter (m)
standard metric and SI unit of length; 1 m = approximately 1.094 yards

milliliter (mL)
1/1,000 of a liter; equal to 1 cm3

second (s)
SI unit of time

SI units (International System of Units)

standards fixed by international agreement in the International System of Units (Le Système International d’Unités)

unit
standard of comparison for measurements

volume
amount of space occupied by an object

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).

This page titled 1.5: Making Measurements is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.

Access for free at OpenStax 1.5.6 [Link]

1.6: Limits on Measurements
Skills to Develop
Define accuracy and precision
Distinguish exact and uncertain numbers
Correctly represent uncertainty in quantities using significant figures
Apply proper rounding rules to computed quantities

Counting is the only type of measurement that is free from uncertainty, provided the number of objects being counted does not
change while the counting process is underway. The result of such a counting measurement is an example of an exact number. If
we count eggs in a carton, we know exactly how many eggs the carton contains. The numbers of defined quantities are also exact.
By definition, 1 foot is exactly 12 inches, 1 inch is exactly 2.54 centimeters, and 1 gram is exactly 0.001 kilogram. Quantities
derived from measurements other than counting, however, are uncertain to varying extents due to practical limitations of the
measurement process used.

Significant Figures in Measurement

The numbers of measured quantities, unlike defined or directly counted quantities, are not exact. To measure the volume of liquid
in a graduated cylinder, you should make a reading at the bottom of the meniscus, the lowest point on the curved surface of the
liquid.

Figure 1.6.1: To measure the volume of liquid in this graduated cylinder, you must mentally subdivide the distance between the
21 and 22 mL marks into tenths of a milliliter, and then make a reading (estimate) at the bottom of the meniscus.
Refer to the illustration in Figure 1.6.1. The bottom of the meniscus in this case clearly lies between the 21 and 22 markings,
meaning the liquid volume is certainly greater than 21 mL but less than 22 mL. The meniscus appears to be a bit closer to the 22-
mL mark than to the 21-mL mark, and so a reasonable estimate of the liquid’s volume would be 21.6 mL. In the number 21.6, then,
the digits 2 and 1 are certain, but the 6 is an estimate. Some people might estimate the meniscus position to be equally distant from
each of the markings and estimate the tenth-place digit as 5, while others may think it to be even closer to the 22-mL mark and
estimate this digit to be 7. Note that it would be pointless to attempt to estimate a digit for the hundredths place, given that the
tenths-place digit is uncertain. In general, numerical scales such as the one on this graduated cylinder will permit measurements to
one-tenth of the smallest scale division. The scale in this case has 1-mL divisions, and so volumes may be measured to the nearest
0.1 mL.
This concept holds true for all measurements, even if you do not actively make an estimate. If you place a quarter on a standard
electronic balance, you may obtain a reading of 6.72 g. The digits 6 and 7 are certain, and the 2 indicates that the mass of the
quarter is likely between 6.71 and 6.73 grams. The quarter weighs about 6.72 grams, with a nominal uncertainty in the
measurement of ± 0.01 gram. If we weigh the quarter on a more sensitive balance, we may find that its mass is 6.723 g. This means
its mass lies between 6.722 and 6.724 grams, an uncertainty of 0.001 gram. Every measurement has some uncertainty, which
depends on the device used (and the user’s ability). All of the digits in a measurement, including the uncertain last digit, are called
significant figures or significant digits. Note that zero may be a measured value; for example, if you stand on a scale that shows
weight to the nearest pound and it shows “120,” then the 1 (hundreds), 2 (tens) and 0 (ones) are all significant (measured) values.
Whenever you make a measurement properly, all the digits in the result are significant. But what if you were analyzing a reported
value and trying to determine what is significant and what is not? Well, for starters, all nonzero digits are significant, and it is only

Access for free at OpenStax 1.6.1 [Link]

zeros that require some thought. We will use the terms “leading,” “trailing,” and “captive” for the zeros and will consider how to
deal with them.

Starting with the first nonzero digit on the left, count this digit and all remaining digits to the right. This is the number of
significant figures in the measurement unless the last digit is a trailing zero lying to the left of the decimal point.

Captive zeros result from measurement and are therefore always significant. Leading zeros, however, are never significant—they
merely tell us where the decimal point is located.

The leading zeros in this example are not significant. We could use exponential notation (as described in Appendix B) and express
the number as 8.32407 × 10−3; then the number 8.32407 contains all of the significant figures, and 10−3 locates the decimal point.
The number of significant figures is uncertain in a number that ends with a zero to the left of the decimal point location. The zeros
in the measurement 1,300 grams could be significant or they could simply indicate where the decimal point is located. The
ambiguity can be resolved with the use of exponential notation: 1.3 × 103 (two significant figures), 1.30 × 103 (three significant
figures, if the tens place was measured), or 1.300 × 103 (four significant figures, if the ones place was also measured). In cases
where only the decimal-formatted number is available, it is prudent to assume that all trailing zeros are not significant.

When determining significant figures, be sure to pay attention to reported values and think about the measurement and significant
figures in terms of what is reasonable or likely—that is, whether the value makes sense. For example, the official January 2014
census reported the resident population of the US as 317,297,725. Do you think the US population was correctly determined to the
reported nine significant figures, that is, to the exact number of people? People are constantly being born, dying, or moving into or
out of the country, and assumptions are made to account for the large number of people who are not actually counted. Because of
these uncertainties, it might be more reasonable to expect that we know the population to within perhaps a million or so, in which
case the population should be reported as 317 million, or 3.17 × 10 people.
8

Significant Figures in Calculations

A second important principle of uncertainty is that results calculated from a measurement are at least as uncertain as the
measurement itself. We must take the uncertainty in our measurements into account to avoid misrepresenting the uncertainty in
calculated results. One way to do this is to report the result of a calculation with the correct number of significant figures, which is
determined by the following three rules for rounding numbers:
1. When we add or subtract numbers, we should round the result to the same number of decimal places as the number with the
least number of decimal places (the least precise value in terms of addition and subtraction).
2. When we multiply or divide numbers, we should round the result to the same number of digits as the number with the least
number of significant figures (the least precise value in terms of multiplication and division).

Access for free at OpenStax 1.6.2 [Link]

 3. If the digit to be dropped (the one immediately to the right of the digit to be retained) is less than 5, we “round down” and leave
the retained digit unchanged; if it is more than 5, we “round up” and increase the retained digit by 1; if the dropped digit is 5,
we round up or down, whichever yields an even value for the retained digit. (The last part of this rule may strike you as a bit
odd, but it’s based on reliable statistics and is aimed at avoiding any bias when dropping the digit “5,” since it is equally close to
both possible values of the retained digit.)
The following examples illustrate the application of this rule in rounding a few different numbers to three significant figures:
0.028675 rounds “up” to 0.0287 (the dropped digit, 7, is greater than 5)
18.3384 rounds “down” to 18.3 (the dropped digit, 3, is less than 5)
6.8752 rounds “up” to 6.88 (the dropped digit is 5, and the retained digit is even)
92.85 rounds “down” to 92.8 (the dropped digit is 5, and the retained digit is even)
Let’s work through these rules with a few examples.

Example 1.6.1 : Rounding Numbers

Round the following to the indicated number of significant figures:
a. 31.57 (to two significant figures)
b. 8.1649 (to three significant figures)
c. 0.051065 (to four significant figures)
d. 0.90275 (to four significant figures)
Solution
a. 31.57 rounds “up” to 32 (the dropped digit is 5, and the retained digit is even)
b. 8.1649 rounds “down” to 8.16 (the dropped digit, 4, is less than 5)
c. 0.051065 rounds “down” to 0.05106 (the dropped digit is 5, and the retained digit is even)
d. 0.90275 rounds “up” to 0.9028 (the dropped digit is 5, and the retained digit is even)

Exercise 1.6.1
Round the following to the indicated number of significant figures:
a. 0.424 (to two significant figures)
b. 0.0038661 (to three significant figures)
c. 421.25 (to four significant figures)
d. 28,683.5 (to five significant figures)

Answer a
0.42
Answer b
0.00387
Answer c
421.2
Answer d
28,684

Example 1.6.2 : Addition and Subtraction with Significant Figures Rule:

When we add or subtract numbers, we should round the result to the same number of decimal places as the number with the
least number of decimal places (i.e., the least precise value in terms of addition and subtraction).
a. Add 1.0023 g and 4.383 g.
b. Subtract 421.23 g from 486 g.
Solution

Access for free at OpenStax 1.6.3 [Link]

(a)
1.0023 g

+ 4.383 g
––––––––
5.3853 g

Answer is 5.385 g (round to the thousandths place; three decimal places)

(b)
486 g

− 421.23 g
––––––––
64.77 g

Answer is 65 g (round to the ones place; no decimal places)

Exercise 1.6.2
a. Add 2.334 mL and 0.31 mL.
b. Subtract 55.8752 m from 56.533 m.

Answer a
2.64 mL
Answer b
0.658 m

Example 1.6.3 : Multiplication and Division with Significant Figures

Rule: When we multiply or divide numbers, we should round the result to the same number of digits as the number with the
least number of significant figures (the least precise value in terms of multiplication and division).
a. Multiply 0.6238 cm by 6.6 cm.
b. Divide 421.23 g by 486 mL.
Solution
(a)
2 2
0.6238 cm × 6.6 cm = 4.11708 cm → result is 4.1 cm (round to two significant figures) (1.6.1)

four significant figures × two significant figures → two significant figures answer (1.6.2)

(b)
421.23 g
= 0.86728... g/mL → result is 0.867 g/mL (round to three significant figures) (1.6.3)
486 mL

f ive signif icant f igures

→ three signif icant f igures answer (1.6.4)
three signif icant f igures

Access for free at OpenStax 1.6.4 [Link]

 Exercise 1.6.3
a. Multiply 2.334 cm and 0.320 cm.
b. Divide 55.8752 m by 56.53 s.

Answer a
0.747 cm2
Answer b
0.9884 m/s

In the midst of all these technicalities, it is important to keep in mind the reason why we use significant figures and rounding rules
—to correctly represent the certainty of the values we report and to ensure that a calculated result is not represented as being more
certain than the least certain value used in the calculation.

Example 1.6.4 : Calculation with Significant Figures

One common bathtub is 13.44 dm long, 5.920 dm wide, and 2.54 dm deep. Assume that the tub is rectangular and calculate its
approximate volume in liters.
Solution
V = l×w ×d

= 13.44 dm × 5.920 dm × 2.54 dm

3
= 202.09459...dm (value from calculator)

3
= 202 dm , or 202 L (answer rounded to three significant figures)

Exercise 1.6.4 : Determination of Density Using Water Displacement

What is the density of a liquid with a mass of 31.1415 g and a volume of 30.13 cm3?

Answer
1.034 g/mL

Example 1.6.4
A piece of rebar is weighed and then submerged in a graduated cylinder partially filled with water, with results as shown.

a. Use these values to determine the density of this piece of rebar.

b. Rebar is mostly iron. Does your result in (a) support this statement? How?
Solution
The volume of the piece of rebar is equal to the volume of the water displaced:
3
volume = 22.4 mL − 13.5 mL = 8.9 mL = 8.9 cm onumber (1.6.5)

Access for free at OpenStax 1.6.5 [Link]

 (rounded to the nearest 0.1 mL, per the rule for addition and subtraction)
The density is the mass-to-volume ratio:
mass 69.658 g
3
density = = = 7.8 g/cm onumber (1.6.6)
3
volume 8.9 cm

(rounded to two significant figures, per the rule for multiplication and division)
The density of iron is 7.9 g/cm3, very close to that of rebar, which lends some support to the fact that rebar is mostly iron.

Exercise 1.6.4
An irregularly shaped piece of a shiny yellowish material is weighed and then submerged in a graduated cylinder, with results as
shown.

a. Use these values to determine the density of this material.

b. Do you have any reasonable guesses as to the identity of this material? Explain your reasoning.

Answer a
19 g/cm3
Answer b
It is likely gold; it has the right appearance for gold and very close to the density given for gold.

Accuracy and Precision

Scientists typically make repeated measurements of a quantity to ensure the quality of their findings and to know both the precision
and the accuracy of their results. Measurements are said to be precise if they yield very similar results when repeated in the same
manner. A measurement is considered accurate if it yields a result that is very close to the true or accepted value. Precise values
agree with each other; accurate values agree with a true value. These characterizations can be extended to other contexts, such as
the results of an archery competition (Figure 1.6.2).

Figure 1.6.2 : (a) These arrows are close to both the bull’s eye and one another, so they are both accurate and precise. (b) These
arrows are close to one another but not on target, so they are precise but not accurate. (c) These arrows are neither on target nor
close to one another, so they are neither accurate nor precise.
Suppose a quality control chemist at a pharmaceutical company is tasked with checking the accuracy and precision of three
different machines that are meant to dispense 10 ounces (296 mL) of cough syrup into storage bottles. She proceeds to use each

Access for free at OpenStax 1.6.6 [Link]

machine to fill five bottles and then carefully determines the actual volume dispensed, obtaining the results tabulated in Table
1.6.2.

Table 1.6.2: Volume (mL) of Cough Medicine Delivered by 10-oz (296 mL) Dispensers
Dispenser #1 Dispenser #2 Dispenser #3

283.3 298.3 296.1

284.1 294.2 295.9

283.9 296.0 296.1

284.0 297.8 296.0

284.1 293.9 296.1

Considering these results, she will report that dispenser #1 is precise (values all close to one another, within a few tenths of a
milliliter) but not accurate (none of the values are close to the target value of 296 mL, each being more than 10 mL too low).
Results for dispenser #2 represent improved accuracy (each volume is less than 3 mL away from 296 mL) but worse precision
(volumes vary by more than 4 mL). Finally, she can report that dispenser #3 is working well, dispensing cough syrup both
accurately (all volumes within 0.1 mL of the target volume) and precisely (volumes differing from each other by no more than 0.2
mL).

Summary
Quantities can be exact or measured. Measured quantities have an associated uncertainty that is represented by the number of
significant figures in the measurement. The uncertainty of a calculated value depends on the uncertainties in the values used in the
calculation and is reflected in how the value is rounded. Measured values can be accurate (close to the true value) and/or precise
(showing little variation when measured repeatedly).

Glossary
uncertainty
estimate of amount by which measurement differs from true value

significant figures
(also, significant digits) all of the measured digits in a determination, including the uncertain last digit

rounding
procedure used to ensure that calculated results properly reflect the uncertainty in the measurements used in the calculation

precision
how closely a measurement matches the same measurement when repeated

exact number
number derived by counting or by definition

accuracy
how closely a measurement aligns with a correct value

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).

Access for free at OpenStax 1.6.7 [Link]

This page titled 1.6: Limits on Measurements is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.

Access for free at OpenStax 1.6.8 [Link]

1.7: Dimensional Analysis
Skills to Develop
Explain the dimensional analysis (factor label) approach to mathematical calculations involving quantities
Use dimensional analysis to carry out unit conversions for a given property and computations involving two or more
properties

It is often the case that a quantity of interest may not be easy (or even possible) to measure directly but instead must be calculated
from other directly measured properties and appropriate mathematical relationships. For example, consider measuring the average
speed of an athlete running sprints. This is typically accomplished by measuring the time required for the athlete to run from the
starting line to the finish line, and the distance between these two lines, and then computing speed from the equation that relates
these three properties:
distance
speed = (1.7.1)
time

An Olympic-quality sprinter can run 100 m in approximately 10 s, corresponding to an average speed of

100 m 10 m
= (1.7.2)
10 s s

Note that this simple arithmetic involves dividing the numbers of each measured quantity to yield the number of the computed
quantity (100/10 = 10) and likewise dividing the units of each measured quantity to yield the unit of the computed quantity (m/s =
m/s). Now, consider using this same relation to predict the time required for a person running at this speed to travel a distance of 25
m. The same relation between the three properties is used, but in this case, the two quantities provided are a speed (10 m/s) and a
distance (25 m). To yield the sought property, time, the equation must be rearranged appropriately:
distance
time = (1.7.3)
speed

The time can then be computed as:

1 s
25 m × = 2.5 s (1.7.4)
10 m

Again, arithmetic on the numbers (25/10 = 2.5) was accompanied by the same arithmetic on the units (m/m/s = s) to yield the
number and unit of the result, 2.5 s. Note that, just as for numbers, when a unit is divided by an identical unit (in this case, m/m),
the result is “1”—or, as commonly phrased, the units “cancel.”
These calculations are examples of a versatile mathematical approach known as dimensional analysis (or the factor-label method).
Dimensional analysis is based on this premise: the units of quantities must be subjected to the same mathematical operations as
their associated numbers. This method can be applied to computations ranging from simple unit conversions to more complex,
multi-step calculations involving several different quantities.

Conversion Factors and Dimensional Analysis

A ratio of two equivalent quantities expressed with different measurement units can be used as a unit conversion factor. For
example, the lengths of 2.54 cm and 1 in. are equivalent (by definition), and so a unit conversion factor may be derived from the
ratio,
2.54 cm cm
(2.54 cm = 1 in. ) or 2.54 (1.7.5)
1 in. in.

Several other commonly used conversion factors are given in Table 1.7.1.
Table 1.7.1: Common Conversion Factors
Length Volume Mass

1 m = 1.0936 yd 1 L = 1.0567 qt 1 kg = 2.2046 lb

1 in. = 2.54 cm (exact) 1 qt = 0.94635 L 1 lb = 453.59 g

Access for free at OpenStax 1.7.1 [Link]

 Length Volume Mass

1 km = 0.62137 mi 1 ft3 = 28.317 L 1 (avoirdupois) oz = 28.349 g

1 mi = 1609.3 m 1 tbsp = 14.787 mL 1 (troy) oz = 31.103 g

When we multiply a quantity (such as distance given in inches) by an appropriate unit conversion factor, we convert the quantity to
an equivalent value with different units (such as distance in centimeters). For example, a basketball player’s vertical jump of 34
inches can be converted to centimeters by:
2.54 cm
34 in. × = 86 cm (1.7.6)
1 in.

Since this simple arithmetic involves quantities, the premise of dimensional analysis requires that we multiply both numbers and
units. The numbers of these two quantities are multiplied to yield the number of the product quantity, 86, whereas the units are
multiplied to yield
in. ×cm
. (1.7.7)
in.

Just as for numbers, a ratio of identical units is also numerically equal to one,
in.
=1 (1.7.8)
in.

and the unit product thus simplifies to cm. (When identical units divide to yield a factor of 1, they are said to “cancel.”) Using
dimensional analysis, we can determine that a unit conversion factor has been set up correctly by checking to confirm that the
original unit will cancel, and the result will contain the sought (converted) unit.

Example 1.7.1 : Using a Unit Conversion Factor

The mass of a competition Frisbee is 125 g. Convert its mass to ounces using the unit conversion factor derived from the
relationship 1 oz = 28.349 g (Table 1.7.1).
Solution
If we have the conversion factor, we can determine the mass in kilograms using an equation similar the one used for converting
length from inches to centimeters.

x oz = 125 g × unit conversion f actor

We write the unit conversion factor in its two forms:

1 oz 28.349 g
and
28.349 g 1 oz

The correct unit conversion factor is the ratio that cancels the units of grams and leaves ounces.
1 oz
x oz = 125 g ×
28.349 g

125
=( ) oz
28.349

= 4.41 oz (three signif icant f igures)

Exercise 1.7.1
Convert a volume of 9.345 qt to liters.

Answer
8.844 L

Access for free at OpenStax 1.7.2 [Link]

Beyond simple unit conversions, the factor-label method can be used to solve more complex problems, such as multidimensional
conversions. For example density is a two-dimensional property because it relates mass and volume. Thus, when you carry out a
calculation involving density, you need to pay attention to both mass units and volume units. Fortunately, these units can be treated
separately and independently, as shown in Example 1.7.2, below. Regardless of the details, the basic approach is the same—all the
factors involved in the calculation must be appropriately oriented to insure that their labels (units) will appropriately cancel and/or
combine to yield the desired unit in the result. This is why it is referred to as the factor-label method. As your study of chemistry
continues, you will encounter many opportunities to apply this approach.

Example 1.7.2 : Computing Quantities from Measurement Results

What is the density of common antifreeze in units of g/mL? A 4.00-qt sample of the antifreeze weighs 9.26 lb.
Solution
mass
Since density = , we need to divide the mass in grams by the volume in milliliters. In general: the number of units of
volume
B = the number of units of A × unit conversion factor. The necessary conversion factors are given in Table 1.7.1: 1 lb = 453.59
g; 1 L = 1.0567 qt; 1 L = 1,000 mL. We can convert mass from pounds to grams in one step:
453.59 g
3
9.26 lb × = 4.20 × 10 g
1 lb

We need to use two steps to convert volume from quarts to milliliters.

1. Convert quarts to liters.
1 L
4.00 qt × = 3.78 L
1.0567 qt

2. Convert liters to milliliters.

1000 mL
3
3.78 L × = 3.78 × 10 mL
1 L

Then,
3
4.20 × 10 g
density = = 1.11 g/mL
3
3.78 × 10 mL

Alternatively, the calculation could be set up in a way that uses three unit conversion factors sequentially as follows:

9.26 lb 1.0567 qt 1 L
453.59 g
× × × = 1.11 g/mL
4.00 qt 1 lb 1 L 1000 mL

Exercise 1.7.2
What is the volume in liters of 1.000 oz, given that 1 L = 1.0567 qt and 1 qt = 32 oz (exactly)?

Answer
−2
2.956 × 10 L

Example 1.7.3 : Computing Quantities from Measurement Results

While being driven from Philadelphia to Atlanta, a distance of about 1250 km, a 2014 Lamborghini Aventador Roadster uses
213 L gasoline.
a. What (average) fuel economy, in miles per gallon, did the Roadster get during this trip?
b. If gasoline costs $3.80 per gallon, what was the fuel cost for this trip?
Solution
(a) We first convert distance from kilometers to miles:

Access for free at OpenStax 1.7.3 [Link]

 0.62137 mi
1250 km × = 777 mi
1 km

and then convert volume from liters to gallons:

1.0567 qt
1 gal
213 L × × = 56.3 gal
1 L 4 qt

Then,
777 mi
(average) mileage = = 13.8 miles/gallon = 13.8 mpg
56.3 gal

Alternatively, the calculation could be set up in a way that uses all the conversion factors sequentially, as follows:

1250 km 0.62137 mi 1 L 4 qt
× × × = 13.8 mpg
213 L 1 km 1.0567 qt 1 gal

(b) Using the previously calculated volume in gallons, we find:

$3.80
56.3 gal × = $214
1 gal

Exercise 1.7.3
A Toyota Prius Hybrid uses 59.7 L gasoline to drive from San Francisco to Seattle, a distance of 1300 km (two significant
digits).
a. What (average) fuel economy, in miles per gallon, did the Prius get during this trip?
b. If gasoline costs $3.90 per gallon, what was the fuel cost for this trip?

Answer a
51 mpg
Answer b
$62

Conversion of Temperature Units

We use the word temperature to refer to the hotness or coldness of a substance. One way we measure a change in temperature is to
use the fact that most substances expand when their temperature increases and contract when their temperature decreases. The
mercury or alcohol in a common glass thermometer changes its volume as the temperature changes. Because the volume of the
liquid changes more than the volume of the glass, we can see the liquid expand when it gets warmer and contract when it gets
cooler.
To mark a scale on a thermometer, we need a set of reference values: Two of the most commonly used are the freezing and boiling
temperatures of water at a specified atmospheric pressure. On the Celsius scale, 0 °C is defined as the freezing temperature of water
and 100 °C as the boiling temperature of water. The space between the two temperatures is divided into 100 equal intervals, which
we call degrees. On the Fahrenheit scale, the freezing point of water is defined as 32 °F and the boiling temperature as 212 °F. The
space between these two points on a Fahrenheit thermometer is divided into 180 equal parts (degrees).
Defining the Celsius and Fahrenheit temperature scales as described in the previous paragraph results in a slightly more complex
relationship between temperature values on these two scales than for different units of measure for other properties. Most
measurement units for a given property are directly proportional to one another (y = mx). Using familiar length units as one
example:
1 ft
length in f eet = ( ) × length in inches (1.7.9)
12 in.

Access for free at OpenStax 1.7.4 [Link]

where
y = length in feet,
x = length in inches, and
the proportionality constant, m, is the conversion factor.
The Celsius and Fahrenheit temperature scales, however, do not share a common zero point, and so the relationship between these
two scales is a linear one rather than a proportional one (y = mx + b ). Consequently, converting a temperature from one of these
scales into the other requires more than simple multiplication by a conversion factor, m, it also must take into account differences
in the scales’ zero points (b ).
The linear equation relating Celsius and Fahrenheit temperatures is easily derived from the two temperatures used to define each
scale. Representing the Celsius temperature as x and the Fahrenheit temperature as y , the slope, m, is computed to be:
Δy
m =
Δx
∘ ∘
212 F − 32 F
=
∘ ∘
100 C −0 C

∘
180 F
=
∘
100 C

∘
9 F
=
∘
5 C

The y-intercept of the equation, b, is then calculated using either of the equivalent temperature pairs, (100 °C, 212 °F) or (0 °C, 32
°F), as:
b = y − mx

∘
9 F
∘ ∘
= 32 F− ×0 C
∘
5 C

∘
= 32 F

The equation relating the temperature scales is then:

∘
9 F ∘
T∘ F = ( × T∘ C ) + 32 C (1.7.10)
∘
5 C

An abbreviated form of this equation that omits the measurement units is:
9
T∘ F = × T∘ C + 32 (1.7.11)
5

Rearrangement of this equation yields the form useful for converting from Fahrenheit to Celsius:
5
T∘ C = (T∘ F + 32) (1.7.12)
9

As mentioned earlier in this chapter, the SI unit of temperature is the kelvin (K). Unlike the Celsius and Fahrenheit scales, the
kelvin scale is an absolute temperature scale in which 0 (zero) K corresponds to the lowest temperature that can theoretically be
achieved. The early 19th-century discovery of the relationship between a gas's volume and temperature suggested that the volume
of a gas would be zero at −273.15 °C. In 1848, British physicist William Thompson, who later adopted the title of Lord Kelvin,
proposed an absolute temperature scale based on this concept (further treatment of this topic is provided in this text’s chapter on
gases).
The freezing temperature of water on this scale is 273.15 K and its boiling temperature 373.15 K. Notice the numerical difference
in these two reference temperatures is 100, the same as for the Celsius scale, and so the linear relation between these two
K
temperature scales will exhibit a slope of 1 ∘
. Following the same approach, the equations for converting between the kelvin and
C
Celsius temperature scales are derived to be:
TK = T∘ C + 273.15 (1.7.13)

Access for free at OpenStax 1.7.5 [Link]

 T∘ C = TK − 273.15 (1.7.14)

The 273.15 in these equations has been determined experimentally, so it is not exact. Figure 1.7.1 shows the relationship among the
three temperature scales. Recall that we do not use the degree sign with temperatures on the kelvin scale.

Figure 1.7.1: The Fahrenheit, Celsius, and kelvin temperature scales are compared.
Although the kelvin (absolute) temperature scale is the official SI temperature scale, Celsius is commonly used in many scientific
contexts and is the scale of choice for nonscience contexts in almost all areas of the world. Very few countries (the U.S. and its
territories, the Bahamas, Belize, Cayman Islands, and Palau) still use Fahrenheit for weather, medicine, and cooking.

Example 1.7.4 : Conversion from Celsius

Normal body temperature has been commonly accepted as 37.0 °C (although it varies depending on time of day and method of
measurement, as well as among individuals). What is this temperature on the kelvin scale and on the Fahrenheit scale?
Solution
∘
K= C + 273.15 = 37.0 + 273.2 = 310.2 K

9 9
∘ ∘ ∘
F = C + 32.0 = ( × 37.0) + 32.0 = 66.6 + 32.0 = 98.6 F
5 5

Exercise 1.7.4
Convert 80.92 °C to K and °F.

Answer
354.07 K, 177.7 °F

Example 1.7.5 : Conversion from Fahrenheit

Baking a ready-made pizza calls for an oven temperature of 450 °F. If you are in Europe, and your oven thermometer uses the
Celsius scale, what is the setting? What is the kelvin temperature?
Solution
5 5 5
∘ ∘ ∘ ∘
C = ( F − 32) = (450 − 32) = × 418 = 232 C → set oven to 230 C (two significant figures)
9 9 9

∘ 2
K= C + 273.15 = 230 + 273 = 503 K → 5.0 × 10 K (two signif icant f igures)

Access for free at OpenStax 1.7.6 [Link]

 Exercise 1.7.5
Convert 50 °F to °C and K.

Answer
10 °C, 280 K

Summary
Measurements are made using a variety of units. It is often useful or necessary to convert a measured quantity from one unit into
another. These conversions are accomplished using unit conversion factors, which are derived by simple applications of a
mathematical approach called the factor-label method or dimensional analysis. This strategy is also employed to calculate sought
quantities using measured quantities and appropriate mathematical relations.

Key Equations
5
T∘ C = × T∘ F − 32
9
9
T∘ F = × T∘ C + 32
5
∘
TK = C + 273.15

T ∘
C = K − 273.15

Glossary
dimensional analysis
(also, factor-label method) versatile mathematical approach that can be applied to computations ranging from simple unit
conversions to more complex, multi-step calculations involving several different quantities

Fahrenheit
unit of temperature; water freezes at 32 °F and boils at 212 °F on this scale

unit conversion factor

ratio of equivalent quantities expressed with different units; used to convert from one unit to a different unit

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).

This page titled 1.7: Dimensional Analysis is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.

Access for free at OpenStax 1.7.7 [Link]

1.8: Matter, Measurement, and Problem Solving (Exercises)
These are homework exercises to accompany the Textmap created for Chemistry: A Molecular Approach by Nivaldo Tro.
Complementary General Chemistry question banks can be found for other Textmaps and can be accessed here. In addition to these
publicly available questions, access to private problems bank for use in exams and homework is available to faculty only on an
individual basis; please contact Delmar Larsen for an account with access permission.

Additional Questions
A1
Preform the following mathematical operations and give the answer with the correct number of significant figures:
4 7
(9.008 × 10 )(6.5227 × 10 )
a. −4
6.53 × 10
−−−−−−−−−−−−− −
b. √(7.1 × 10 2 4
) + 924 7.508 × 10

4 7
(9.008 × 10 )(6.5227 × 10 )
c. −4
6.53 × 10

A2
Perform the following unit conversions. Express your answers in scientific notation with the appropriate number of significant
figures.
a. Convert 78.01 inches into: feet, meters, centimeters, millimeters and kilometers.
b. Convert 14511 feet into miles, kilometers and meters.
c. Convert 15.42 meters into kilometers, centimeters, millimeters, micrometers, and nanometers.
d. Convert 98.6 °F into °C and K.
e. Convert 75 miles per hour into: km per hour and m s-1 .
f. Convert 23.15 m2 into ft2 , in2 , and cm2

A3
In the movie Goldfinger, James Bond foils a plot to break into Fort Knox. 007 does some quick mental calculations to determine
the feasibility of removing the gold. If the price of gold is $14.00 per troy ounce (31.1035 grams) at the time the movie was
produced, what is the mass (in kg) of 1 million dollars of gold? What is the volume of 1 million dollars of gold in L. How much
would this gold be worth today if the price of gold is $9068.77 per kg?

A4
The following experiment is performed with an unknown liquid. The liquid is added to a graduated cylinder with a mass of 54.6789
grams. After 20.00 mL of the liquid is added to the cylinder (at 298 K), the mass is 74.6215 grams. Is the liquid water? How do you
know? If it is not water, what could it be?

A5
The experiment above is repeated with a second liquid, after 21.3 mL of this liquid (at 20 °C) is added the mass of the cylinder is
72.7364 grams. Is the second liquid ethanol? How do you know? If it is not ethanol, what could it be?

Answers
Exercise 1.8.1
A1

Answer
a) and c) (Sorry, I can't take out the repeat!) 9.00 x 1015 only 3 sig dig because of denominator
b) 9600 or 9.6 x 103 only 2 sig dig because of 7.1 x 102

1.8.1 [Link]
 Exercise 1.8.2
A2

Answer
a) 6.501 ft; 1.981 m; 198.1 cm; 1981 mm; 1.981 x 10-3 km
b) 2.7483 miles; 4.4230 km; 4423.0 m
c) 0.01542 km; 1542 cm; 15,420 mm; 1.542 x 108 μ m; 1.542 x 1011 pm
d) 37.0oC; 310.2 K
e) 1.2 x 102 km/h; 34 m/s
f) 2.492 x 102 ft2; 2.315 x 104 cm2; 3.588 x 103 in2

Exercise 1.8.3
A3

Answer
2.222 x 103kg; To get the volume you need the density of gold, which is 19.32 g/ml. The volume is 1.150 x 102 L; the value
today is $2.015 x 107

Exercise 1.8.4
A4

Answer
The density is found by first finding the mass of the liquid ( 74.6215-54.6789 = 19.9426 g), then dividing the mass by the
volume (19.9426/20.00 = 0.9771 g/mL). That is the density of water at 25 oC. There are not any other common liquids with
this density. You could create a mixture that has this density.

Exercise 1.8.5
A5

Answer
The density is found by first finding the mass of the liquid ( 72.7364-54.6789 = 18.0575 g), then dividing the mass by the
volume (18.0575/21.3 = 0.848 g/mL). That is the not density of ethanol at 20 oC. The liquid could be mineral oil, which a
mixture of many CxHy compounds.

1.8: Matter, Measurement, and Problem Solving (Exercises) is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or
curated by LibreTexts.

1.8.2 [Link]
 CHAPTER OVERVIEW

2: Atomic Structure
2.1: Modern Atomic Theory and the Laws That Led to It
2.2 The Structure of the Atom
2.3 Molar Mass - Counting Atoms by Weighing Them
2.4 Nuclear Reactions
2.5 The Belt of Stability - Predicting the Type of Radioactivity
2.6 Half-lives and the Rate of Radioactive Decay
2.7 Mass Defect - The Source of Nuclear Energy
2.8 Nuclear Energy - Fission and Fusion
2.9 The Nature of Light
2.10 Quantum Mechanics and The Atom
2.11 Trends of the Periodic Table
2.12 Example Problems

2: Atomic Structure is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
2.1: Modern Atomic Theory and the Laws That Led to It
Skills to Develop
By the end of this section, you will be able to:
State the postulates of Dalton’s atomic theory
Use postulates of Dalton’s atomic theory to explain the laws of definite and multiple proportions

The language used in chemistry is seen and heard in many disciplines, ranging from medicine to engineering to forensics to art.
The language of chemistry includes its own vocabulary as well as its own form of shorthand. Chemical symbols are used to
represent atoms and elements. Chemical formulas depict molecules as well as the composition of compounds. Chemical equations
provide information about the quality and quantity of the changes associated with chemical reactions.
This chapter will lay the foundation for our study of the language of chemistry. The concepts of this foundation include the atomic
theory, ion formation, the composition and mass of an atom, the variability of the composition of isotopes, nuclear stability, and
atomic electronic structure. We will also discuss in greater detail one of the most powerful tools for organizing chemical
knowledge: the periodic table.

Atomic Theory through the Nineteenth Century

The earliest recorded discussion of the basic structure of matter comes from ancient Greek philosophers, the scientists of their day.
In the fifth century BC, Leucippus and Democritus argued that all matter was composed of small, finite particles that they called
atomos, a term derived from the Greek word for “indivisible.” They thought of atoms as moving particles that differed in shape and
size, and which could join together. Later, Aristotle and others came to the conclusion that matter consisted of various
combinations of the four “elements”—fire, earth, air, and water—and could be infinitely divided. Interestingly, these philosophers
thought about atoms and “elements” as philosophical concepts, but apparently never considered performing experiments to test
their ideas.
The Aristotelian view of the composition of matter held sway for over two thousand years, until English schoolteacher John Dalton
helped to revolutionize chemistry with his hypothesis that the behavior of matter could be explained using an atomic theory. First
published in 1807, many of Dalton’s hypotheses about the microscopic features of matter are still valid in modern atomic theory.
Here are the postulates of Dalton’s atomic theory.
1. Matter is composed of exceedingly small particles called atoms. An atom is the smallest unit of an element that can participate
in a chemical change.
2. An element consists of only one type of atom, which has a mass that is characteristic of the element and is the same for all
atoms of that element (Figure 2.1.1). A macroscopic sample of an element contains an incredibly large number of atoms, all of
which have identical chemical properties.

Figure 2.1.1 : A pre-1982 copper penny (left) contains approximately 3 × 1022 copper atoms (several dozen are represented as
brown spheres at the right), each of which has the same chemical properties. (credit: modification of work by “slgckgc”/Flickr)
3. Atoms of one element differ in properties from atoms of all other elements.
4. A compound consists of atoms of two or more elements combined in a small, whole-number ratio. In a given compound, the
numbers of atoms of each of its elements are always present in the same ratio (Figure 2.1.2).

2.1.1 [Link]
Figure 2.1.2 : Copper(II) oxide, a powdery, black compound, results from the combination of two types of atoms—copper (brown
spheres) and oxygen (red spheres)—in a 1:1 ratio. (credit: modification of work by “Chemicalinterest”/Wikimedia Commons)
5. Atoms are neither created nor destroyed during a chemical change, but are instead rearranged to yield substances that are
different from those present before the change (Figure 2.1.3).

Figure 2.1.3 : When the elements copper (a shiny, red-brown solid, shown here as brown spheres) and oxygen (a clear and
colorless gas, shown here as red spheres) react, their atoms rearrange to form a compound containing copper and oxygen (a
powdery, black solid). (credit copper: modification of work by [Link]
Dalton’s atomic theory provides a microscopic explanation of the many macroscopic properties of matter that you’ve learned about.
For example, if an element such as copper consists of only one kind of atom, then it cannot be broken down into simpler
substances, that is, into substances composed of fewer types of atoms. And if atoms are neither created nor destroyed during a
chemical change, then the total mass of matter present when matter changes from one type to another will remain constant (the law
of conservation of matter). We will see that Dalton's atomic theory was not entirely correct because Dalton was unaware of the
existence of both isotopes and nuclear reactions.

Discovery of the Electron

Long before the end of the 19th century, it was well known that applying a high voltage to a gas contained at low pressure in a
sealed tube (called a gas discharge tube) caused electricity to flow through the gas, which then emitted light (Figure 2.1.4).
Researchers trying to understand this phenomenon found that an unusual form of energy was also emitted from the cathode, or
negatively charged electrode; this form of energy was called a cathode ray.

2.1.2 [Link]
 Figure
Figure 2.1.4 : A Gas Discharge Tube Producing Cathode Rays. When a high voltage is applied to a gas contained at low pressure
in a gas discharge tube, electricity flows through the gas, and energy is emitted in the form of light. Image used with Permission
(CC BY-SA-NC).
In 1897, the British physicist J. J. Thomson (1856–1940) proved that atoms were not the most basic form of matter. He
demonstrated that cathode rays could be deflected, or bent, by magnetic or electric fields, which indicated that cathode rays consist
of charged particles (Figure 2.1.5) More important, by measuring the extent of the deflection of the cathode rays in magnetic or
electric fields of various strengths, Thomson was able to calculate the mass-to-charge ratio of the particles. These particles were
emitted by the negatively charged cathode and repelled by the negative terminal of an electric field. Because like charges repel each
other and opposite charges attract, Thomson concluded that the particles had a net negative charge; these particles are now called
electrons. Most relevant to the field of chemistry, Thomson found that the mass-to-charge ratio of cathode rays is independent of
the nature of the metal electrodes or the gas, which suggested that electrons were fundamental components of all atoms.

Figure 2.1.5 : Deflection of Cathode Rays by an Electric Field. As the cathode rays travel toward the right, they are deflected
toward the positive electrode (+), demonstrating that they are negatively charged. Image used with Permission (CC BY-SA-NC).
Subsequently, the American scientist Robert Millikan (1868–1953) carried out a series of experiments using electrically charged oil
droplets, which allowed him to calculate the charge on a single electron. With this information and Thomson’s mass-to-charge
ratio, Millikan determined the mass of an electron:
mass
x charge = mass
charge

It was at this point that two separate lines of investigation began to converge, both aimed at determining how and why matter emits
energy. The video below shows how JJ Thompson used such a tube to measure the ratio of charge over mass of an electron

2.1.3 [Link]
 Physics Lab Demo 7: Thompson Experi…
Experi…

Measuring e/m For an Electron. Video from Davidson College demonstrating Thompson's e/m experiment.

Radioactivity
The second line of investigation began in 1896, when the French physicist Henri Becquerel (1852–1908) discovered that certain
minerals, such as uranium salts, emitted a new form of energy. Becquerel’s work was greatly extended by Marie Curie (1867–1934)
and her husband, Pierre (1854–1906); all three shared the Nobel Prize in Physics in 1903. Marie Curie coined the term radioactivity
(from the Latin radius, meaning “ray”) to describe the emission of energy rays by matter. She found that one particular uranium
ore, pitchblende, was substantially more radioactive than most, which suggested that it contained one or more highly radioactive
impurities. Starting with several tons of pitchblende, the Curies isolated two new radioactive elements after months of work:
polonium, which was named for Marie’s native Poland, and radium, which was named for its intense radioactivity. Pierre Curie
carried a vial of radium in his coat pocket to demonstrate its greenish glow, a habit that caused him to become ill from radiation
poisoning well before he was run over by a horse-drawn wagon and killed instantly in 1906. Marie Curie, in turn, died of what was
almost certainly radiation poisoning.

Figure 2.1.6 : Radium bromide illuminated by its own radioactive glow. This 1922 photo was taken in the dark in the Curie
laboratory.
Building on the Curies’ work, the British physicist Ernest Rutherford (1871–1937) performed decisive experiments that led to the
modern view of the structure of the atom. While working in Thomson’s laboratory shortly after Thomson discovered the electron,
Rutherford showed that compounds of uranium and other elements emitted at least two distinct types of radiation. One was readily
absorbed by matter and seemed to consist of particles that had a positive charge and were massive compared to electrons. Because
it was the first kind of radiation to be discovered, Rutherford called these substances α particles. Rutherford also showed that the
particles in the second type of radiation, β particles, had the same charge and mass-to-charge ratio as Thomson’s electrons; they are
now known to be high-speed electrons. A third type of radiation, γ rays, was discovered somewhat later and found to be similar to
the lower-energy form of radiation called x-rays, now used to produce images of bones and teeth.

2.1.4 [Link]
Figure 2.1.7 : Effect of an Electric Field on α Particles, β Particles, and γ Rays. A negative electrode deflects negatively charged
β particles, whereas a positive electrode deflects positively charged α particles. Uncharged γ rays are unaffected by an electric
field. (Relative deflections are not shown to scale.) Image used with Permission (CC BY-SA-NC).
These three kinds of radiation—α particles, β particles, and γ rays—are readily distinguished by the way they are deflected by an
electric field and by the degree to which they penetrate matter. As (Figure 2.1.7) illustrates, α particles and β particles are deflected
in opposite directions; α particles are deflected to a much lesser extent because of their higher mass-to-charge ratio. In contrast, γ
rays have no charge, so they are not deflected by electric or magnetic fields. Figure 2.1.8 hows that α particles have the least
penetrating power and are stopped by a sheet of paper, whereas β particles can pass through thin sheets of metal but are absorbed
by lead foil or even thick glass. In contrast, γ-rays can readily penetrate matter; thick blocks of lead or concrete are needed to stop
them.

Figure 2.1.8 : Relative Penetrating Power of the Three Types of Radiation. A sheet of paper stops comparatively massive α
particles, whereas β particles easily penetrate paper but are stopped by a thin piece of lead foil. Uncharged γ rays penetrate the
paper and lead foil; a much thicker piece of lead or concrete is needed to absorb them. Image used with Permission (CC BY-SA-
NC).

The Atomic Model

Once scientists concluded that all matter contains negatively charged electrons, it became clear that atoms, which are electrically
neutral, must also contain positive charges to balance the negative ones. Thomson proposed that the electrons were embedded in a
uniform sphere that contained both the positive charge and most of the mass of the atom, much like raisins in plum pudding or
chocolate chips in a cookie (Figure 2.1.9)

2.1.5 [Link]
Figure 2.1.9 : Thomson’s Plum Pudding or Chocolate Chip Cookie Model of the Atom. In this model, the electrons are embedded
in a uniform sphere of positive charge. Image used with Permission (CC BY-SA-NC).
In a single famous experiment, however, Rutherford showed unambiguously that Thomson’s model of the atom was incorrect.
Rutherford aimed a stream of α particles at a very thin gold foil target (Figure 2.1.10a) and examined how the α particles were
scattered by the foil. Gold was chosen because it could be easily hammered into extremely thin sheets, minimizing the number of
atoms in the target. If Thomson’s model of the atom were correct, the positively-charged α particles should crash through the
uniformly distributed mass of the gold target like cannonballs through the side of a wooden house. They might be moving a little
slower when they emerged, but they should pass essentially straight through the target (Figure 2.1.10b)To Rutherford’s amazement,
a small fraction of the α particles were deflected at large angles, and some were reflected directly back at the source (Figure
2.1.10c). According to Rutherford, “It was almost as incredible as if you fired a 15-inch shell at a piece of tissue paper and it came

back and hit you.”

Figure 2.1.10 : A Summary of Rutherford’s Experiments. (a) A representation of the apparatus Rutherford used to detect
deflections in a stream of α particles aimed at a thin gold foil target. The particles were produced by a sample of radium. (b) If
Thomson’s model of the atom were correct, the α particles should have passed straight through the gold foil. (c) However, a small
number of α particles were deflected in various directions, including right back at the source. This could be true only if the positive
charge were much more massive than the α particle. It suggested that the mass of the gold atom is concentrated in a very small
region of space, which he called the nucleus. Image used with Permission (CC BY-SA-NC).
Rutherford’s results were not consistent with a model in which the mass and positive charge are distributed uniformly throughout
the volume of an atom. Instead, they strongly suggested that both the mass and positive charge are concentrated in a tiny fraction of
the volume of an atom, which Rutherford called the nucleus. It made sense that a small fraction of the α particles collided with the

2.1.6 [Link]
dense, positively charged nuclei in either a glancing fashion, resulting in large deflections, or almost head-on, causing them to be
reflected straight back at the source.
Although Rutherford could not explain why repulsions between the positive charges in nuclei that contained more than one positive
charge did not cause the nucleus to disintegrate, he reasoned that repulsions between negatively charged electrons would cause the
electrons to be uniformly distributed throughout the atom’s [Link] it is known that strong nuclear forces, which are much
stronger than electrostatic interactions, hold the protons and the neutrons together in the nucleus. For this and other insights,
Rutherford was awarded the Nobel Prize in Chemistry in 1908. Unfortunately, Rutherford would have preferred to receive the
Nobel Prize in Physics because he considered physics superior to chemistry. In his opinion, “All science is either physics or stamp
collecting.”

Figure 2.1.11 : A Summary of the Historical Development of Models of the Components and Structure of the Atom. The dates in
parentheses are the years in which the key experiments were performed. Image used with Permission (CC BY-SA-NC).
The historical development of the different models of the atom’s structure is summarized in (Figure 2.1.11) Rutherford established
that the nucleus of the hydrogen atom was a positively charged particle, for which he coined the name proton in 1920. He also
suggested that the nuclei of elements other than hydrogen must contain electrically neutral particles with approximately the same
mass as the proton. The neutron, however, was not discovered until 1932, when James Chadwick (1891–1974, a student of
Rutherford; Nobel Prize in Physics, 1935) discovered it. As a result of Rutherford’s work, it became clear that an α particle
contains two protons and neutrons, and is therefore the nucleus of a helium atom.

2.1.7 [Link]
 Figure 2.1.12 : The Evolution of Atomic Theory, as Illustrated by Models of the Oxygen Atom. Bohr’s model and the current
model are described in Chapter 6, "The Structure of Atoms." Image used with Permission (CC BY-SA-NC).
Rutherford’s model of the atom is essentially the same as the modern model, except that it is now known that electrons are not
uniformly distributed throughout an atom’s volume. Instead, they are distributed according to a set of principles described by
Quantum Mechanics. Figure 2.1.12 shows how the model of the atom has evolved over time from the indivisible unit of Dalton to
the modern view taught today.

Summary
The ancient Greeks proposed that matter consists of extremely small particles called atoms. Dalton postulated that each element has
a characteristic type of atom that differs in properties from atoms of all other elements, and that atoms of different elements can
combine in fixed, small, whole-number ratios to form compounds. During any chemical change, atoms are neither created nor
destroyed. Atoms are the ultimate building blocks of all matter. The modern atomic theory establishes the concepts of atoms and
how they compose matter.
Atoms consist of negatively charged electrons around a central nucleus composed of more massive positively charged protons and
electrically neutral neutrons. Radioactivity is the emission of energetic particles and rays (radiation) by some substances. Three
important kinds of radiation are α particles (helium nuclei), β particles (electrons traveling at high speed), and γ rays (similar to x-
rays but higher in energy).

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).

Modified by Tom Neils (Grand Rapids Community College)

2.1: Modern Atomic Theory and the Laws That Led to It is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated
by LibreTexts.

2.1.8 [Link]
2.2 The Structure of the Atom
Skills to Develop
Write and interpret symbols that depict the atomic number, mass number, and charge of an atom or ion
Define the atomic mass unit and average atomic mass
Calculate average atomic mass and isotopic abundance

The development of modern atomic theory revealed much about the inner structure of atoms. It was learned that an atom contains a
very small nucleus composed of positively charged protons and uncharged neutrons, surrounded by a much larger volume of space
containing negatively charged electrons. The nucleus contains the majority of an atom’s mass because protons and neutrons are
much heavier than electrons, whereas electrons occupy almost all of an atom’s volume. The diameter of an atom is on the order of
10−10 m, whereas the diameter of the nucleus is roughly 10−15 m—about 100,000 times smaller. For a perspective about their
relative sizes, consider this: If the nucleus were the size of a blueberry, the atom would be about the size of a football stadium
(Figure 1).

Figure 1 : If an atom could be expanded to the size of a football stadium, the nucleus would be the size of a single blueberry. (credit
middle: modification of work by “babyknight”/Wikimedia Commons; credit right: modification of work by Paxson Woelber).
Atoms—and the protons, neutrons, and electrons that compose them—are extremely small. For example, a carbon atom weighs
less than 2 × 10−23 g, and an electron has a charge of less than 2 × 10−19 C (coulomb). When describing the properties of tiny
objects such as atoms, we use appropriately small units of measure, such as the atomic mass unit (amu) and the fundamental unit of
charge (e). The amu was originally defined based on hydrogen, the lightest element, then later in terms of oxygen. Since 1961, it
has been defined with regard to the most abundant isotope of carbon, atoms of which are assigned masses of exactly 12 amu. (This
isotope is known as “carbon-12” as will be discussed later in this chapter.) Thus, one amu is exactly 1/12 of the mass of one
carbon-12 atom: 1 amu = 1.6605 × 10−24 g. (The Dalton (Da) and the unified atomic mass unit (u) are alternative units that are
equivalent to the amu.) The fundamental unit of charge (also called the elementary charge) equals the magnitude of the charge of an
electron (e) with e = -1.602 × 10−19 C.
A proton has a mass of 1.0073 amu and a charge of +1.602 × 10−19 C. A neutron is a slightly heavier particle than a proton, with a
mass 1.0087 amu and a charge of zero; as its name suggests, it is neutral. The electron has a charge of -1.602 × 10−19 C and is a
much lighter particle, with a mass of about 0.00055 amu. (It would take about 1800 electrons to equal the mass of one proton.) The
properties of these fundamental particles are summarized in Table 1. (An observant student might notice that the sum of an atom’s
subatomic particles does not equal the atom’s actual mass: The total mass of six protons, six neutrons, and six electrons is 12.0993
amu, slightly larger than the 12.00 amu of an actual carbon-12 atom. This “missing” mass is known as the mass defect, and you
will learn about it in the chapter on nuclear chemistry.)
Table 1 : Properties of Subatomic Particles
Name Location Charge (C) Relative Charge Mass (amu) Mass (g)

electron outside nucleus −1.602 × 10

−19
−1 0.00055 0.00091 × 10
−24

proton nucleus 1.602 × 10

−19
+1 1.00727 1.67262 × 10
−24

neutron nucleus 0 0 1.00866 1.67493 × 10

−24

Access for free at OpenStax 1 [Link]

The number of protons in the nucleus of an atom is its atomic number (Z). This is the defining trait of an element: the number
of protons determines the identity of the atom. For example, any atom that contains six protons is a carbon atom and has the
atomic number 6, regardless of how many neutrons or electrons it may have.
A neutral atom must contain the same number of positive and negative charges, so the number of protons equals the number of
electrons. Therefore, the atomic number also indicates the number of electrons in an atom. The total number of protons and
neutrons in an atom is called its mass number (A). The number of neutrons is therefore the difference between the mass number
and the atomic number: A – Z = number of neutrons.

atomic number (Z) = number of protons

mass number (A) = number of protons + number of neutrons

A−Z = number of neutrons

Atoms are electrically neutral if they contain the same number of positively charged protons and negatively charged electrons.
When the numbers of these subatomic particles are not equal, the atom is electrically charged and is called an ion. The charge of an
atom is defined as follows:
the atomic charge = the number of protons − the number of electrons
It is also true that:
the number of electrons = the number of protons - the atomic charge
As will be discussed in more detail later in this chapter, atoms (and molecules) acquire charge by gaining or losing electrons. An
atom that gains one or more electrons will exhibit a negative charge and is called an anion. A positively charged atom is called a
cation. A cation is formed when an atom loses one or more electrons. For example, a neutral sodium atom (Z = 11) has 11
electrons. If this atom loses one electron, it will become a cation with a +1 charge (11 − 10 = +1). A neutral oxygen atom (Z = 8)
has eight electrons, and if it gains two electrons it will become an anion with a −2 charge (8 − 10 = −2).
By convention, the charge of an ion is written as a superscript on the right side of the element symbol, with the magnitude of the
charge written first, followed by the sign of the charge. Thus, the sodium ion with a +1 charge is written as N a or simply N a .
1+ +

The sulfur ion with a -2 charge is written as S .

2−

Example 1 : Composition of an Atom

Iodine is an essential trace element in our diet; it is needed to produce thyroid hormone. Insufficient iodine in the diet can lead
to the development of a goiter, an enlargement of the thyroid gland (Figure 2).

Figure 2 : (a) Insufficient iodine in the diet can cause an enlargement of the thyroid gland called a goiter. (b) The addition of
small amounts of iodine to salt, which prevents the formation of goiters, has helped eliminate this concern in the US where salt
consumption is high. (credit a: modification of work by “Almazi”/Wikimedia Commons; credit b: modification of work by Mike
Mozart)

Access for free at OpenStax 2 [Link]

 The addition of small amounts of iodine to table salt (iodized salt) has essentially eliminated this health concern in the United
States, but as much as 40% of the world’s population is still at risk of iodine deficiency. The iodine atoms are added as anions,
and each has a −1 charge and a mass number of 127. Determine the numbers of protons, neutrons, and electrons in an iodine
anion.
Solution
The atomic number of iodine (53) tells us that a neutral iodine atom contains 53 protons in its nucleus and 53 electrons outside
its nucleus. Because the sum of the numbers of protons and neutrons equals the mass number, 127, the number of neutrons is 74
(127 − 53 = 74). Since the iodine is added as a −1 anion, the number of electrons is 54 [53 – (–1) = 54].

Exercise 1
An ion of platinum has a mass number of 195 and contains 74 electrons. How many protons and neutrons does it contain, and
what is its charge?

Answer
78 protons; 117 neutrons; charge is +4

Chemical Symbols
A chemical symbol is an abbreviation that we use to indicate an element or an atom of an element. For example, the symbol for
mercury is Hg (Figure 3). We use the same symbol to indicate one atom of mercury (microscopic domain) or to label a container of
many atoms of the element mercury (macroscopic domain).

Figure 3 : The symbol Hg represents the element mercury regardless of the amount; it could represent one atom of mercury or a
large amount of mercury. Image used with permission from Wikipedia (user: Materialscientist).
The symbols for several common elements and their atoms are listed in Table 2. Some symbols are derived from the common name
of the element; others are abbreviations of the name in another language. Symbols have one or two letters, for example, H for
hydrogen and Cl for chlorine. To avoid confusion with other notations, only the first letter of a symbol is capitalized. For example,
Co is the symbol for the element cobalt, but CO is the notation for the compound carbon monoxide, which contains atoms of the
elements carbon (C) and oxygen (O). All known elements and their symbols are in the periodic table.
Table 2 : Some Common Elements and Their Symbols
Element Symbol Element Symbol

aluminum Al iron Fe (from ferrum)

bromine Br lead Pb (from plumbum)

calcium Ca magnesium Mg

Access for free at OpenStax 3 [Link]

 Element Symbol Element Symbol

carbon C mercury Hg (from hydrargyrum)

chlorine Cl nitrogen N

chromium Cr oxygen O

cobalt Co potassium K (from kalium)

copper Cu (from cuprum) silicon Si

fluorine F silver Ag (from argentum)

gold Au (from aurum) sodium Na (from natrium)

helium He sulfur S

hydrogen H tin Sn (from stannum)

iodine I zinc Zn

Traditionally, the discoverer (or discoverers) of a new element names the element. However, until the name is recognized by the
International Union of Pure and Applied Chemistry (IUPAC), the recommended name of the new element is based on the Latin
word(s) for its atomic number. For example, element 106 was called unnilhexium (Unh), element 107 was called unnilseptium
(Uns), and element 108 was called unniloctium (Uno) for several years. These elements are now named after scientists or locations;
for example, element 106 is now known as seaborgium (Sg) in honor of Glenn Seaborg, a Nobel Prize winner who was active in
the discovery of several heavy elements.

Isotopes
Isotopes are atoms of the same element that have different numbers of neutrons. The symbol for a specific isotope of any element is
written by placing the mass number as a superscript to the left of the element symbol (Figure 4). The atomic number is sometimes
written as a subscript preceding the symbol, but since this number defines the element’s identity, as does its symbol, it is often
omitted. For example, magnesium exists as a mixture of three isotopes, each with an atomic number of 12 and with mass numbers
of 24, 25, and 26, respectively. These isotopes can be identified as 24Mg, 25Mg, and 26Mg. These isotope symbols are read as
“element, mass number” and can be symbolized consistent with this reading. For instance, 24Mg is read as “magnesium 24,” and
can be written as “magnesium-24” or “Mg-24.” 25Mg is read as “magnesium 25,” and can be written as “magnesium-25” or “Mg-
25.” All magnesium atoms have 12 protons in their nucleus. They differ only because a 24Mg atom has 12 neutrons in its nucleus, a
25
Mg atom has 13 neutrons, and a 26Mg has 14 neutrons.

Figure 4 : The symbol for an atom indicates the element via its usual two-letter symbol, the mass number as a left superscript, the
atomic number as a left subscript (sometimes omitted), and the charge as a right superscript.
Information about the naturally occurring isotopes of elements with atomic numbers 1 through 10 is given in Table 2. Note that in
addition to standard names and symbols, the isotopes of hydrogen are often referred to using common names and accompanying
symbols. Hydrogen-2, symbolized 2H, is also called deuterium and sometimes symbolized D. Hydrogen-3, symbolized 3H, is also
called tritium and sometimes symbolized T.
Table 2 : Nuclear Compositions of Atoms of the Very Light Elements

Access for free at OpenStax 4 [Link]

Element Symbol Atomic Number of Number of Mass (amu) % Natural
Number Protons Neutrons Abundance

1
1
H 1 1 0 1.0078 99.989
(protium)

2
H 1 1 1 2.0141 0.0115
hydrogen 1

(deuterium)

3
1
H 1 1 2 3.01605 — (trace)
(tritium)

3
2
He 2 2 1 3.01603 0.00013
helium
4
2
He 2 2 2 4.0026 100

6
3
Li 3 3 3 6.0151 7.59
lithium
7
3
Li 3 3 4 7.0160 92.41

beryllium 9
4
Be 4 4 5 9.0122 100

10
5
B 5 5 5 10.0129 19.9
boron
11
5
B 5 5 6 11.0093 80.1

12
6
C 6 6 6 12.0000 98.89

carbon 13
6
C 6 6 7 13.0034 1.11

14

6
C 6 6 8 14.0032 — (trace)

14
7
N 7 7 7 14.0031 99.63
nitrogen
15
7
N 7 7 8 15.0001 0.37

16
8
O 8 8 8 15.9949 99.757

oxygen 17

8
O 8 8 9 16.9991 0.038

18
8
O 8 8 10 17.9992 0.205

fluorine 19
9
F 9 9 10 18.9984 100

20
10
Ne 10 10 10 19.9924 90.48

neon 21
10
Ne 10 10 11 20.9938 0.27

22
10
Ne 10 10 12 21.9914 9.25

Access for free at OpenStax 5 [Link]

Atomic Mass
Because each proton and each neutron contribute approximately one amu to the mass of an atom, and each electron contributes far
less, the atomic mass of a single atom is approximately equal to its mass number (a whole number). However, the average masses
of atoms of most elements are not whole numbers because most elements exist naturally as mixtures of two or more isotopes.
The mass of an element shown in a periodic table or listed in a table of atomic masses is a weighted, average mass of all the
isotopes present in a naturally occurring sample of that element. This weighted average mass is equal to the sum of each individual
isotope’s mass multiplied by its fractional abundance.

weighted average mass = ∑(f ractional abundance × isotopic mass)i (1)

For example, the element boron is composed of two isotopes: About 19.9% of all boron atoms are 10B with a mass of 10.0129 amu,
and the remaining 80.1% are 11B with a mass of 11.0093 amu. The average atomic mass for boron is calculated to be:
boron average mass = (0.199 × 10.0129 amu) + (0.801 × 11.0093 amu)

= 1.99 amu + 8.82 amu

= 10.81 amu

It is important to understand that no single boron atom weighs exactly 10.81 amu; 10.81 amu is the weighted average mass of all
boron atoms, and individual boron atoms weigh either approximately 10 amu or 11 amu.

Example 2 : Calculation of Average Atomic Mass

A meteorite found in central Indiana contains traces of the noble gas neon picked up from the solar wind during the meteorite’s
trip through the solar system. Analysis of a sample of the gas showed that it consisted of 91.84% 20Ne (mass 19.9924 amu),
0.47% 21Ne (mass 20.9940 amu), and 7.69% 22Ne (mass 21.9914 amu). What is the average mass of the neon in the solar wind?
Solution
average mass = (0.9184 × 19.9924 amu) + (0.0047 × 20.9940 amu) + (0.0769 × 21.9914 amu)

= (18.36 + 0.099 + 1.69) amu

= 20.15 amu

The average mass of a neon atom in the solar wind is 20.15 amu. (The average mass of a terrestrial neon atom is 20.1796 amu.
This result demonstrates that we may find slight differences in the natural abundance of isotopes, depending on their origin.)

Exercise 2
A sample of magnesium is found to contain 78.70% of 24Mg atoms (mass 23.98 amu), 10.13% of 25Mg atoms (mass 24.99
amu), and 11.17% of 26Mg atoms (mass 25.98 amu). Calculate the average mass of a Mg atom.

Answer
24.31 amu

We can also do variations of this type of calculation, as shown in the next example.

Example 3 : Calculation of Percent Abundance

Naturally occurring chlorine consists of 35Cl (mass 34.96885 amu) and 37Cl (mass 36.96590 amu), with a weighted average
mass of 35.453 amu. What is the percent composition of Cl in terms of these two isotopes?
Solution
The weighted average mass of chlorine is the fraction that is 35Cl times the mass of 35Cl plus the fraction that is 37Cl times the
mass of 37Cl.
35 35 37 37
weighted average mass = (f raction of Cl × mass of Cl) + (f raction of Cl × mass of Cl) (2)

If we let x represent the fraction that is 35Cl, then the fraction that is 37Cl is represented by 1.00 − x.

Access for free at OpenStax 6 [Link]

 35 37 37
(The fraction that is Cl + the fraction that is Cl must add up to 1, so the fraction of Cl must equal 1.00 − the fraction of
35
Cl.)
Substituting this into the average mass equation, we have:

35.453 amu = (x × 34.96885 amu) + [(1.00 − x) × 36.96590 amu]

35.453 = 34.96885x + 36.96590 − 36.96590x

1.99705x = 1.513

1.513
x = = 0.7576
1.99705

35
So solving yields: x = 0.7576, which means that 1.00 − 0.7576 = 0.2424. Therefore, chlorine consists of 75.76% Cl and
24.24% 37Cl.

Exercise 3
Naturally occurring copper consists of 63Cu (mass 62.9296 amu) and 65Cu (mass 64.9278 amu), with a weighted average mass
of 63.546 amu. What is the percent composition of Cu in terms of these two isotopes?

Answer
69.15% Cu-63 and 30.85% Cu-65

Figure 5 : Analysis of zirconium in a mass spectrometer produces a mass spectrum with peaks showing the different isotopes of Zr.
The occurrence and natural abundance of isotopes can be experimentally determined using an instrument called a mass
spectrometer. Mass spectrometry (MS) is widely used in chemistry, forensics, medicine, environmental science, and many other
fields to analyze and help identify the substances in a sample of material. In a typical mass spectrometer (Figure 5), the sample is
vaporized and exposed to a high-energy electron beam that causes the sample’s atoms (or molecules) to become electrically
charged, typically by losing one or more electrons. These cations then pass through a (variable) electric or magnetic field that
deflects each cation’s path to an extent that depends on both its mass and charge (similar to how the path of a large steel ball
bearing rolling past a magnet is deflected to a lesser extent that that of a small steel BB). The ions are detected, and a plot of the
relative number of ions generated versus their mass-to-charge ratios (a mass spectrum) is made. The height of each vertical feature
or peak in a mass spectrum is proportional to the fraction of cations with the specified mass-to-charge ratio. Since its initial use
during the development of modern atomic theory, MS has evolved to become a powerful tool for chemical analysis in a wide range
of applications.

Access for free at OpenStax 7 [Link]

 Mass Spectrometry MS

Video 1 : Watch this video from the Royal Society for Chemistry for a brief description of the rudiments of mass spectrometry.

Summary
An atom consists of a small, positively charged nucleus surrounded by electrons. The nucleus contains protons and neutrons; its
diameter is about 100,000 times smaller than that of the atom. The mass of one atom is usually expressed in atomic mass units
(amu), which is referred to as the atomic mass. An amu is defined as exactly 1/12 of the mass of a carbon-12 atom and is equal to
1.6605 × 10−24 g.
Protons are relatively heavy particles with a charge of +1 and a mass of 1.0073 amu. Neutrons are relatively heavy particles with no
charge and a mass of 1.0087 amu. Electrons are light particles with a charge of −1 and a mass of 0.00055 amu. The number of
protons in the nucleus is called the atomic number (Z) and is the property that defines an atom’s elemental identity. The sum of the
numbers of protons and neutrons in the nucleus is called the mass number and, expressed in amu, is approximately equal to the
mass of the atom. An atom is neutral when it contains equal numbers of electrons and protons.
Isotopes of an element are atoms with the same atomic number but different mass numbers; isotopes of an element, therefore, differ
from each other only in the number of neutrons within the nucleus. When a naturally occurring element is composed of several
isotopes, the atomic mass of the element represents the average of the masses of the isotopes involved. A chemical symbol
identifies the atoms in a substance using symbols, which are one-, or two-letter abbreviations for the atoms.

Key Equations
weighted average mass = ∑ (f ractional abundance × isotopic mass)i
i

Glossary
anion
negatively charged atom or molecule (contains more electrons than protons)

atomic mass
average mass of atoms of an element, expressed in amu

atomic mass unit (amu)

1
(also, unified atomic mass unit, u, or Dalton, Da) unit of mass equal to of the mass of a 12C atom
12

atomic number (Z)

number of protons in the nucleus of an atom

cation
positively charged atom or molecule (contains fewer electrons than protons)

chemical symbol

Access for free at OpenStax 8 [Link]

 one-, or two-letter abbreviation used to represent an element or its atoms

Dalton (Da)
alternative unit equivalent to the atomic mass unit

fundamental unit of charge

(also called the elementary charge) equals the magnitude of the charge of an electron (e) with e = 1.602 × 10−19 C

ion
electrically charged atom or molecule (contains unequal numbers of protons and electrons)

mass number (A)

sum of the numbers of neutrons and protons in the nucleus of an atom
unified atomic mass unit (u)
alternative unit equivalent to the atomic mass unit

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).

modified by Tom Neils (Grand Rapids Community College)

This page titled 2.2 The Structure of the Atom is shared under a CC BY license and was authored, remixed, and/or curated by OpenStax.

Access for free at OpenStax 9 [Link]

2.3 Molar Mass - Counting Atoms by Weighing Them
Skills to Develop
After reading this section you should be able to
Define Avogadro's number and explain why it is important to know.
Define the mole.
Be able to calculate the number of moles in a given mass of an element, or the mass corresponding to a given number of
moles.
Define atomic weight and molar mass; explain how the latter differs from the former.
Be able to find the number of atoms in a given mass of a substance.

The chemical changes we observe always involve discrete numbers of atoms that rearrange themselves into new configurations.
These numbers are HUGE— far too large in magnitude for us to count or even visualize, but they are still numbers, and we need to
have a way to deal with them. We also need a bridge between these numbers, which we are unable to measure directly, and the
weights of substances, which we do measure and observe. The mole concept provides this bridge, and is central to all of
quantitative chemistry.

Counting Atoms: Avogadro's Number

Owing to their tiny size, atoms and molecules cannot be counted by direct observation. But much as we do when "counting" beans
in a jar, we can estimate the number of particles in a sample of an element or compound if we have some idea of the volume
occupied by each particle and the volume of the container. Once this has been done, we know the number of formula units (to use
the most general term for any combination of atoms we wish to define) in any arbitrary weight of the substance. The number will of
course depend both on the formula of the substance and on the mass of the sample. However, if we consider a mass of substance
that is the same as its atomic or molecular mass, expressed in grams, we have only one number to know: Avogadro's number,
abbreviated as N . A

Avogadro's number
Avogadro's number is known to nine significant digits:
23
NA = 6.02214076 × 10 . (1)

However, for most calculations you only need to know it to four significant figures:
23
NA ≈ 6.022 × 10 . (2)

So 6.022 × 10 of what? Well, of anything you like: apples, stars in the sky, burritos. However, the only practical use for N is
23
A

for expressing the huge numbers of the tiny particles such as atoms or molecules that we deal with in chemistry. Avogadro's
number is a counting number, just like a dozen (12 things), or a gross (144 things), or a ream (500 things). Students can think of
6.022 × 10
23
as the "chemist's dozen".
Before getting into the use of Avogadro's number in problems, take a moment to convince yourself of the reasoning embodied in
the following examples.

Example 1 : Mass ratio from atomic weights

The atomic weights of oxygen and carbon are 16.0 and 12.0 atomic mass units (amu), respectively. How much heavier is the
oxygen atom in relation to carbon?
Solution
Atomic weights represent the relative masses of different kinds of atoms. This means that the atom of oxygen has a mass that is
16 amu 4
= ≈ 1.33
12 amu 3

as great as the mass of a carbon atom.

1 [Link]
Example 2 : Mass of a single atom
The absolute mass of a carbon atom is 12.0 atomic mass units (amu). How many grams will a single oxygen atom weigh?
Solution
The absolute mass of a carbon atom is 12.0 amu or
–24
1.6605 × 10 g
–23
12 amu × = 1.99 × 10 g (per carbon atom)
1 amu

The mass of the oxygen atom will be 4/3 greater (from Example 1):
4
–23 –23
( ) 1.99 × 10 g = 2.66 × 10 g (per oxygen atom)
3

Alternatively we can do the calculation directly like with carbon:

–24
1.6605 × 10 g –23
16 amu × = 2.66 × 10 g (per oxygen atom)
1 amu

Example 3 : Relative masses from atomic weights

Suppose that we have N carbon atoms, where N is a number large enough to give us a pile of carbon atoms whose mass is 12.0
grams. How much would the same number, N , of oxygen atoms weigh?
Solution
We use the results from Example 1 again. The collection of N oxygen atoms would have a mass of
4
× 12 g = 16.0 g.
3

Exercise 1
What is the numerical value of N in Example 3?

Answer
Using the results of Examples 2 and 3.
–23
N × 1.99 × 10 g (per carbon atom) = 12 g

or
12 g
23
N = = 6.03 × 10 atoms
–23
1.99 × 10 g (per carbon atom)

There are a lot of atoms in 12 g of carbon.

Things to understand about Avogadro's number

It is a number, just as is "dozen", and thus is dimensionless.
It is a huge number, far greater in magnitude than we can visualize
Its practical use is limited to counting tiny things like atoms, molecules, "formula units", electrons, or photons.
The value of NA can be known only to the precision that the number of atoms in a measurable weight of a substance can be
estimated. Because large numbers of atoms cannot be counted directly, a variety of ingenious indirect measurements have
been made involving such things as Brownian motion and X-ray scattering.
The current value was determined by measuring the distances between the atoms of silicon in an ultrapure crystal of this
element that was shaped into a perfect sphere. (The measurement was made by X-ray scattering.) When combined with the
measured mass of this sphere, it yields Avogadro's number. However, there are two problems with this:

2 [Link]
 The silicon sphere is an artifact, rather than being something that occurs in nature, and thus may not be perfectly
reproducible.
The standard of mass, the kilogram, is not precisely known, and its value appears to be changing. For these reasons, there
are proposals to revise the definitions of both NA and the kilogram.

Moles and their Uses

The mole (abbreviated mol) is the the SI measure of quantity of a "chemical entity", which can be an atom, molecule, formula unit,
electron or photon. One mole of anything is just Avogadro's number of that something. Or, if you think like a lawyer, you might
prefer the official SI definition:
Definition: The Mole
The mole is the amount of substance of a system which contains as many elementary entities as there are atoms in 0.01200
kilogram of carbon 12

Avogadro's number (Equation 2) like any pure number, is dimensionless. However, it also defines the mole, so we can also express
NA as 6.022 × 1023 mol–1; in this form, it is properly known as Avogadro's constant. This construction emphasizes the role of
Avogadro's number as a conversion factor between number of moles and number of "entities".

Example 4 : number of moles in N particles

How many moles of nickel atoms are there in 80 nickel atoms?
Solution
1 mole N i atoms −22
80 N i atoms × = 1.33 × 10 mole N i atoms
23
6.022 × 10 N i atoms

Is this answer reasonable? Yes, because 80 is an extremely small fraction of N .

A

Molar Mass
The mass of one mole of the fundamental units (atoms, molecules, or groups of atoms that correspond to the formula of a pure
substance) is the ratio of its mass to 1/12 the mass of one mole of C-12 atoms, and being a ratio, is dimensionless. But at the same
time, this molar mass (as many now prefer to call it) is also the observable mass of one mole (NA) of the substance, so we
frequently emphasize this by stating it explicitly as so many grams (or kilograms) per mole: g mol–1.

It is important always to bear in mind that the mole is a number and not a mass. But each
individual particle of a pure substance has a mass of its own, so a mole of any specific
substance will always correspond to a certain mass, the molar mass, of that substance.
Example 5 : Manganese atoms
The molar mass of manganese (Mn) is 54.938 grams per mole
a. How many moles of manganese atoms are present in 20.0 g of manganese?
b. How many atoms of manganese are present in 20.0 g of manganese?
c. How many grams of manganese atoms are present in 3.47 x 1024 manganese atoms?
Solution
1 mole M n atoms
a. 20.0 grams M n atoms × = 0.364 moles of M n atoms
54.938 grams of M n atoms

23
1 mole M n atoms 6.022 × 10 M n atoms
b. 20.0 grams M n atoms × × = 2.19 × 10
23
M n atoms
54.938 grams of M n atoms 1 mole M n atoms

1 moleM n atoms 54.938 grams of M n atoms

c. 3.47 × 10
24
M n atoms ×
23
= 317 grams M n atoms
6.022 × 10 M n atoms 1 moleM n atoms

Exercise 1

3 [Link]
 The molar mass of ruthenium (Ru) is 101.07 grams per mole
a. How many moles of ruthenium atoms are present in 200.0 g of manganese?
b. How many atoms of ruthenium are present in 200.0 g of manganese?
c. How many grams of ruthenium atoms are present in 3.47 x 1024 manganese atoms?

Answer
1 mole Ru atoms
200.0 grams Ru atoms × = 1.979 moles of Ru atoms
101.07 grams of Ru atoms

23
1 mole Ru atoms 6.022 × 10 Ru atoms 24
200.0 grams Ru atoms × × = 1.192 × 10 Ru atoms
101.07 grams of Ru atoms 1 mole Ru atoms

1 moleRu atoms 101.07 grams of Ru atoms

24
3.47 × 10 Ru atoms × = 582.4 grams Ru atoms
23
6.022 × 10 Ru atoms 1 moleRu atoms

Contributors
Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook
modified by Tom Neils (Grand Rapids Community College)

2.3 Molar Mass - Counting Atoms by Weighing Them is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

4 [Link]
2.4 Nuclear Reactions
Skills to Develop
Write and balance nuclear equations
Know the different kinds of radioactive decay.

Nuclear chemistry is the study of reactions that involve changes in nuclear structure. The sections on atoms, molecules, and ions
introduced the basic idea of nuclear structure; that the nucleus of an atom is composed of protons and neutrons (with the exception
of H ). Recall that the number of protons in the nucleus is called the atomic number (Z ) of the element, and the sum of the number
1
1

of protons and the number of neutrons is the mass number (A ). Atoms with the same atomic number but different mass numbers
are isotopes of the same element. When referring to a single type of nucleus, we often use the term nuclide and identify it by the
notation:
A
X (1)
Z

where
X is the symbol for the element,
A is the mass number, and
Z is the atomic number.
Often a nuclide is referenced by the name of the element followed by a hyphen and the mass number. For example, 14
6
C is called
“carbon-14.”
Protons and neutrons, collectively called nucleons, are packed together tightly in a nucleus. With a radius of about 10−15 meters, a
nucleus is quite small compared to the radius of the entire atom, which is about 10−10 meters. Nuclei are extremely dense compared
to bulk matter, averaging 1.8 × 10 grams per cubic centimeter. For example, water has a density of 1 gram per cubic centimeter,
14

and iridium, one of the densest elements known, has a density of 22.6 g/cm3. If the earth’s density were equal to the average
nuclear density, the earth’s radius would be only about 200 meters (earth’s actual radius is approximately 6.4 × 10 meters, 30,000
6

times larger).
Changes of nuclei that result in changes in their atomic numbers, mass numbers, or energy states are nuclear reactions. To describe
a nuclear reaction, we use an equation that identifies the nuclides involved in the reaction, their mass numbers and atomic numbers,
and the other particles involved in the reaction.

Nuclear Equations
A balanced chemical reaction equation reflects the fact that during a chemical reaction, bonds break and form, and atoms are
rearranged, but the total numbers of atoms of each element are conserved and do not change. A balanced nuclear reaction equation
indicates that there is a rearrangement during a nuclear reaction, but subatomic particles are rearranged rather than atoms. Nuclear
reactions also follow conservation laws, and they are balanced in two ways:
1. The sum of the mass numbers of the reactants equals the sum of the mass numbers of the products.
2. The sum of the charges of the reactants equals the sum of the charges of the products.
If the atomic number and the mass number of all but one of the particles in a nuclear reaction are known, we can identify the
particle by balancing the reaction. For instance, we could determine that O is a product of the nuclear reaction of N and He if
17
8
14
7
4
2

we knew that a proton, H , was one of the two products. Example 1 shows how we can identify a nuclide by balancing the nuclear
1
1

reaction.

Example 1 : Balancing Equations for Nuclear Reactions

The reaction of an α particle with magnesium-25 ( 25
12
Mg ) produces a proton and a nuclide of another element. Identify the new
nuclide produced.
Solution
The nuclear reaction can be written as:
25 4 1 A
12
Mg + 2 He → 1
H+ Z
X (2)

1 [Link]
 where
A is the mass number and
Z is the atomic number of the new nuclide, X .
Because the sum of the mass numbers of the reactants must equal the sum of the mass numbers of the products:
25 + 4 = A + 1 (3)

so
A = 28 (4)

Similarly, the charges must balance, so:

12 + 2 = Z + 1 (5)

so
Z = 13 (6)

Check the periodic table: The element with nuclear charge = +13 is aluminum. Thus, the product is 28

13
Al .

Exercise 1
The nuclide 125
53
I combines with an electron and produces a new nucleus and no other massive particles. What is the equation for
this reaction?

Answer
125 0 125
53
I+ e → 52
Te
−1

The two general kinds of nuclear reactions are nuclear decay reactions and nuclear transmutation reactions. In a nuclear decay
reaction, also called radioactive decay, an unstable nucleus emits radiation and is transformed into the nucleus of one or more other
elements. The resulting daughter nuclei have a lower mass and are lower in energy (more stable) than the parent nucleus that
decayed. In contrast, in a nuclear transmutation reaction, a nucleus reacts with a subatomic particle or another nucleus to form a
product nucleus that is more massive than the starting material. As we shall see, nuclear decay reactions occur spontaneously under
all conditions, but nuclear transmutation reactions occur only under very special conditions, such as the collision of a beam of
highly energetic particles with a target nucleus or in the interior of stars. We begin this section by considering the different classes
of radioactive nuclei, along with their characteristic nuclear decay reactions and the radiation they emit.

Nuclear decay reactions occur spontaneously under all conditions, whereas nuclear
transmutation reactions are induced.

Nuclear Decay Reactions

Just as we use the number and type of atoms present to balance a chemical equation, we can use the number and type of nucleons
present to write a balanced nuclear equation for a nuclear decay reaction. This procedure also allows us to predict the identity of
either the parent or the daughter nucleus if the identity of only one is known. Regardless of the mode of decay, the total number of
nucleons is conserved in all nuclear reactions.
To describe nuclear decay reactions, chemists have extended the X notation for nuclides to include radioactive emissions. Table 1
A
Z

lists the name and symbol for each type of emitted radiation. The most notable addition is the positron, a particle that has the same
mass as an electron but a positive charge rather than a negative charge.
Table 1 : Nuclear Decay Emissions and Their Symbols
Identity Symbol Charge Mass (amu)

helium nucleus 4
2
α +2 4.001506

electron 0
−1
β or β −
−1 0.000549

2 [Link]
 Identity Symbol Charge Mass (amu)

photon 0
0
γ — —

neutron 1
0
n 0 1.008665

proton 1
1
p +1 1.007276

positron 0
+1
β or β +
+1 0.000549

Like the notation used to indicate isotopes, the upper left superscript in the symbol for a particle gives the mass number, which is
the total number of protons and neutrons. For a proton or a neutron, A = 1. Because neither an electron nor a positron contains
protons or neutrons, its mass number is 0. The numbers should not be taken literally, however, as meaning that these particles have
zero mass; ejection of a beta particle (an electron) simply has a negligible effect on the mass of a nucleus.
Similarly, the lower left subscript gives the charge of the particle. Because protons carry a positive charge, Z = +1 for a proton. In
contrast, a neutron contains no protons and is electrically neutral, so Z = 0. In the case of an electron, Z = −1, and for a positron, Z =
+1. Because γ rays are high-energy photons, both A and Z are 0. In some cases, two different symbols are used for particles that are
identical but produced in different ways. For example, the symbol e, which is usually simplified to e−, represents a free electron
0
−1

or an electron associated with an atom, whereas the symbol β, which is often simplified to β−, denotes an electron that originates
0
−1

from within the nucleus, which is a β particle. Similarly, He refers to the nucleus of a helium atom, and α denotes an identical
4
2
2+ 4
2

particle that has been ejected from a heavier nucleus.

There are six fundamentally different kinds of nuclear decay reactions, and each releases a different kind of particle or energy. The
essential features of each reaction are shown in Figure 1. The most common are alpha and beta decay and gamma emission, but the
others are essential to an understanding of nuclear decay reactions.

Figure 1 : Common Modes of Nuclear Decay

3 [Link]
Alpha αDecay
Many nuclei with mass numbers greater than 200 undergo alpha (α) decay, which results in the emission of a helium-4 nucleus as
an alpha (α) particle, α . The general reaction is as follows:
4
2

A A−4 ′ 4
X → X + α (7)
Z Z−2 2
parent daughter alpha

particle

The daughter nuclide contains two fewer protons and two fewer neutrons than the parent. Thus α-particle emission produces a
daughter nucleus with a mass number A − 4 and a nuclear charge Z − 2 compared to the parent nucleus. Radium-226, for example,
undergoes alpha decay to form radon-222:
226 222 4
Ra → Rn + α (8)
88 86 2

Because nucleons are conserved in this and all other nuclear reactions, the sum of the mass numbers of the products, 222 + 4 = 226,
equals the mass number of the parent. Similarly, the sum of the atomic numbers of the products, 86 + 2 = 88, equals the atomic
number of the parent. Thus the nuclear equation is balanced.
Note
Just as the total number of atoms is conserved in a chemical reaction, the total number of nucleons is conserved in a nuclear
reaction.

Beta β −
Decay
Nuclei that contain too many neutrons often undergo beta (β) decay, in which a neutron is converted to a proton and a high-energy
electron that is ejected from the nucleus as a β particle:
1 1 0
n → p + β (9)
0 1 −1
unstable proton beta particle

neutron in retained emitted by

nucleus by nucleus
nucleus

The general reaction for beta decay is therefore

A A ′ 0
X → X + β (10)
Z Z+1 −1
parent daughter beta particle

Although beta decay does not change the mass number of the nucleus, it does result in an increase of +1 in the atomic number
because of the addition of a proton in the daughter nucleus. Thus beta decay decreases the neutron-to-proton ratio, moving the
nucleus toward the band of stable nuclei. For example, carbon-14 undergoes beta decay to form nitrogen-14:
14 14 0
C → N+ β (11)
6 7 −1

Once again, the number of nucleons is conserved, and the charges are balanced. The parent and the daughter nuclei have the same
mass number, 14, and the sum of the atomic numbers of the products is 6, which is the same as the atomic number of the carbon-14
parent.

Positron β +
Emission
Because a positron has the same mass as an electron but opposite charge, positron emission is the opposite of beta decay. Thus
positron emission is characteristic of neutron-poor nuclei, which decay by transforming a proton to a neutron and emitting a high-
energy positron:
1 + 1 0 +
p → n+ β (12)
1 0 +1

The general reaction for positron emission is therefore

A A ′ 0 +
X → X + β (13)
Z Z−1 +1
parent daughter positron

Like beta decay, positron emission does not change the mass number of the nucleus. In this case, however, the atomic number of
the daughter nucleus is lower by 1 than that of the parent. Thus the neutron-to-proton ratio has increased, again moving the nucleus
closer to the band of stable nuclei. For example, carbon-11 undergoes positron emission to form boron-11:

4 [Link]
 11 11 0 +
C → B+ β (14)
6 5 +1

Nucleons are conserved, and the charges balance. The mass number, 11, does not change, and the sum of the atomic numbers of the
products is 6, the same as the atomic number of the parent carbon-11 nuclide.

Electron Capture
A neutron-poor nucleus can decay by either positron emission or electron capture (EC), in which an electron in an inner shell
reacts with a proton to produce a neutron:
1 0 1
p+ e → n (15)
1 −1 0

When a second electron moves from an outer shell to take the place of the lower-energy electron that was absorbed by the nucleus,
an x-ray is emitted. The overall reaction for electron capture is thus
A 0 A ′
X + e → X + x-ray (16)
Z −1 Z−1
parent electron daughter

Electron capture does not change the mass number of the nucleus because both the proton that is lost and the neutron that is formed
have a mass number of 1. As with positron emission, however, the atomic number of the daughter nucleus is lower by 1 than that of
the parent. Once again, the neutron-to-proton ratio has increased, moving the nucleus toward the band of stable nuclei. For
example, iron-55 decays by electron capture to form manganese-55, which is often written as follows:
EC
55 55
Fe → Mn + x-ray (17)
26 25

The atomic numbers of the parent and daughter nuclides differ in Equation 20.2.11, although the mass numbers are the same. To
write a balanced nuclear equation for this reaction, we must explicitly include the captured electron in the equation:
55 0 55
Fe + e → Mn + x-ray (18)
26 −1 25

Both positron emission and electron capture are usually observed for nuclides with low neutron-to-proton ratios, but the decay rates
for the two processes can be very different.

Gamma γ Emission
Many nuclear decay reactions produce daughter nuclei that are in a nuclear excited state, which is similar to an atom in which an
electron has been excited to a higher-energy orbital to give an electronic excited state. Just as an electron in an electronic excited
state emits energy in the form of a photon when it returns to the ground state, a nucleus in an excited state releases energy in the
form of a photon when it returns to the ground state. These high-energy photons are γ rays. Gamma (γ) emission can occur
virtually instantaneously, as it does in the alpha decay of uranium-238 to thorium-234, where the asterisk denotes an excited state:
relaxation
238 234 4 234 0
U → Th* + α −−−−−−→ Th + γ (19)
92 90 2 90 0
excited

nuclear

state

If we disregard the decay event that created the excited nucleus, then
234 234 0
Th* → Th + γ (20)
88 88 0

or more generally,
A A 0
X* → X+ γ (21)
Z Z 0

Gamma emission can also occur after a significant delay. For example, technetium-99m has a half-life of about 6 hours before
emitting a γ ray to form technetium-99 (the m is for metastable). Because γ rays are energy, their emission does not affect either the
mass number or the atomic number of the daughter nuclide. Gamma-ray emission is therefore the only kind of radiation that does
not necessarily involve the conversion of one element to another, although it is almost always observed in conjunction with some
other nuclear decay reaction.

5 [Link]
Spontaneous Fission
Only very massive nuclei with high neutron-to-proton ratios can undergo spontaneous fission, in which the nucleus breaks into
two pieces that have different atomic numbers and atomic masses. This process is most important for the transactinide elements,
with Z ≥ 104. Spontaneous fission is invariably accompanied by the release of large amounts of energy, and it is usually
accompanied by the emission of several neutrons as well. An example is the spontaneous fission of Cf , which gives a
254
98

distribution of fission products; one possible set of products is shown in the following equation:
254 118 132 1
Cf → Pd + Te + 40 n (22)
98 46 52

Once again, the number of nucleons is conserved. Thus the sum of the mass numbers of the products (118 + 132 + 4 = 254) equals
the mass number of the reactant. Similarly, the sum of the atomic numbers of the products [46 + 52 + (4 × 0) = 98] is the same as
the atomic number of the parent nuclide.

Example 2
Write a balanced nuclear equation to describe each reaction.
a. the beta decay of S
35
16

b. the decay of Hg by electron capture

201
80

c. the decay of P by positron emission

30
15

Given: radioactive nuclide and mode of decay

Asked for: balanced nuclear equation
Strategy:
A Identify the reactants and the products from the information given.
B Use the values of A and Z to identify any missing components needed to balance the equation.
Solution:
a.
A We know the identities of the reactant and one of the products (a β particle). We can therefore begin by writing an
equation that shows the reactant and one of the products and indicates the unknown product as X: A
Z

35 A 0
S→ X+ β (23)
16 Z −1

B Because both protons and neutrons must be conserved in a nuclear reaction, the unknown product must have a mass
number of A = 35 − 0 = 35 and an atomic number of Z = 16 − (−1) = 17. The element with Z = 17 is chlorine, so the
balanced nuclear equation is as follows:
35 35 0
S→ Cl + β (24)
16 17 −1

b.
A We know the identities of both reactants: 201
80
Hg and an inner electron, 0
−1
. The reaction is as follows:
e

201 0 A
Hg + e → X
80 −1 Z

B Both protons and neutrons are conserved, so the mass number of the product must be A = 201 + 0 = 201, and the atomic
number of the product must be Z = 80 + (−1) = 79, which corresponds to the element gold. The balanced nuclear equation
is thus
201 0 201
Hg + e → Au
80 −1 79

c.
A As in part (a), we are given the identities of the reactant and one of the products—in this case, a positron. The
unbalanced nuclear equation is therefore
30 A 0
P → X+ β
15 Z +1

B The mass number of the second product is A = 30 − 0 = 30, and its atomic number is Z = 15 − 1 = 14, which
corresponds to silicon. The balanced nuclear equation for the reaction is as follows:

6 [Link]
 30 30 0
P → Si + β
15 14 +1

Exercise 2
Write a balanced nuclear equation to describe each reaction.
a. C by positron emission
11
6

b. the beta decay of molybdenum-99

c. the emission of an α particle followed by gamma emission from 185
74
W

Answer a
11 11 0
C → B+ β
6 5 +1

Answer d
99 99m 0
Mo → Tc + β
42 43 −1

Answer c
185 181 4 0
W → Hf + α+ γ
74 72 2 0

Radioactive Decay Series

The nuclei of all elements with atomic numbers greater than 83 are unstable. Thus all isotopes of all elements beyond bismuth in
the periodic table are radioactive. Because alpha decay decreases Z by only 2, and positron emission or electron capture decreases Z
by only 1, it is impossible for any nuclide with Z > 85 to decay to a stable daughter nuclide in a single step, except via nuclear
fission. Consequently, radioactive isotopes with Z > 85 usually decay to a daughter nucleus that is radiaoctive, which in turn decays
to a second radioactive daughter nucleus, and so forth, until a stable nucleus finally results. This series of sequential alpha- and
beta-decay reactions is called a radioactive decay series. The most common is the uranium-238 decay series, which produces lead-
206 in a series of 14 sequential alpha- and beta-decay reactions (Figure 2). Although a radioactive decay series can be written for
almost any isotope with Z > 85, only two others occur naturally: the decay of uranium-235 to lead-207 (in 11 steps) and thorium-
232 to lead-208 (in 10 steps). A fourth series, the decay of neptunium-237 to bismuth-209 in 11 steps, is known to have occurred
on the primitive Earth. With a half-life of “only” 2.14 million years, all the neptunium-237 present when Earth was formed decayed
long ago, and today all the neptunium on Earth is synthetic.

Figure 2 A Radioactive Decay Series. Three naturally occurring radioactive decay series are known to occur currently: the
uranium-238 decay series, the decay of uranium-235 to lead-207, and the decay of thorium-232 to lead-208.
Due to these radioactive decay series, small amounts of very unstable isotopes are found in ores that contain uranium or thorium.
These rare, unstable isotopes should have decayed long ago to stable nuclei with a lower atomic number, and they would no longer
be found on Earth. Because they are generated continuously by the decay of uranium or thorium, however, their amounts have

7 [Link]
reached a steady state, in which their rate of formation is equal to their rate of decay. In some cases, the abundance of the daughter
isotopes can be used to date a material or identify its origin.

Induced Nuclear Reactions

The discovery of radioactivity in the late 19th century showed that some nuclei spontaneously transform into nuclei with a different
number of protons, thereby producing a different element. When scientists realized that these naturally occurring radioactive
isotopes decayed by emitting subatomic particles, they realized that—in principle—it should be possible to carry out the reverse
reaction, converting a stable nucleus to another more massive nucleus by bombarding it with subatomic particles in a nuclear
transmutation reaction.
The first successful nuclear transmutation reaction was carried out in 1919 by Ernest Rutherford, who showed that α particles
emitted by radium could react with nitrogen nuclei to form oxygen nuclei. As shown in the following equation, a proton is emitted
in the process:
4 14 17 1
α+ N → O+ p
2 7 8 1

Rutherford’s nuclear transmutation experiments led to the discovery of the neutron. He found that bombarding the nucleus of a
light target element with an α particle usually converted the target nucleus to a product that had an atomic number higher by 1 and a
mass number higher by 3 than the target nucleus. Such behavior is consistent with the emission of a proton after reaction with the α
particle. Very light targets such as Li, Be, and B reacted differently, however, emitting a new kind of highly penetrating radiation
rather than a proton. Because neither a magnetic field nor an electrical field could deflect these high-energy particles, Rutherford
concluded that they were electrically neutral. Other observations suggested that the mass of the neutral particle was similar to the
mass of the proton. In 1932, James Chadwick (Nobel Prize in Physics, 1935), who was a student of Rutherford’s at the time, named
these neutral particles neutrons and proposed that they were fundamental building blocks of the atom. The reaction that Chadwick
initially used to explain the production of neutrons was as follows:
4 9 12 1
α+ Be → C+ n (25)
2 4 6 0

Because α particles and atomic nuclei are both positively charged, electrostatic forces cause them to repel each other. Only α
particles with very high kinetic energy can overcome this repulsion and collide with a nucleus (Figure 3). Neutrons have no
electrical charge, however, so they are not repelled by the nucleus. Hence bombardment with neutrons is a much easier way to
prepare new isotopes of the lighter elements. In fact, carbon-14 is formed naturally in the atmosphere by bombarding nitrogen-14
with neutrons generated by cosmic rays:
1 14 14 1
n+ N → C+ p (26)
0 7 6 1

Figure 3 A Nuclear Transmutation Reaction. Bombarding a target of one element with high-energy nuclei or subatomic particles
can create new elements. Electrostatic repulsions normally prevent a positively charged particle from colliding and reacting with a
positively charged nucleus. If the positively charged particle is moving at a very high speed, however, its kinetic energy may be
great enough to overcome the electrostatic repulsions, and it may collide with the target nucleus. Such collisions can result in a
nuclear transmutation reaction.

Example 4
In 1933, Frédéric Joliot and Iréne Joliot-Curie (daughter of Marie and Pierre Curie) prepared the first artificial radioactive
isotope by bombarding aluminum-27 with α particles. For each 27Al that reacted, one neutron was released. Identify the product
nuclide and write a balanced nuclear equation for this transmutation reaction.

8 [Link]
 Given: reactants in a nuclear transmutation reaction
Asked for: product nuclide and balanced nuclear equation
Strategy:
A Based on the reactants and one product, identify the other product of the reaction. Use conservation of mass and charge to
determine the values of Z and A of the product nuclide and thus its identity.
B Write the balanced nuclear equation for the reaction.
Solution:
A Bombarding an element with α particles usually produces an element with an atomic number that is 2 greater than the atomic
number of the target nucleus. Thus we expect that aluminum (Z = 13) will be converted to phosphorus (Z = 15). With one
neutron released, conservation of mass requires that the mass number of the other product be 3 greater than the mass number of
the target. In this case, the mass number of the target is 27, so the mass number of the product will be 30. The second product is
therefore phosphorus-30, P. 30
15

B The balanced nuclear equation for the reaction is as follows:

27 4 30 1
Al + α → P+ n (27)
13 2 15 0

Exercise 4
Because all isotopes of technetium are radioactive and have short half-lives, it does not exist in nature. Technetium can,
however, be prepared by nuclear transmutation reactions. For example, bombarding a molybdenum-96 target with deuterium
nuclei ( H) produces technetium-97. Identify the other product of the reaction and write a balanced nuclear equation for this
2
1

transmutation reaction.

Answer
neutron, 1
0
n ; 96
42
Mo +
2
1
H →
97
43
Tc +
1
0
n :

We noted earlier in this section that very heavy nuclides, corresponding to Z ≥ 104, tend to decay by spontaneous fission. Nuclides
with slightly lower values of Z, such as the isotopes of uranium (Z = 92) and plutonium (Z = 94), do not undergo spontaneous
fission at any significant rate. Some isotopes of these elements, however, such as U and Pu undergo induced nuclear fission
235
92
239
94

when they are bombarded with relatively low-energy neutrons, as shown in the following equation for uranium-235 and in Figure
4:

235 1 236 141 92 1

U+ n→ U → Ba + Kr + 30 n (28)
92 0 92 56 36

Figure 4 Neutron-Induced Nuclear Fission. Collision of a relatively slow-moving neutron with a fissile nucleus can split it into two
smaller nuclei with the same or different masses. Neutrons are also released in the process, along with a great deal of energy.
Any isotope that can undergo a nuclear fission reaction when bombarded with neutrons is called a fissile isotope.
During nuclear fission, the nucleus usually divides asymmetrically rather than into two equal parts, as shown in Figure 4.
Moreover, every fission event of a given nuclide does not give the same products; more than 50 different fission modes have been
identified for uranium-235, for example. Consequently, nuclear fission of a fissile nuclide can never be described by a single
equation. Instead, as shown in Figure 5, a distribution of many pairs of fission products with different yields is obtained, but the
mass ratio of each pair of fission products produced by a single fission event is always roughly 3:2.

9 [Link]
 Figure 5 Mass Distribution of Nuclear Fission Products of 235U. Nuclear fission usually produces a range of products with
different masses and yields, although the mass ratio of each pair of fission products from a fission event is approximately 3:2. As
shown in this plot, more than 50 different fission products are known for235U. Data source: T. R. England and B. F. Rider, Los
Alamos National Laboratory, LA-UR-94-3106, ENDF-349 (1993).

Synthesis of Transuranium Elements

Uranium (Z = 92) is the heaviest naturally occurring element. Consequently, all the elements with Z > 92, the transuranium
elements, are artificial and have been prepared by bombarding suitable target nuclei with smaller particles. The first of the
transuranium elements to be prepared was neptunium (Z = 93), which was synthesized in 1940 by bombarding a 238U target with
neutrons. As shown in Equation 20.21, this reaction occurs in two steps. Initially, a neutron combines with a 238U nucleus to form
239
U, which is unstable and undergoes beta decay to produce 239Np:
238 1 239 239 0
U+ n→ U → Np + β
92 0 92 93 −1

Subsequent beta decay of 239Np produces the second transuranium element, plutonium (Z = 94):
239 239 0
Np → Pu + β
93 94 −1

Bombarding the target with more massive nuclei creates elements that have atomic numbers significantly greater than that of the
target nucleus (Table 2). Such techniques have resulted in the creation of the superheavy elements 114 and 116, both of which lie in
or near the “island of stability."
Table 2 : Some Reactions Used to Synthesize Transuranium Elements
239 4 242 1
Pu + α → Cm + n
94 2 96 0

239 4 241 1 1
Pu + α → Am + p+ n
94 2 95 1 0

242 4 243 1 1
Cm + α → Bk + p+2 n
96 2 97 1 0

253 4 256 1
Es + α → Md + n
99 2 101 0

238 12 246 1
U + C → Cf + 4 n
92 6 98 0

252 10 256 1
Cf + B → Lr + 6 n
98 5 103 0

A device called a particle accelerator is used to accelerate positively charged particles to the speeds needed to overcome the
electrostatic repulsions between them and the target nuclei by using electrical and magnetic fields. Operationally, the simplest
particle accelerator is the linear accelerator (Figure 6), in which a beam of particles is injected at one end of a long evacuated tube.
Rapid alternation of the polarity of the electrodes along the tube causes the particles to be alternately accelerated toward a region of
opposite charge and repelled by a region with the same charge, resulting in a tremendous acceleration as the particle travels down
the tube. A modern linear accelerator such as the Stanford Linear Accelerator (SLAC) at Stanford University is about 2 miles long.

10 [Link]
 Figure 6 : A Linear Particle Accelerator. (a) An aerial view of the SLAC, the longest linear particle accelerator in the world; the
overall length of the tunnel is 2 miles. (b) Rapidly reversing the polarity of the electrodes in the tube causes the charged particles to
be alternately attracted as they enter one section of the tube and repelled as they leave that section. As a result, the particles are
continuously accelerated along the length of the tube.
To achieve the same outcome in less space, a particle accelerator called a cyclotron forces the charged particles to travel in a
circular path rather than a linear one. The particles are injected into the center of a ring and accelerated by rapidly alternating the
polarity of two large D-shaped electrodes above and below the ring, which accelerates the particles outward along a spiral path
toward the target.
The length of a linear accelerator and the size of the D-shaped electrodes in a cyclotron severely limit the kinetic energy that
particles can attain in these devices. These limitations can be overcome by using a synchrotron, a hybrid of the two designs. A
synchrotron contains an evacuated tube similar to that of a linear accelerator, but the tube is circular and can be more than a mile in
diameter. Charged particles are accelerated around the circle by a series of magnets whose polarities rapidly alternate.

Summary and Key Takeaway

Nuclear decay reactions occur spontaneously under all conditions and produce more stable daughter nuclei, whereas nuclear
transmutation reactions are induced and form a product nucleus that is more massive than the starting material.
In nuclear decay reactions (or radioactive decay), the parent nucleus is converted to a more stable daughter nucleus. Nuclei with
too many neutrons decay by converting a neutron to a proton, whereas nuclei with too few neutrons decay by converting a proton
to a neutron. Very heavy nuclei (with A ≥ 200 and Z > 83) are unstable and tend to decay by emitting an α particle. When an
unstable nuclide undergoes radioactive decay, the total number of nucleons is conserved, as is the total positive charge. Six
different kinds of nuclear decay reactions are known. Alpha decay results in the emission of an α particle, α , and produces a
4
2

daughter nucleus with a mass number that is lower by 4 and an atomic number that is lower by 2 than the parent nucleus. Beta
decay converts a neutron to a proton and emits a high-energy electron, producing a daughter nucleus with the same mass number as
the parent and an atomic number that is higher by 1. Positron emission is the opposite of beta decay and converts a proton to a
neutron plus a positron. Positron emission does not change the mass number of the nucleus, but the atomic number of the daughter
nucleus is lower by 1 than the parent. In electron capture (EC), an electron in an inner shell reacts with a proton to produce a
neutron, with emission of an x-ray. The mass number does not change, but the atomic number of the daughter is lower by 1 than the
parent. In gamma emission, a daughter nucleus in a nuclear excited state undergoes a transition to a lower-energy state by emitting
a γ ray. Very heavy nuclei with high neutron-to-proton ratios can undergo spontaneous fission, in which the nucleus breaks into
two pieces that can have different atomic numbers and atomic masses with the release of neutrons. Many very heavy nuclei decay
via a radioactive decay series—a succession of some combination of alpha- and beta-decay reactions. In nuclear transmutation
reactions, a target nucleus is bombarded with energetic subatomic particles to give a product nucleus that is more massive than the
original. All transuranium elements—elements with Z > 92—are artificial and must be prepared by nuclear transmutation
reactions. These reactions are carried out in particle accelerators such as linear accelerators, cyclotrons, and synchrotrons.

Key Equations
alpha decay
A A−4 ′ 4
X → X + α
Z Z−2 2

beta decay
A A ′ 0
X → X + β
Z Z+1 −1

11 [Link]
positron emission
A A ′ 0
X → X + β
Z Z−1 +1

electron capture
A 0 A ′
X+ e → X + x-ray
Z −1 Z−1

gamma emission
A A 0
X* → X+ γ
Z Z 0

modified by Tom Neils (Grand Rapids Community College)

2.4 Nuclear Reactions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

12 [Link]
2.5 The Belt of Stability - Predicting the Type of Radioactivity
Skills to Develop
To understand the factors that affect nuclear stability.

Although most of the known elements have at least one isotope whose atomic nucleus is stable indefinitely, all elements have
isotopes that are unstable and disintegrate, or decay, at measurable rates by emitting radiation. Some elements have no stable
isotopes and eventually decay to other elements. In contrast to the chemical reactions that are the main focus of all the other
chapters, and are due to changes in the arrangements of the valence electrons of atoms, the process of nuclear decay results in
changes inside an atomic nucleus. We begin our discussion of nuclear reactions by reviewing the conventions used to describe the
components of the nucleus.

The Atomic Nucleus

Each element can be represented by the notation X, where A, the mass number, is the sum of the number of protons and the
A
Z

number of neutrons, and Z, the atomic number, is the number of protons. The protons and neutrons that make up the nucleus of an
atom are called nucleons, and an atom with a particular number of protons and neutrons is called a nuclide. Nuclides with the
same number of protons but different numbers of neutrons are called isotopes. Isotopes can also be represented by an alternative
notation that uses the name of the element followed by the mass number, such as carbon-12. The stable isotopes of oxygen, for
example, can be represented in any of the following ways:
A 16 17 18
X 8O 8O 8O
Z

A 16 17 18
X O O O

element-A: oxygen-16 oxygen-17 oxygen-18

Because the number of neutrons is equal to A − Z, we see that the first isotope of oxygen has 8 neutrons, the second isotope 9
neutrons, and the third isotope 10 neutrons. Isotopes of all naturally occurring elements on Earth are present in nearly fixed
proportions, with each proportion constituting an isotope’s natural abundance. For example, in a typical terrestrial sample of
oxygen, 99.76% of the O atoms is oxygen-16, 0.20% is oxygen-18, and 0.04% is oxygen-17. Any nucleus that is unstable and
decays spontaneously is said to be radioactive, emitting subatomic particles and electromagnetic radiation. The emissions are
collectively called radioactivity and can be measured. Isotopes that emit radiation are called radioisotopes.

Nuclear Stability
The nucleus of an atom occupies a tiny fraction of the volume of an atom and contains the number of protons and neutrons that is
characteristic of a given isotope. Electrostatic repulsions would normally cause the positively charged protons to repel each other,
but the nucleus does not fly apart because of the strong nuclear force, an extremely powerful but very short-range attractive force
between nucleons (Figure 1). All stable nuclei except the hydrogen-1 nucleus (1H) contain at least one neutron to overcome the
electrostatic repulsion between protons. As the number of protons in the nucleus increases, the number of neutrons needed for a
stable nucleus increases even more rapidly. Too many protons (or too few neutrons) in the nucleus result in an imbalance between
forces, which leads to nuclear instability.

1 [Link]
 Figure 1 : Competing Interactions within the Atomic Nucleus. Electrostatic repulsions between positively charged protons would
normally cause the nuclei of atoms (except H) to fly apart. In stable atomic nuclei, these repulsions are overcome by the strong
nuclear force, a short-range but powerful attractive interaction between nucleons. If the attractive interactions due to the strong
nuclear force are weaker than the electrostatic repulsions between protons, the nucleus is unstable, and it will eventually decay.
The relationship between the number of protons and the number of neutrons in stable nuclei, arbitrarily defined as having a half-life
longer than 10 times the age of Earth, is shown graphically in Figure 2. The stable isotopes form a “peninsula of stability” in a “sea
of instability.” Only two stable isotopes, 1H and 3He, have a neutron-to-proton ratio less than 1. Several stable isotopes of light
atoms have a neutron-to-proton ratio equal to 1 (e.g., He, B, and Ca). All other stable nuclei have a higher neutron-to-proton
4
2
10
5
40
20

ratio, which increases steadily to about 1.5 for the heaviest nuclei. Regardless of the number of neutrons, however, all elements
with Z > 83 are unstable and radioactive.

Figure 2 : The Relationship between Nuclear Stability and the Neutron-to-Proton Ratio. In this plot of the number of neutrons
versus the number of protons, each black point corresponds to a stable nucleus. In this classification, a stable nucleus is arbitrarily
defined as one with a half-life longer than 46 billion years (10 times the age of Earth). As the number of protons (the atomic
number) increases, the number of neutrons required for a stable nucleus increases even more rapidly. Isotopes shown in red,
yellow, green, and blue are progressively less stable and more radioactive; the farther an isotope is from the diagonal band of
stable isotopes, the shorter its half-life. The purple dots indicate superheavy nuclei that are predicted to be relatively stable,
meaning that they are expected to be radioactive but to have relatively long half-lives. In most cases, these elements have not yet
been observed or synthesized. Data source: National Nuclear Data Center, Brookhaven National Laboratory, Evaluated Nuclear
Structure Data File (ENSDF), Chart of Nuclides, [Link]
As shown in Figure 3, more than half of the stable nuclei (166 out of 279) have even numbers of both neutrons and protons; only 6
of the 279 stable nuclei do not have odd numbers of both. Moreover, certain numbers of neutrons or protons result in especially
stable nuclei; these are the so-called magic numbers 2, 8, 20, 50, 82, and 126. For example, tin (Z = 50) has 10 stable isotopes, but
the elements on either side of tin in the periodic table, indium (Z = 49) and antimony (Z = 51), have only 2 stable isotopes each.
Nuclei with magic numbers of both protons and neutrons are said to be “doubly magic” and are even more stable. Examples of

2 [Link]
elements with doubly magic nuclei are He, with 2 protons and 2 neutrons, and
4
2
208
82
, with 82 protons and 126 neutrons, which is
Pb

the heaviest known stable isotope of any element.

Figure 3 : The Relationship between the Number of Protons and the Number of Neutrons and Nuclear Stability.

Most stable nuclei contain even numbers of both neutrons and protons
The pattern of stability suggested by the magic numbers of nucleons is reminiscent of the stability associated with the closed-shell
electron configurations of the noble gases in group 18 and has led to the hypothesis that the nucleus contains shells of nucleons that
are in some ways analogous to the shells occupied by electrons in an atom. As shown in Figure 2, the “peninsula” of stable isotopes
is surrounded by a “reef” of radioactive isotopes, which are stable enough to exist for varying lengths of time before they
eventually decay to produce other nuclei.
Origin of the Magic Numbers
Multiple models have been formulated to explain the origin of the magic numbers and two popular ones are the Nuclear Shell
Model and the Liquid Drop Model. Unfortuneatly, both require advanced quantum mechanics to fully understand and are
beyond the scope of this text.

Superheavy Elements
In addition to the “peninsula of stability” there is a small “island of stability” that is predicted to exist in the upper right corner. This
island corresponds to the superheavy elements, with atomic numbers near the magic number 126. Because the next magic number
for neutrons should be 184, it was suggested that an element with 114 protons and 184 neutrons might be stable enough to exist in
nature. Although these claims were met with skepticism for many years, since 1999 a few atoms of isotopes with Z = 114 and Z =
116 have been prepared and found to be surprisingly stable. One isotope of element 114 lasts 2.7 seconds before decaying,
described as an “eternity” by nuclear chemists. Moreover, there is recent evidence for the existence of a nucleus with A = 292 that
was found in 232Th. With an estimated half-life greater than 108 years, the isotope is particularly stable. Its measured mass is
consistent with predictions for the mass of an isotope with Z = 122. Thus a number of relatively long-lived nuclei may well be
accessible among the superheavy elements.

Summary
Subatomic particles of the nucleus (protons and neutrons) are called nucleons. A nuclide is an atom with a particular number of
protons and neutrons. An unstable nucleus that decays spontaneously is radioactive, and its emissions are collectively called
radioactivity. Isotopes that emit radiation are called radioisotopes. Each nucleon is attracted to other nucleons by the strong
nuclear force. Stable nuclei generally have even numbers of both protons and neutrons and a neutron-to-proton ratio of at least 1.
Nuclei that contain magic numbers of protons and neutrons are often especially stable. Superheavy elements, with atomic
numbers near 126, may even be stable enough to exist in nature.
modified by Tom Neils (Grand Rapids Community College)

2.5 The Belt of Stability - Predicting the Type of Radioactivity is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or
curated by LibreTexts.

3 [Link]
2.6 Half-lives and the Rate of Radioactive Decay
Skills to Develop
To know how to use half-lives to describe the rates of first-order reactions

Radioactive Decay Rates

Radioactivity, or radioactive decay, is the emission of a particle or a photon that results from the spontaneous decomposition of the
unstable nucleus of an atom. The rate of radioactive decay is an intrinsic property of each radioactive isotope that is independent of
the chemical and physical form of the radioactive isotope. The rate is also independent of temperature. Because there are so many
unstable nuclei that decay, we need a method to describe and compare the rates at which these nuclei decay. One approach to
describing reaction rates is based on the time required for the number of unstable nuclei to decrease to one-half the initial value.
This period of time is called the half-life of the process, written as t1/2. Thus the half-life of a nuclear decay process is the time
required for the number of unstable nuclei to decrease from [A]0 to 1/2[A]0.

Number of Half-Lives Percentage of Reactant Remaining

100% 1
1 = 50% (100%) = 50%
2 2

50% 1 1
2 = 25% ( ) (100%) = 25%
2 2 2

25% 1 1 1
3 = 12.5% ( )( ) (100%) = 12.5%
2 2 2 2

n n
100% 1 1
n n
( ) (100%) = ( ) %
2 2 2

As you can see from this table, the amount of reactant left after n half-lives of a first-order reaction is (1/2)n times the initial
concentration.

For a first-order reaction, the concentration of the reactant decreases by a constant with
each half-life and is independent of [A].
For a given number of atoms, isotopes with shorter half-lives decay more rapidly, undergoing a greater number of radioactive
decays per unit time than do isotopes with longer half-lives. The half-lives of several isotopes are listed in Table 14.6, along with
some of their applications.
Table 2 : Half-Lives and Applications of Some Radioactive Isotopes
Radioactive Isotope Half-Life Typical Uses

hydrogen-3 (tritium) 12.32 yr biochemical tracer

positron emission tomography (biomedical

carbon-11 20.33 min
imaging)

carbon-14 5.70 × 103 yr dating of artifacts

sodium-24 14.951 h cardiovascular system tracer

phosphorus-32 14.26 days biochemical tracer

potassium-40 1.248 × 109 yr dating of rocks

iron-59 44.495 days red blood cell lifetime tracer

cobalt-60 5.2712 yr radiation therapy for cancer

technetium-99m* 6.006 h biomedical imaging

iodine-131 8.0207 days thyroid studies tracer

*The m denotes metastable, where an excited state nucleus decays to the ground state of the same isotope.

1 [Link]
 Radioactive Isotope Half-Life Typical Uses

radium-226 1.600 × 103 yr radiation therapy for cancer

uranium-238 4.468 × 109 yr dating of rocks and Earth’s crust

americium-241 432.2 yr smoke detectors

*The m denotes metastable, where an excited state nucleus decays to the ground state of the same isotope.

Note
Radioactive decay is a first-order process.

Example 1
If you have a 120 gram sample of a radioactive element, how many grams of that element will be left after 3 half-lives have
passed?
Solution
Given: mass of radioactive sample of an element, number of half-lives
Asked to Solve For: mass of radioactive element after so many half-lives
Solve:
All radioactive samples lose half of their mass after each half-life. Thus, one solution is to calculate the mass after each half-life.
(This method only works if you are asked to solve for a whole number of half-lives). Let the passing of time equal to one half-
life be represented by and arrow, →. Then the solution is:
120 g → 60 g → 30 g → 15 g
If you want to solve for any number of half-lives, including fractional half-lives, then you use the equation: amount remaining =
n
1
( ) (amount at start) , where n= number of half-lives. Then the solution is:
2

3
1
amount remaining = ( ) (120g) = 15g
2

Exercise 1
If you have a 300. gram sample of a radioactive element, how many grams of that element will be left after 4.30 half-lives have
passed?

Answer
4.30
1
amount left = ( ) (300.g) = 15.2g
2

Exercise 2
A certain radioactive nuclide has a half-life of 5.25 days. If you start with 100. grams of this nuclide, how many grams of the
nuclide will be left after 20.0 days?

Answer
1 half − lif e
20.0 days × = 3.81 half − lives
5.25 days

3.81
1
amount left = ( ) (100.g) = 7.13g
2

2 [Link]
Radioisotope Dating Techniques
In our earlier discussion, we used the half-life of a first-order reaction to calculate how long the reaction had been occurring.
Because nuclear decay reactions follow first-order kinetics and have a rate constant that is independent of temperature and the
chemical or physical environment, we can perform similar calculations using the half-lives of isotopes to estimate the ages of
geological and archaeological artifacts. The techniques that have been developed for this application are known as radioisotope
dating techniques.
The most common method for measuring the age of ancient objects is carbon-14 dating. The carbon-14 isotope, created
continuously in the upper regions of Earth’s atmosphere, reacts with atmospheric oxygen or ozone to form 14CO2. As a result, the
CO2 that plants use as a carbon source for synthesizing organic compounds always includes a certain proportion of 14CO2
molecules as well as nonradioactive 12CO2 and 13CO2. Any animal that eats a plant ingests a mixture of organic compounds that
contains approximately the same proportions of carbon isotopes as those in the atmosphere. When the animal or plant dies, the
carbon-14 nuclei in its tissues decay to nitrogen-14 nuclei by a radioactive process known as beta decay, which releases low-energy
electrons (β particles) that can be detected and measured:
14 14 −
C → N+β (1)

The half-life for this reaction is 5700 ± 30 yr.

The 14C/12C ratio in living organisms is 1.3 × 10−12, with a decay rate of 15 dpm/g of carbon. Comparing the disintegrations per
minute per gram of carbon from an archaeological sample with those from a recently living sample enables scientists to estimate
the age of the artifact, as illustrated in Example [Link] this method implicitly assumes that the 14CO2/12CO2 ratio in the
atmosphere is constant, which is not strictly correct. Other methods, such as tree-ring dating, have been used to calibrate the dates
obtained by radiocarbon dating, and all radiocarbon dates reported are now corrected for minor changes in the 14CO2/12CO2 ratio
over time.

Summary
The half-life of a first-order reaction is independent of the concentration of the reactants.
The half-lives of radioactive isotopes can be used to date objects.
The rate of decay, or activity, of a sample of a radioactive substance is the rate of decrease in the number of radioactive nuclei per
unit time. The half-life of a reaction is the time required for the reactant concentration to decrease to one-half its initial value.
Radioactive decay reactions are first-order reactions.
Modified by Tom Neils (Grand Rapids Community College)

2.6 Half-lives and the Rate of Radioactive Decay is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

3 [Link]
2.7 Mass Defect - The Source of Nuclear Energy
Skills to Develop
To calculate a mass-energy balance and a nuclear binding energy.
To understand the differences between nuclear fission and fusion.

Nuclear reactions, like chemical reactions, are accompanied by changes in energy. The energy changes in nuclear reactions,
however, are enormous compared with those of even the most energetic chemical reactions. In fact, the energy changes in a typical
nuclear reaction are so large that they result in a measurable change of mass. In this section, we describe the relationship between
mass and energy in nuclear reactions and show how the seemingly small changes in mass that accompany nuclear reactions result
in the release of enormous amounts of energy.

Mass–Energy Balance
The relationship between mass (m) and energy (E) is expressed in the following equation:
2
E = mc (1)

where
cis the speed of light (2.998 × 10 m/s), and
8

E and m are expressed in units of joules and kilograms, respectively.

Albert Einstein first derived this relationship in 1905 as part of his special theory of relativity: the mass of a particle is directly
proportional to its energy. Thus according to Equation 1, every mass has an associated energy, and similarly, any reaction that
involves a change in energy must be accompanied by a change in mass. This implies that all exothermic reactions should be
accompanied by a decrease in mass, and all endothermic reactions should be accompanied by an increase in mass. Given the law of
conservation of mass, how can this be true? The solution to this apparent contradiction is that chemical reactions are indeed
accompanied by changes in mass, but these changes are simply too small to be detected. As you may recall, all particles exhibit
wavelike behavior, but the wavelength is inversely proportional to the mass of the particle (actually, to its momentum, the product
of its mass and velocity). Consequently, wavelike behavior is detectable only for particles with very small masses, such as
electrons. For example, the chemical equation for the combustion of graphite to produce carbon dioxide is as follows:
1
∘
C(graphite) + O2 (g) → C O2 (g) ΔH = −393.5 kJ/mol (2)
2

Combustion reactions are typically carried out at constant pressure, and under these conditions, the heat released or absorbed is
equal to ΔH. When a reaction is carried out at constant volume, the heat released or absorbed is equal to ΔE. For most chemical
reactions, however, ΔE ≈ ΔH. If we rewrite Einstein’s equation as
2
ΔE = (Δm)c (3)

we can rearrange the equation to obtain the following relationship between the change in mass and the change in energy:

ΔE
Δm = (4)
2
c

Because 1 J = 1 (kg•m2)/s2, the change in mass is as follows:

5 2 2
−393.5 kJ/mol −3.935 × 10 (kg ⋅ m )/(s ⋅ mol)
−12
Δm = = = −4.38 × 10 kg/mol (5)
8 2 8 2
(2.998 × 10 m/s) (2.998 × 10 m/s)

This is a mass change of about 3.6 × 10−10 g/g carbon that is burned, or about 100-millionths of the mass of an electron per atom of
carbon. In practice, this mass change is much too small to be measured experimentally and is negligible.
In contrast, for a typical nuclear reaction, such as the radioactive decay of 14C to 14N and an electron (a β particle), there is a much
larger change in mass:
14 14 0
C → N+ β (6)
−1

1 [Link]
We can use the experimentally measured masses of subatomic particles and common isotopes given in Table 20.1 to calculate the
change in mass directly. The reaction involves the conversion of a neutral 14C atom to a positively charged 14N ion (with six, not
seven, electrons) and a negatively charged β particle (an electron), so the mass of the products is identical to the mass of a neutral
14
N atom. The total change in mass during the reaction is therefore the difference between the mass of a neutral 14N atom
(14.003074 amu) and the mass of a 14C atom (14.003242 amu):
Δm = massproducts − massreactants (7)

= 14.003074 amu − 14.003242 amu = −0.000168 amu (8)

The difference in mass, which has been released as energy, corresponds to almost one-third of an electron. The change in mass for
the decay of 1 mol of 14C is −0.000168 g = −1.68 × 10−4 g = −1.68 × 10−7 kg. Although a mass change of this magnitude may seem
small, it is about 1000 times larger than the mass change for the combustion of graphite. The energy change is as follows:
2 −7 8 2
ΔE = (Δm)c = (−1.68 × 10 kg)(2.998 × 10 m/s) (9)
10 2 2 10 7
= −1.51 × 10 (kg ⋅ m )/ s = −1.51 × 10 J = −1.51 × 10 kJ (10)

The energy released in this nuclear reaction is more than 100,000 times greater than that of a typical chemical reaction, even
though the decay of 14C is a relatively low-energy nuclear reaction.
Because the energy changes in nuclear reactions are so large, they are often expressed in kiloelectronvolts (1 keV = 103 eV),
megaelectronvolts (1 MeV = 106 eV), and even gigaelectronvolts (1 GeV = 109 eV) per atom or particle. The change in energy that
accompanies a nuclear reaction can be calculated from the change in mass using the relationship 1 amu = 931 MeV. The energy
released by the decay of one atom of 14C is thus
931 MeV
−4
(−1.68 × 10 amu) ( ) = −0.156 MeV = −156 keV
amu

Nuclear Binding Energies

We have seen that energy changes in both chemical and nuclear reactions are accompanied by changes in mass. Einstein’s equation,
which allows us to interconvert mass and energy, has another interesting consequence: The mass of an atom is always less than the
sum of the masses of its component particles. The only exception to this rule is hydrogen-1 (1H), whose measured mass of
1.007825 amu is identical to the sum of the masses of a proton and an electron. In contrast, the experimentally measured mass of an
atom of deuterium (2H) is 2.014102 amu, although its calculated mass is 2.016490 amu:
m2 H = mneutron + mproton + melectron (11)

= 1.008665 amu + 1.007276 amu + 0.000549 amu = 2.016490 amu (12)

The difference between the sum of the masses of the components and the measured atomic mass is called the mass defect of the
nucleus. Just as a molecule is more stable than its isolated atoms, a nucleus is more stable (lower in energy) than its isolated
components. Consequently, when isolated nucleons assemble into a stable nucleus, energy is released. According to Equation 4,
this release of energy must be accompanied by a decrease in the mass of the nucleus.

Figure 1 : Nuclear Binding Energy in Deuterium. The mass of a 2H atom is less than the sum of the masses of a proton, a neutron,
and an electron by 0.002388 amu; the difference in mass corresponds to the nuclear binding energy. The larger the value of the

2 [Link]
 mass defect, the greater the nuclear binding energy and the more stable the nucleus.
The amount of energy released when a nucleus forms from its component nucleons is the nuclear binding energy (Figure 1). In
the case of deuterium, the mass defect is 0.002388 amu, which corresponds to a nuclear binding energy of 2.22 MeV for the
deuterium nucleus. Because the magnitude of the mass defect is proportional to the nuclear binding energy, both values indicate the
stability of the nucleus.

Just as a molecule is more stable (lower in energy) than its isolated atoms, a nucleus is
more stable than its isolated components.
Not all nuclei are equally stable. Chemists describe the relative stability of different nuclei by comparing the binding energy per
nucleon, which is obtained by dividing the nuclear binding energy by the mass number (A) of the nucleus. As shown in Figure 2,
the binding energy per nucleon increases rapidly with increasing atomic number until about Z = 26, where it levels off to about 8–9
MeV per nucleon and then decreases slowly. The initial increase in binding energy is not a smooth curve but exhibits sharp peaks
corresponding to the light nuclei that have equal numbers of protons and neutrons (e.g., 4He, 12C, and 16O). As mentioned earlier,
these are particularly stable combinations.

Figure 2 : The Curve of Nuclear Binding Energy. This plot of the average binding energy per nucleon as a function of atomic
number shows that the binding energy per nucleon increases with increasing atomic number until about Z = 26, levels off, and then
decreases. The sharp peaks correspond to light nuclei that have equal numbers of protons and neutrons.
Because the maximum binding energy per nucleon is reached at 56Fe, all other nuclei are thermodynamically unstable with regard
to the formation of 56Fe. Consequently, heavier nuclei (toward the right in Figure 2) should spontaneously undergo reactions such
as alpha decay, which result in a decrease in atomic number. Conversely, lighter elements (on the left in Figure 2) should
spontaneously undergo reactions that result in an increase in atomic number. This is indeed the observed pattern.

Heavier nuclei spontaneously undergo nuclear reactions that decrease their atomic
number. Lighter nuclei spontaneously undergo nuclear reactions that increase their
atomic number.

Summary
Unlike a chemical reaction, a nuclear reaction results in a significant change in mass and an associated change of energy, as
described by Einstein’s equation. Nuclear reactions are accompanied by large changes in energy, which result in detectable changes
in mass. The change in mass is related to the change in energy according to Einstein’s equation: ΔE = (Δm)c2. Large changes in
energy are usually reported in kiloelectronvolts or megaelectronvolts (thousands or millions of electronvolts). With the exception of
1
H, the experimentally determined mass of an atom is always less than the sum of the masses of the component particles (protons,
neutrons, and electrons) by an amount called the mass defect of the nucleus. The energy corresponding to the mass defect is the
nuclear binding energy, the amount of energy released when a nucleus forms from its component particles. In nuclear fission,
nuclei split into lighter nuclei with an accompanying release of multiple neutrons and large amounts of energy. The critical mass is
the minimum mass required to support a self-sustaining nuclear chain reaction. Nuclear fusion is a process in which two light
nuclei combine to produce a heavier nucleus plus a great deal of energy.

3 [Link]
2.7 Mass Defect - The Source of Nuclear Energy is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

4 [Link]
2.8 Nuclear Energy - Fission and Fusion

Skills to Develop
Explain nuclear fission
Relate the concepts of critical mass and nuclear chain reactions
Summarize basic requirements for nuclear fission

Many heavier elements with smaller binding energies per nucleon can decompose into more stable elements that have intermediate mass numbers
and larger binding energies per nucleon—that is, mass numbers and binding energies per nucleon that are closer to the “peak” of the binding energy
graph near 56. Sometimes neutrons are also produced. This decomposition is called fission, the breaking of a large nucleus into smaller pieces. The
breaking is rather random with the formation of a large number of different products. Fission usually does not occur naturally, but is induced by
bombardment with neutrons. The first reported nuclear fission occurred in 1939 when three German scientists, Lise Meitner, Otto Hahn, and Fritz
Strassman, bombarded uranium-235 atoms with slow-moving neutrons that split the U-238 nuclei into smaller fragments that consisted of several
neutrons and elements near the middle of the periodic table. Since then, fission has been observed in many other isotopes, including most actinide
isotopes that have an odd number of neutrons. A typical nuclear fission reaction is shown in Figure 1.

Figure 1: When a slow neutron hits a fissionable U-235 nucleus, it is absorbed and forms an unstable U-236 nucleus. The U-236 nucleus then
rapidly breaks apart into two smaller nuclei (in this case, Ba-141 and Kr-92) along with several neutrons (usually two or three), and releases a very
large amount of energy.
Among the products of Meitner, Hahn, and Strassman’s fission reaction were barium, krypton, lanthanum, and cerium, all of which have nuclei that
are more stable than uranium-235. Since then, hundreds of different isotopes have been observed among the products of fissionable substances. A
few of the many reactions that occur for U-235, and a graph showing the distribution of its fission products and their yields, are shown in Figure 2.
Similar fission reactions have been observed with other uranium isotopes, as well as with a variety of other isotopes such as those of plutonium.

Figure 2: (a) Nuclear fission of U-235 produces a range of fission products. (b) The larger fission products of U-235 are typically one isotope with a
mass number around 85–105, and another isotope with a mass number that is about 50% larger, that is, about 130–150.
A tremendous amount of energy is produced by the fission of heavy elements. For instance, when one mole of U-235 undergoes fission, the products
weigh about 0.2 grams less than the reactants; this “lost” mass is converted into a very large amount of energy, about 1.8 × 1010 kJ per mole of U-
235. Nuclear fission reactions produce incredibly large amounts of energy compared to chemical reactions. The fission of 1 kilogram of uranium-
235, for example, produces about 2.5 million times as much energy as is produced by burning 1 kilogram of coal.

1 [Link]
As described earlier, when undergoing fission U-235 produces two “medium-sized” nuclei, and two or three neutrons. These neutrons may then
cause the fission of other uranium-235 atoms, which in turn provide more neutrons that can cause fission of even more nuclei, and so on. If this
occurs, we have a nuclear chain reaction (Figure 3). On the other hand, if too many neutrons escape the bulk material without interacting with a
nucleus, then no chain reaction will occur.

Figure 3: The fission of a large nucleus, such as U-235, produces two or three neutrons, each of which is capable of causing fission of another
nucleus by the reactions shown. If this process continues, a nuclear chain reaction occurs.
Material that can sustain a nuclear fission chain reaction is said to be fissile or fissionable. (Technically, fissile material can undergo fission with
neutrons of any energy, whereas fissionable material requires high-energy neutrons.) Nuclear fission becomes self-sustaining when the number of
neutrons produced by fission equals or exceeds the number of neutrons absorbed by splitting nuclei plus the number that escape into the
surroundings. The amount of a fissionable material that will support a self-sustaining chain reaction is a critical mass. An amount of fissionable
material that cannot sustain a chain reaction is a subcritical mass. An amount of material in which there is an increasing rate of fission is known as a
supercritical mass. The critical mass depends on the type of material: its purity, the temperature, the shape of the sample, and how the neutron
reactions are controlled (Figure 4).

Figure 4: (a) In a subcritical mass, the fissile material is too small and allows too many neutrons to escape the material, so a chain reaction does not
occur. (b) In a critical mass, a large enough number of neutrons in the fissile material induce fission to create a chain reaction.
An atomic bomb (Figure 5) contains several pounds of fissionable material, U or Pu, a source of neutrons, and an explosive device for
235
92
239
94

compressing it quickly into a small volume. When fissionable material is in small pieces, the proportion of neutrons that escape through the

2 [Link]
relatively large surface area is great, and a chain reaction does not take place. When the small pieces of fissionable material are brought together
quickly to form a body with a mass larger than the critical mass, the relative number of escaping neutrons decreases, and a chain reaction and
explosion result.

Figure 5 : (a) The nuclear fission bomb that destroyed Hiroshima on August 6, 1945, consisted of two subcritical masses of U-235, where
conventional explosives were used to fire one of the subcritical masses into the other, creating the critical mass for the nuclear explosion. (b) The
plutonium bomb that destroyed Nagasaki on August 12, 1945, consisted of a hollow sphere of plutonium that was rapidly compressed by
conventional explosives. This led to a concentration of plutonium in the center that was greater than the critical mass necessary for the nuclear
explosion.

Fission Reactors
Chain reactions of fissionable materials can be controlled and sustained without an explosion in a nuclear reactor (Figure 6). Any nuclear reactor
that produces power via the fission of uranium or plutonium by bombardment with neutrons must have at least five components: nuclear fuel
consisting of fissionable material, a nuclear moderator, reactor coolant, control rods, and a shield and containment system. We will discuss these
components in greater detail later in the section. The reactor works by separating the fissionable nuclear material such that a critical mass cannot be
formed, controlling both the flux and absorption of neutrons to allow shutting down the fission reactions. In a nuclear reactor used for the production
of electricity, the energy released by fission reactions is trapped as thermal energy and used to boil water and produce steam. The steam is used to
turn a turbine, which powers a generator for the production of electricity.

Figure 6: (a) The Diablo Canyon Nuclear Power Plant near San Luis Obispo is the only nuclear power plant currently in operation in California. The
domes are the containment structures for the nuclear reactors, and the brown building houses the turbine where electricity is generated. Ocean water
is used for cooling. (b) The Diablo Canyon uses a pressurized water reactor, one of a few different fission reactor designs in use around the world, to
produce electricity. Energy from the nuclear fission reactions in the core heats water in a closed, pressurized system. Heat from this system produces
steam that drives a turbine, which in turn produces electricity. (credit a: modification of work by “Mike” Michael L. Baird; credit b: modification of
work by the Nuclear Regulatory Commission)

Nuclear Fuels
Nuclear fuel consists of a fissionable isotope, such as uranium-235, which must be present in sufficient quantity to provide a self-sustaining chain
reaction. In the United States, uranium ores contain from 0.05–0.3% of the uranium oxide U3O8; the uranium in the ore is about 99.3%

3 [Link]
nonfissionable U-238 with only 0.7% fissionable U-235. Nuclear reactors require a fuel with a higher concentration of U-235 than is found in nature;
it is normally enriched to have about 5% of uranium mass as U-235. At this concentration, it is not possible to achieve the supercritical mass
necessary for a nuclear explosion. Uranium can be enriched by gaseous diffusion (the only method currently used in the US), using a gas centrifuge,
or by laser separation.
In the gaseous diffusion enrichment plant where U-235 fuel is prepared, UF6 (uranium hexafluoride) gas at low pressure moves through barriers that
have holes just barely large enough for UF6 to pass through. The slightly lighter 235UF6 molecules diffuse through the barrier slightly faster than the
heavier 238UF6 molecules. This process is repeated through hundreds of barriers, gradually increasing the concentration of 235UF6 to the level needed
by the nuclear reactor. The basis for this process, Graham’s law, is described in the chapter on gases. The enriched UF6 gas is collected, cooled until
it solidifies, and then taken to a fabrication facility where it is made into fuel assemblies. Each fuel assembly consists of fuel rods that contain many
thimble-sized, ceramic-encased, enriched uranium (usually UO2) fuel pellets. Modern nuclear reactors may contain as many as 10 million fuel
pellets. The amount of energy in each of these pellets is equal to that in almost a ton of coal or 150 gallons of oil.

Nuclear Moderators
Neutrons produced by nuclear reactions move too fast to cause fission (Figure 4). They must first be slowed to be absorbed by the fuel and produce
additional nuclear reactions. A nuclear moderator is a substance that slows the neutrons to a speed that is low enough to cause fission. Early reactors
2
used high-purity graphite as a moderator. Modern reactors in the US exclusively use heavy water ( H O) or light water (ordinary H2O), whereas
1 2

some reactors in other countries use other materials, such as carbon dioxide, beryllium, or graphite.

Reactor Coolants
A nuclear reactor coolant is used to carry the heat produced by the fission reaction to an external boiler and turbine, where it is transformed into
electricity. Two overlapping coolant loops are often used; this counteracts the transfer of radioactivity from the reactor to the primary coolant loop.
All nuclear power plants in the US use water as a coolant. Other coolants include molten sodium, lead, a lead-bismuth mixture, or molten salts.

Control Rods
Nuclear reactors use control rods (Figure 8) to control the fission rate of the nuclear fuel by adjusting the number of slow neutrons present to keep
the rate of the chain reaction at a safe level. Control rods are made of boron, cadmium, hafnium, or other elements that are able to absorb neutrons.
Boron-10, for example, absorbs neutrons by a reaction that produces lithium-7 and alpha particles:
10 1 7 4
B+ n ⟶ Li + He (1)
5 0 3 2

When control rod assemblies are inserted into the fuel element in the reactor core, they absorb a larger fraction of the slow neutrons, thereby slowing
the rate of the fission reaction and decreasing the power produced. Conversely, if the control rods are removed, fewer neutrons are absorbed, and the
fission rate and energy production increase. In an emergency, the chain reaction can be shut down by fully inserting all of the control rods into the
nuclear core between the fuel rods.

Figure 7: The nuclear reactor core shown in (a) contains the fuel and control rod assembly shown in (b). (credit: modification of work by E.
Generalic, [Link]

4 [Link]
Shield and Containment System
During its operation, a nuclear reactor produces neutrons and other radiation. Even when shut down, the decay products are radioactive. In addition,
an operating reactor is thermally very hot, and high pressures result from the circulation of water or another coolant through it. Thus, a reactor must
withstand high temperatures and pressures, and must protect operating personnel from the radiation. Reactors are equipped with a containment
system (or shield) that consists of three parts:
1. The reactor vessel, a steel shell that is 3–20-centimeters thick and, with the moderator, absorbs much of the radiation produced by the reactor
2. A main shield of 1–3 meters of high-density concrete
3. A personnel shield of lighter materials that protects operators from γ rays and X-rays
In addition, reactors are often covered with a steel or concrete dome that is designed to contain any radioactive materials might be released by a
reactor accident.

The Design and Safe Operation of a Nuclear Reactor

Video 1 : Click here to watch a 3-minute video from the Nuclear Energy Institute on how nuclear reactors work.
Nuclear power plants are designed in such a way that they cannot form a supercritical mass of fissionable material and therefore cannot create a
nuclear explosion. But as history has shown, failures of systems and safeguards can cause catastrophic accidents, including chemical explosions and
nuclear meltdowns (damage to the reactor core from overheating). The following Chemistry in Everyday Life feature explores three infamous
meltdown incidents.

Nuclear Accidents
The importance of cooling and containment are amply illustrated by three major accidents that occurred with the nuclear reactors at nuclear power
generating stations in the United States (Three Mile Island), the former Soviet Union (Chernobyl), and Japan (Fukushima).
In March 1979, the cooling system of the Unit 2 reactor at Three Mile Island Nuclear Generating Station in Pennsylvania failed, and the cooling
water spilled from the reactor onto the floor of the containment building. After the pumps stopped, the reactors overheated due to the high
radioactive decay heat produced in the first few days after the nuclear reactor shut down. The temperature of the core climbed to at least 2200 °C,
and the upper portion of the core began to melt. In addition, the zirconium alloy cladding of the fuel rods began to react with steam and produced
hydrogen:
Zr(s) + 2 H O(g) ⟶ ZrO (s) + 2 H (g) (2)
2 2 2

The hydrogen accumulated in the confinement building, and it was feared that there was danger of an explosion of the mixture of hydrogen and air
in the building. Consequently, hydrogen gas and radioactive gases (primarily krypton and xenon) were vented from the building. Within a week,
cooling water circulation was restored and the core began to cool. The plant was closed for nearly 10 years during the cleanup process.
Although zero discharge of radioactive material is desirable, the discharge of radioactive krypton and xenon, such as occurred at the Three Mile
Island plant, is among the most tolerable. These gases readily disperse in the atmosphere and thus do not produce highly radioactive areas.
Moreover, they are noble gases and are not incorporated into plant and animal matter in the food chain. Effectively none of the heavy elements of the
core of the reactor were released into the environment, and no cleanup of the area outside of the containment building was necessary (Figure 8).

5 [Link]
 Figure 8: (a) In this 2010 photo of Three Mile Island, the remaining structures from the damaged Unit 2 reactor are seen on the left, whereas the
separate Unit 1 reactor, unaffected by the accident, continues generating power to this day (right). (b) President Jimmy Carter visited the Unit 2
control room a few days after the accident in 1979.
Another major nuclear accident involving a reactor occurred in April 1986, at the Chernobyl Nuclear Power Plant in Ukraine, which was still a part
of the former Soviet Union. While operating at low power during an unauthorized experiment with some of its safety devices shut off, one of the
reactors at the plant became unstable. Its chain reaction became uncontrollable and increased to a level far beyond what the reactor was designed for.
The steam pressure in the reactor rose to between 100 and 500 times the full power pressure and ruptured the reactor. Because the reactor was not
enclosed in a containment building, a large amount of radioactive material spewed out, and additional fission products were released, as the graphite
(carbon) moderator of the core ignited and burned. The fire was controlled, but over 200 plant workers and firefighters developed acute radiation
sickness and at least 32 soon died from the effects of the radiation. It is predicted that about 4000 more deaths will occur among emergency workers
and former Chernobyl residents from radiation-induced cancer and leukemia. The reactor has since been encapsulated in steel and concrete, a now-
decaying structure known as the sarcophagus. Almost 30 years later, significant radiation problems still persist in the area, and Chernobyl largely
remains a wasteland.
In 2011, the Fukushima Daiichi Nuclear Power Plant in Japan was badly damaged by a 9.0-magnitude earthquake and resulting tsunami. Three
reactors up and running at the time were shut down automatically, and emergency generators came online to power electronics and coolant systems.
However, the tsunami quickly flooded the emergency generators and cut power to the pumps that circulated coolant water through the reactors.
High-temperature steam in the reactors reacted with zirconium alloy to produce hydrogen gas. The gas escaped into the containment building, and
the mixture of hydrogen and air exploded. Radioactive material was released from the containment vessels as the result of deliberate venting to
reduce the hydrogen pressure, deliberate discharge of coolant water into the sea, and accidental or uncontrolled events.
An evacuation zone around the damaged plant extended over 12.4 miles away, and an estimated 200,000 people were evacuated from the area. All
48 of Japan’s nuclear power plants were subsequently shut down, remaining shuttered as of December 2014. Since the disaster, public opinion has
shifted from largely favoring to largely opposing increasing the use of nuclear power plants, and a restart of Japan’s atomic energy program is still
stalled (Figure 10).

Figure 9 : (a) After the accident, contaminated waste had to be removed, and (b) an evacuation zone was set up around the plant in areas that
received heavy doses of radioactive fallout. (credit a: modification of work by “Live Action Hero”/Flickr)
The energy produced by a reactor fueled with enriched uranium results from the fission of uranium as well as from the fission of plutonium
produced as the reactor operates. As discussed previously, the plutonium forms from the combination of neutrons and the uranium in the fuel. In any
nuclear reactor, only about 0.1% of the mass of the fuel is converted into energy. The other 99.9% remains in the fuel rods as fission products and
unused fuel. All of the fission products absorb neutrons, and after a period of several months to a few years, depending on the reactor, the fission
products must be removed by changing the fuel rods. Otherwise, the concentration of these fission products would increase and absorb more
neutrons until the reactor could no longer operate.
Spent fuel rods contain a variety of products, consisting of unstable nuclei ranging in atomic number from 25 to 60, some transuranium elements,
including plutonium and americium, and unreacted uranium isotopes. The unstable nuclei and the transuranium isotopes give the spent fuel a
dangerously high level of radioactivity. The long-lived isotopes require thousands of years to decay to a safe level. The ultimate fate of the nuclear
reactor as a significant source of energy in the United States probably rests on whether or not a politically and scientifically satisfactory technique
for processing and storing the components of spent fuel rods can be developed.

6 [Link]
Fusion
Skills to Develop
Describe the nuclear reactions in a nuclear fusion reaction
Quantify the energy released or absorbed in a fusion reaction

The process of converting very light nuclei into heavier nuclei is also accompanied by the conversion of mass into large amounts of energy, a
process called fusion. The principal source of energy in the sun is a net fusion reaction in which four hydrogen nuclei fuse and produce one helium
nucleus and two positrons. This is a net reaction of a more complicated series of events:
1 4 0
4 H ⟶ 2
He + 2 n (3)
1 +1

A helium nucleus has a mass that is 0.7% less than that of four hydrogen nuclei; this lost mass is converted into energy during the fusion. This
reaction produces about 3.6 × 1011 kJ of energy per mole of He produced. This is somewhat larger than the energy produced by the nuclear fission
4
2

of one mole of U-235 (1.8 × 1010 kJ), and over 3 million times larger than the energy produced by the (chemical) combustion of one mole of octane
(5471 kJ).
It has been determined that the nuclei of the heavy isotopes of hydrogen, a deuteron, 2
1
H and a triton, 3
1
H , undergo fusion at extremely high
temperatures (thermonuclear fusion). They form a helium nucleus and a neutron:
2 3 4 1
1
H + 1H ⟶ 2
He + 2 n (4)
0

This change proceeds with a mass loss of 0.0188 amu, corresponding to the release of 1.69 × 109 kilojoules per mole of He formed. The very high 4
2

temperature is necessary to give the nuclei enough kinetic energy to overcome the very strong repulsive forces resulting from the positive charges on
their nuclei so they can collide.

Figure 1: Fusion of deuterium with tritium creating helium-4, freeing a neutron, and releasing 17.59 MeV of energy, as an appropriate amount of
mass changing forms to appear as the kinetic energy of the products, in agreement with kinetic E = Δmc , where Δm is the change in rest mass of
2

particles.[Image use with permission via Wikipedia (Wykis)

The most important fusion process in nature is the one that powers stars. In the 20th century, it was realized that the energy released from nuclear
fusion reactions accounted for the longevity of the Sun and other stars as a source of heat and light. The fusion of nuclei in a star, starting from its
initial hydrogen and helium abundance, provides that energy and synthesizes new nuclei as a byproduct of that fusion process. The prime energy
producer in the Sun is the fusion of hydrogen to form helium, which occurs at a solar-core temperature of 14 million kelvin. The net result is the
fusion of four protons into one alpha particle, with the release of two positrons, two neutrinos (which changes two of the protons into neutrons), and
energy (Figure 2).

7 [Link]
 Figure 2: (left) The Sun is a main-sequence star, and thus generates its energy by nuclear fusion of hydrogen nuclei into helium. In its core, the Sun
fuses 620 million metric tons of hydrogen each second. (right) The proton-proton chain dominates in stars the size of the Sun or smaller.
Example 1
Calculate the energy released in each of the following hypothetical processes.
a. 3 4
2
He →
12
6
C

b. 6 1
1
H+6
1
0
n →
12
6
C

c. 6 2
1
D →
12
6
C

Discuss your results.

a. Q a = 3 × 4.0026 − 12.000) amu × (1.4924 × 10
−10
J/amu) = 1.17 × 10
−12
J

b. Q b = (6 × (1.007825 + 1.008665) − 12.00000) amu × (1.4924 × 10

1−0
J/amu) = 1.476 × 10
−11
J

c. Q c = 6 × 2.014102 − 12.00000 amu × (1.4924 × 10

−10
J/amu) = 1.263 × 10
−11
J

Fusion of He to give C releases the least amount of energy, because the fusion to produce He has released a large amount. The difference
between the second and the third is the binding energy of deuterium. The conservation of mass-and-energy is well illustrated in these
calculations. On the other hand, the calculation is based on the conservation of mass-and-energy.

Nuclear Reactors
Useful fusion reactions require very high temperatures for their initiation—about 15,000,000 K or more. At these temperatures, all molecules
dissociate into atoms, and the atoms ionize, forming plasma. These conditions occur in an extremely large number of locations throughout the
universe—stars are powered by fusion. Humans have already figured out how to create temperatures high enough to achieve fusion on a large scale
in thermonuclear weapons. A thermonuclear weapon such as a hydrogen bomb contains a nuclear fission bomb that, when exploded, gives off
enough energy to produce the extremely high temperatures necessary for fusion to occur.

8 [Link]
 Figure 3: (a) This model is of the International Thermonuclear Experimental Reactor (ITER) reactor. Currently under construction in the south of
France with an expected completion date of 2027, the ITER will be the world’s largest experimental Tokamak nuclear fusion reactor with a goal of
achieving larg\times 10^{scale sustained energy production. (b) In 2012, the National Ignition Facility at Lawrence Livermore National Laboratory
briefly produced over 500,000,000,000 watts (500 terawatts, or 500 TW) of peak power and delivered 1,850,000 joules (1.85 MJ) of energy, the
largest laser energy ever produced and 1000 times the power usage of the entire United States in any given moment. Although lasting only a few
billionths of a second, the 192 lasers attained the conditions needed for nuclear fusion ignition. This image shows the target prior to the laser shot.
(credit a: modification of work by Stephan Mosel)
Another much more beneficial way to create fusion reactions is in a fusion reactor, a nuclear reactor in which fusion reactions of light nuclei are
controlled. Because no solid materials are stable at such high temperatures, mechanical devices cannot contain the plasma in which fusion reactions
occur. Two techniques to contain plasma at the density and temperature necessary for a fusion reaction are currently the focus of intensive research
efforts: containment by a magnetic field and by the use of focused laser beams (Figure 3). A number of large projects are working to attain one of
the biggest goals in science: getting hydrogen fuel to ignite and produce more energy than the amount supplied to achieve the extremely high
temperatures and pressures that are required for fusion. At the time of this writing, there are no self-sustaining fusion reactors operating in the world,
although small-scale controlled fusion reactions have been run for very brief [Link]

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley (Stephen F. Austin
State University) with contributing authors. Textbook content produced by OpenStax College is licensed under a Creative Commons Attribution
License 4.0 license. Download for free at [Link]

2.8 Nuclear Energy - Fission and Fusion is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

9 [Link]
2.9 The Nature of Light
Skills to Develop
To learn about the characteristics of electromagnetic waves. Light, X-Rays, infrared and microwaves are among the types of
electromagnetic waves.

Scientists discovered much of what we know about the structure of the atom by observing the interaction of atoms with various
forms of radiant, or transmitted, energy, such as the energy associated with the visible light we detect with our eyes, the infrared
radiation we feel as heat, the ultraviolet light that causes sunburn, and the x-rays that produce images of our teeth or bones. All
these forms of radiant energy should be familiar to you. We begin our discussion of the development of our current atomic model
by describing the properties of waves and the various forms of electromagnetic radiation.

Figure 1: A Wave in Water. When a drop of water falls onto a smooth water surface, it generates a set of waves that travel outward
in a circular direction.

Properties of Waves
A wave is a periodic oscillation that transmits energy through space. Anyone who has visited a beach or dropped a stone into a
puddle has observed waves traveling through water (Figure 1). These waves are produced when wind, a stone, or some other
disturbance, such as a passing boat, transfers energy to the water, causing the surface to oscillate up and down as the energy travels
outward from its point of origin. As a wave passes a particular point on the surface of the water, anything floating there moves up
and down.

Figure 2: Important Properties of Waves (a) Wavelength (λ in meters), frequency (ν , in Hz), and amplitude are indicated on this
drawing of a wave. (b) The wave with the shortest wavelength has the greatest number of wavelengths per unit time (i.e., the
highest frequency). If two waves have the same frequency and speed, the one with the greater amplitude has the higher energy.
Waves have characteristic properties (Figure 2). As you may have noticed in Figure 1, waves are periodic, that is, they repeat
regularly in both space and time. The distance between two corresponding points in a wave—between the midpoints of two peaks,
for example, or two troughs—is the wavelength (λ , lowercase Greek lambda). Wavelengths are described by a unit of distance,

1 [Link]
typically meters. The frequency (ν , lowercase Greek nu) of a wave is the number of oscillations that pass a particular point in a
given period of time. The usual units are oscillations per second (1/s = s−1), which in the SI system is called the hertz (Hz). It is
named after German physicist Heinrich Hertz (1857–1894), a pioneer in the field of electromagnetic radiation.
The amplitude, or vertical height, of a wave is defined as half the peak-to-trough height; as the amplitude of a wave with a given
frequency increases, so does its energy. As you can see in Figure 2, two waves can have the same amplitude but different
wavelengths and vice versa. The distance traveled by a wave per unit time is its speed (v ), which is typically measured in meters
per second (m/s). The speed of a wave is equal to the product of its wavelength and frequency:

(wavelength)(frequency) = speedonumber (1)

λν = v (2)

meters wave meters

( )( ) = (3)
wave second second

Be careful not to confuse the symbols for the speed, v , with the frequency, ν .

Different types of waves may have vastly different possible speeds and frequencies. Water waves are slow compared to sound
waves, which can travel through solids, liquids, and gases. Whereas water waves may travel a few meters per second, the speed of
sound in dry air at 20°C is 343.5 m/s. Ultrasonic waves, which travel at an even higher speed (>1500 m/s) and have a greater
frequency, are used in such diverse applications as locating underwater objects and the medical imaging of internal organs.

Electromagnetic Radiation
Water waves transmit energy through space by the periodic oscillation of matter (the water). In contrast, energy that is transmitted,
or radiated, through space in the form of periodic oscillations of electric and magnetic fields is known as electromagnetic
radiation. (Figure 3). Some forms of electromagnetic radiation are shown in Figure 4. In a vacuum, all forms of electromagnetic
radiation—whether microwaves, visible light, or gamma rays—travel at the speed of light (c), which turns out to be a fundamental
physical constant with a value of 2.99792458 × 108 m/s (about 3.00 ×108 m/s or 1.86 × 105 mi/s). This is about a million times
faster than the speed of sound.

Figure 3: The Nature of Electromagnetic Radiation. All forms of electromagnetic radiation consist of perpendicular oscillating
electric and magnetic fields.
Because the various kinds of electromagnetic radiation all have the same speed (c), they differ in only wavelength and frequency.
As shown in Figure 4 and Table 1, the wavelengths of familiar electromagnetic radiation range from 101 m for radio waves to 10−12
m for gamma rays, which are emitted by nuclear reactions. By replacing v with c in Equation2, we can show that the frequency of
electromagnetic radiation is inversely proportional to its wavelength:
c = λν (4)

c
ν = (5)
λ

For example, the frequency of radio waves is about 108 Hz, whereas the frequency of gamma rays is about 1020 Hz. Visible light,
which is electromagnetic radiation that can be detected by the human eye, has wavelengths between about 7 × 10−7 m (700 nm, or
4.3 × 1014 Hz) and 4 × 10−7 m (400 nm, or 7.5 × 1014 Hz). Note that when frequency increases, wavelength decreases; c being a
constant stays the same. Similarly, when frequency decreases, the wavelength increases.

2 [Link]
 Figure 4: The Electromagnetic Spectrum. (a) This diagram shows the wavelength and frequency ranges of electromagnetic
radiation. The visible portion of the electromagnetic spectrum is the narrow region with wavelengths between about 400 and 700
nm. (b) When white light is passed through a prism, it is split into light of different wavelengths, whose colors correspond to the
visible spectrum.

Within the visible range our eyes perceive radiation of different wavelengths (or frequencies) as light of different colors, ranging
from red to violet in order of decreasing wavelength. The components of white light—a mixture of all the frequencies of visible
light—can be separated by a prism, as shown in part (b) in Figure 4. A similar phenomenon creates a rainbow, where water
droplets suspended in the air act as tiny prisms.
Table 1 : Common Wavelength Units for Electromagnetic Radiation
Unit Symbol Wavelength (m) Type of Radiation

picometer pm 10−12 gamma ray

angstrom Å 10−10 x-ray

nanometer nm 10−9 UV, visible

micrometer μm 10−6 infrared

millimeter mm 10−3 infrared

centimeter cm 10−2 microwave

meter m 100 radio

As you will soon see, the energy of electromagnetic radiation is directly proportional to its frequency and inversely proportional to
its wavelength:

E ∝ ν (6)

1
∝ (7)
λ

Whereas visible light is essentially harmless to our skin, ultraviolet light, with wavelengths of ≤ 400 nm, has enough energy to
cause severe damage to our skin in the form of sunburn. Because the ozone layer of the atmosphere absorbs sunlight with
wavelengths less than 350 nm, it protects us from the damaging effects of highly energetic ultraviolet radiation.

The energy of electromagnetic radiation increases with increasing frequency and

decreasing wavelength.
Example 1 : Wavelength of Radiowaves

3 [Link]
 Your favorite FM radio station, WXYZ, broadcasts at a frequency of 101.1 MHz. What is the wavelength of this radiation?
Given: frequency
Asked for: wavelength
Strategy:
Substitute the value for the speed of light in meters per second into Equation 5 to calculate the wavelength in meters.
Solution:
From Equation 5, we know that the product of the wavelength and the frequency is the speed of the wave, which for
electromagnetic radiation is 2.998 × 108 m/s:

λν = c

8
= 2.998 × 10 m/s

Thus the wavelength λ is given by

c
λ =
ν

8
2.988 × 10 m/ s 1 M Hz
=( )( )
6 −1
101.1 M Hz 10 s

= 2.965 m

Exercise 1
As the police officer was writing up your speeding ticket, she mentioned that she was using a state-of-the-art radar gun
operating at 35.5 GHz. What is the wavelength of the radiation emitted by the radar gun?

Answer
8.45 mm

Light is also Particulate!

We have just spent quite a bit of space describing the wave-like properties of electromagnetic radiation. It turns out, however, that
several experimental results showed that light did not always act in a wave-like manner, but instead acted as if it consisted of
particles. One of these experimental results involved blackbody radiation. The term “blackbody” was coined by Gustav R.
Kirchhoff in 1862. The blackbody radiation curve was known experimentally, but its shape eluded physical explanation until the
year 1900. The classical approach to the blackbody radiation problem, known as the Rayleigh-Jeans law, in which radiation is
treated as waves (as you have learned above), fails to correctly reproduce experimental results. In the limit of short wavelengths,
the classical approach predicts infinite radiation intensity, which is inconsistent with the experimental results in which radiation
intensity has finite values in the ultraviolet region of the spectrum. This divergence between the results of classical theory and
experiments, which came to be called the ultraviolet catastrophe, shows how classical physics fails to explain the mechanism of
blackbody radiation, Figure 5 .
Graph shows the variation of radiation intensity with wavelength. Experimental data depicted as red dots shoots upwards at a wavelength of just under 1 micrometer, climbing to a maximum intensity of around 2 – 3
micrometers, then declining in a curve until almost reaching a baseline at 10. The Rayleigh—Jeans line is shown next to the experimental data line, and is first depicted coming onto the graph at a wavelength of 5 and
curving down to almost meet the experimental line around 10.

Figure 5 : The ultraviolet catastrophe: The Rayleigh–Jeans law does not explain the observed blackbody emission spectrum.
The blackbody radiation problem was solved in 1900 by Max Planck. The innovative idea that Planck introduced in his model is
the assumption that electromagnetic radiation must exist as individual packets of energy, which he called quanta. Planck related the
energy of electromagnetic radiation to its frequency by the equation

E = h ×ν (8)

4 [Link]
In Equation 8, ν is the frequency of the electromagnetic radiation. The physical constant h is called Planck’s constant:
−34
h = 6.626 × 10 J⋅s (9)

Planck’s blackbody radiation law is in agreement with the experimental blackbody radiation curve (Figure 6):
Graph shows the variation of radiation intensity with wavelength. Experimental data, red dots, show the maximum around 2 – 3 micrometers. Planck fit, line, perfectly matches experimental data.

Figure 6 : Planck’s theoretical result (continuous curve) and the experimental blackbody radiation curve (dots).

When Planck first published his result, the hypothesis of an energy quantum was not taken seriously by the physics community
because it did not follow from any established physics theory at that time. It was perceived, even by Planck himself, as a useful
mathematical trick that led to a good theoretical “fit” to the experimental curve. This perception was changed in 1905 when
Einstein published his explanation of the photoelectric effect, another experiment that was best explained if electromagnetic
radiation was acting as individual particles. In Einstein's explanation of the photoelectric effect, he gave Planck’s energy quantum a
new meaning: that of a particle of light. Einstein also gave a new name to Planck's quantum of electromagnetic enegry: a photon.
The concept of the photon had emerged from experimentation with thermal blackbody radiation, electromagnetic radiation emitted
as the result of a source’s temperature, which produces a continuous spectrum of energies. However, more direct evidence was
needed to verify the quantized nature of energy in all matter. In the next section, we describe how observation of the interaction of
individual atoms with visible light provided this evidence.

Line Spectra
Although objects at high temperature emit a continuous spectrum of electromagnetic radiation, a different kind of spectrum is
observed when pure samples of individual elements are heated. For example, when a high-voltage electrical discharge is passed
through a sample of hydrogen gas at low pressure, the resulting individual isolated hydrogen atoms caused by the dissociation of
H2 emit a red light. Unlike blackbody radiation, the color of the light emitted by the hydrogen atoms does not depend greatly on the
temperature of the gas in the tube. When the emitted light is passed through a prism, only a few narrow lines of particular
wavelengths, called a line spectrum, are observed rather than a continuous range of wavelengths (Figure 6). The light emitted by
hydrogen atoms is red because, of its four characteristic lines, the most intense line in its spectrum is in the red portion of the
visible spectrum, at 656 nm. With sodium, however, we observe a yellow color because the most intense lines in its spectrum are in
the yellow portion of the spectrum, at about 589 nm.

Figure 6: The Emission of Light by Hydrogen Atoms. (a) A sample of excited hydrogen atoms emits a characteristic red light. (b)
When the light emitted by a sample of excited hydrogen atoms is split into its component wavelengths by a prism, four
characteristic violet, blue, green, and red emission lines can be observed, the most intense of which is at 656 nm.
Such emission spectra were observed for many other elements in the late 19th century, which presented a major challenge because
classical physics was unable to explain them. Part of the explanation is provided by Planck’s equation: the observation of only a
few values of λ (or ν ) in the line spectrum meant that only a few values of E were possible. Thus the energy levels of a hydrogen
atom had to be quantized; in other words, only states that had certain values of energy were possible, or allowed. If a hydrogen
atom could have any value of energy, then a continuous spectrum would have been observed, similar to blackbody radiation.

Bohr's Model
In 1913, a Danish physicist, Niels Bohr (1885–1962; Nobel Prize in Physics, 1922), proposed a theoretical model for the hydrogen
atom that explained its emission spectrum. Bohr’s model required only one assumption: The electron moves around the nucleus in
circular orbits that can have only certain allowed radii. Rutherford’s earlier model of the atom had also assumed that electrons

5 [Link]
moved in circular orbits around the nucleus and that the atom was held together by the electrostatic attraction between the
positively charged nucleus and the negatively charged electron. Although we now know that the assumption of circular orbits was
incorrect, Bohr’s insight was to propose that the electron could occupy only certain regions of space.
Bohr’s model of the hydrogen atom gave an exact explanation for its observed emission spectrum. The following are his key
contributions to our understanding of atomic structure:
Electrons can occupy only certain regions of space, called orbits.
Orbits closer to the nucleus are lower in energy.
Electrons can move from one orbit to another by absorbing or emitting energy, giving rise to characteristic spectra.
Unfortunately, Bohr could not explain why the electron should be restricted to particular orbits. Also, despite a great deal of
tinkering, such as assuming that orbits could be ellipses rather than circles, his model could not quantitatively explain the emission
spectra of any element other than hydrogen (Figure 7). In fact, Bohr’s model worked only for species that contained just one
electron: H, He+, Li2+, and so forth. Scientists needed a fundamental change in their way of thinking about the electronic structure
of atoms to advance beyond the Bohr model.

Figure 7 : The Emission Spectra of Elements Compared with Hydrogen. These images show (a) hydrogen gas, which is atomized to
hydrogen atoms in the discharge tube; (b) neon; and (c) mercury. The strongest lines in the hydrogen spectrum are in the far UV
Lyman series starting at 124 nm and below. The strongest lines in the mercury spectrum are at 181 and 254 nm, also in the UV.
These are not shown.

Summary
Understanding the electronic structure of atoms requires an understanding of the properties of waves and electromagnetic radiation.
A wave is a periodic oscillation by which energy is transmitted through space. All waves are periodic, repeating regularly in both
space and time. Waves are characterized by several interrelated properties: wavelength (λ ), the distance between successive
waves; frequency (u), the number of waves that pass a fixed point per unit time; speed (v ), the rate at which the wave propagates
through space; and amplitude, the magnitude of the oscillation about the mean position. The speed of a wave is equal to the
product of its wavelength and frequency. Electromagnetic radiation consists of two perpendicular waves, one electric and one
magnetic, propagating at the speed of light (c ). Electromagnetic radiation is radiant energy that includes radio waves, microwaves,
visible light, x-rays, and gamma rays, which differ in their frequencies and wavelengths.
There is an intimate connection between the atomic structure of an atom and its spectral characteristics. Atoms of individual
elements emit light at only specific wavelengths, producing a line spectrum rather than the continuous spectrum of all wavelengths
produced by a hot object. Niels Bohr explained the line spectrum of the hydrogen atom by assuming that the electron moved in
circular orbits and that orbits with only certain radii were allowed. Lines in the spectrum were due to transitions in which an
electron moved from a higher-energy orbit with a larger radius to a lower-energy orbit with smaller radius. The orbit closest to the
nucleus represented the ground state of the atom and was most stable; orbits farther away were higher-energy excited states.
Transitions from an excited state to a lower-energy state resulted in the emission of light with only a limited number of
wavelengths. Atoms can also absorb light of certain energies, resulting in a transition from the ground state or a lower-energy
excited state to a higher-energy excited state. This produces an absorption spectrum, which has dark lines in the same position as
the bright lines in the emission spectrum of an element. Bohr’s model revolutionized the understanding of the atom but could not
explain the spectra of atoms heavier than hydrogen.

6 [Link]
Contributors
Modified by Joshua Halpern (Howard University)
Modified by Tom Neils (Grand Rapids Community College)

2.9 The Nature of Light is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

7 [Link]
2.10 Quantum Mechanics and The Atom
Skills to Develop
To apply the results of quantum mechanics to chemistry.

The wavelike nature of subatomic particles such as the electron made it impossible to use the equations of classical physics to
describe the motion of electrons in atoms. Scientists needed a new approach that took the wave behavior of the electron into
account. In 1926, an Austrian physicist, Erwin Schrödinger (1887–1961; Nobel Prize in Physics, 1933), developed wave
mechanics, a mathematical technique that describes the relationship between the motion of a particle that exhibits wavelike
properties (such as an electron) and its allowed energies.
Erwin Schrödinger (1887–1961)
Schrödinger’s unconventional approach to atomic theory was typical of his unconventional approach to life. He was notorious
for his intense dislike of memorizing data and learning from books. When Hitler came to power in Germany, Schrödinger
escaped to Italy. He then worked at Princeton University in the United States but eventually moved to the Institute for Advanced
Studies in Dublin, Ireland, where he remained until his retirement in 1955.

Although quantum mechanics uses sophisticated mathematics, you do not need to understand the mathematical details to follow our
discussion of its general conclusions. We focus on the properties of the wavefunctions that are the solutions of Schrödinger’s
equations.

Wavefunctions
A wavefunction (Ψ) is a mathematical function that relates the location of an electron at a given point in space (identified by x, y,
and z coordinates) to the amplitude of its wave, which corresponds to its energy. Thus each wavefunction is associated with a
particular energy E. The properties of wavefunctions derived from quantum mechanics are summarized here:
A wavefunction uses three variables to describe the position of an electron. A fourth variable is usually required to fully
describe the location of objects in motion. Three specify the position in space (as with the Cartesian coordinates x, y, and z), and
one specifies the time at which the object is at the specified location. For example, if you were the captain of a ship trying to
intercept an enemy submarine, you would need to know its latitude, longitude, and depth, as well as the time at which it was
going to be at this position (Figure 6.5.1). For electrons, we can ignore the time dependence because we will be using standing
waves, which by definition do not change with time, to describe the position of an electron.

Figure 1 : The Four Variables (Latitude, Longitude, Depth, and Time) required to precisely locate an object
The square of the wavefunction at a given point is proportional to the probability of finding an electron at that point,
which leads to a distribution of probabilities in space. The square of the wavefunction (Ψ ) is proportional to the probability
2

of finding an electron at a given point. We use probabilities because, according to Heisenberg’s uncertainty principle, we cannot

1 [Link]
 precisely specify the position of an electron. The probability of finding an electron at any point in space depends on several
factors, including the distance from the nucleus and, in many cases, the atomic equivalent of latitude and longitude. As one way
of graphically representing the probability distribution, the probability of finding an electron is indicated by the density of
colored dots, as shown for the ground state of the hydrogen atom in Figure 2.
Each wavefunction is associated with a particular energy. As in Bohr’s model, the energy of an electron in an atom is
quantized; it can have only certain allowed values. The major difference between Bohr’s model and Schrödinger’s approach is
that Bohr had to impose the idea of quantization arbitrarily, whereas in Schrödinger’s approach, quantization is a natural
consequence of describing an electron as a standing wave.

Figure 2 : Probability of Finding the Electron in the Ground State of the Hydrogen Atom at Different Points in Space. (a) The
density of the dots shows electron probability. (b) In this plot of Ψ2 versus r for the ground state of the hydrogen atom, the electron
probability density is greatest at r = 0 (the nucleus) and falls off with increasing r. Because the line never actually reaches the
horizontal axis, the probability of finding the electron at very large values of r is very small but not zero.

Quantum Numbers
Schrödinger’s approach uses three quantum numbers (n, l, and ml) to specify any wavefunction. The quantum numbers provide
information about the spatial distribution of an electron. Although n can be any positive integer, only certain values of l and ml are
allowed for a given value of n.

The Principal Quantum Number

The principal quantum number (n) tells the average relative distance of an electron from the nucleus:
n = 1, 2, 3, 4, … (1)

As n increases for a given atom, so does the average distance of an electron from the nucleus. A negatively charged electron that is,
on average, closer to the positively charged nucleus is attracted to the nucleus more strongly than an electron that is farther out in
space. This means that electrons with higher values of n are easier to remove from an atom. All wavefunctions that have the same
value of n are said to constitute a principal shell because those electrons have similar average distances from the nucleus. As you
will see, the principal quantum number n corresponds to the n used by Bohr to describe electron orbits and by Rydberg to describe
atomic energy levels.

The Azimuthal Quantum Number

The second quantum number is often called the azimuthal quantum number (l). The value of l describes the shape of the region
of space occupied by the electron. The allowed values of l depend on the value of n and can range from 0 to n − 1:

l = 0, 1, 2, … , n − 1 (2)

2 [Link]
For example, if n = 1, l can be only 0; if n = 2, l can be 0 or 1; and so forth. For a given atom, all wavefunctions that have the same
values of both n and l form a subshell. The regions of space occupied by electrons in the same subshell usually have the same
shape, but they are oriented differently in space.

The Magnetic Quantum Number

The third quantum number is the magnetic quantum number (m ). The value of m describes the orientation of the region in space
l l

occupied by an electron with respect to an applied magnetic field. The allowed values of m depend on the value of l: ml can range
l

from −l to l in integral steps:

ml = −l, −l + 1, … , 0, … , l − 1, l (3)

For example, if l = 0 , m can be only 0; if l = 1, ml can be −1, 0, or +1; and if l = 2, ml can be −2, −1, 0, +1, or +2.
l

Each wavefunction with an allowed combination of n, l, and ml values describes an atomic orbital, a particular spatial distribution
for an electron. For a given set of quantum numbers, each principal shell has a fixed number of subshells, and each subshell has a
fixed number of orbitals.

Example1 : n=4 Shell Structure

How many subshells and orbitals are contained within the principal shell with n = 4?
Given: value of n
Asked for: number of subshells and orbitals in the principal shell
Strategy:
A. Given n = 4, calculate the allowed values of l. From these allowed values, count the number of subshells.
B. For each allowed value of l, calculate the allowed values of ml. The sum of the number of orbitals in each subshell is the
number of orbitals in the principal shell.
Solution:
A We know that l can have all integral values from 0 to n − 1. If n = 4, then l can equal 0, 1, 2, or 3. Because the shell has four
values of l, it has four subshells, each of which will contain a different number of orbitals, depending on the allowed values of
ml.
B For l = 0, ml can be only 0, and thus the l = 0 subshell has only one orbital. For l = 1, ml can be 0 or ±1; thus the l = 1 subshell
has three orbitals. For l = 2, ml can be 0, ±1, or ±2, so there are five orbitals in the l = 2 subshell. The last allowed value of l is l
= 3, for which ml can be 0, ±1, ±2, or ±3, resulting in seven orbitals in the l = 3 subshell. The total number of orbitals in the n =
4 principal shell is the sum of the number of orbitals in each subshell and is equal to n2 = 16

Exercise 1 : n=3 Shell Structure

How many subshells and orbitals are in the principal shell with n = 3?

Answer
three subshells; nine orbitals

Rather than specifying all the values of n and l every time we refer to a subshell or an orbital, chemists use an abbreviated system
with lowercase letters to denote the value of l for a particular subshell or orbital:

l= 0 1 2 3

Designation s p d f

The principal quantum number is named first, followed by the letter s, p, d, or f as appropriate. (These orbital designations are
derived from historical terms for corresponding spectroscopic characteristics: sharp, principle, diffuse, and fundamental.) A 1s
orbital has n = 1 and l = 0; a 2p subshell has n = 2 and l = 1 (and has three 2p orbitals, corresponding to ml = −1, 0, and +1); a 3d
subshell has n = 3 and l = 2 (and has five 3d orbitals, corresponding to ml = −2, −1, 0, +1, and +2); and so forth.

3 [Link]
We can summarize the relationships between the quantum numbers and the number of subshells and orbitals as follows (Table
6.5.1):
Each principal shell has n subshells. For n = 1, only a single subshell is possible (1s); for n = 2, there are two subshells (2s and
2p); for n = 3, there are three subshells (3s, 3p, and 3d); and so forth. Every shell has an ns subshell, any shell with n ≥ 2 also
has an np subshell, and any shell with n ≥ 3 also has an nd subshell. Because a 2d subshell would require both n = 2 and l = 2,
which is not an allowed value of l for n = 2, a 2d subshell does not exist.
Each subshell has 2l + 1 orbitals. This means that all ns subshells contain a single s orbital, all np subshells contain three p
orbitals, all nd subshells contain five d orbitals, and all nf subshells contain seven f orbitals.

Each principal shell has n subshells, and each subshell has 2l + 1 orbitals.
Table 1 : Values of n, l, and ml through n = 4
N
u
m
b
e
r
o
f
O
r
b
Number of Orbitals in
n l Subshell Designation ml i
Subshell
t
a
l
s
i
n
S
h
e
l
l

1 0 1s 0 1 1

0 2s 0 1
2 4
1 2p −1, 0, 1 3

0 3s 0 1

3 1 3p −1, 0, 1 3 9

2 3d −2, −1, 0, 1, 2 5

0 4s 0 1

1 4p −1, 0, 1 3 1
4
2 4d −2, −1, 0, 1, 2 5 6

3 4f −3, −2, −1, 0, 1, 2, 3 7

Skills to Develop
To understand the 3D representation of electronic orbitals

An orbital is the quantum mechanical refinement of Bohr’s orbit. In contrast to his concept of a simple circular orbit with a fixed
radius, orbitals are mathematically derived regions of space with different probabilities of containing an electron.

4 [Link]
One way of representing electron probability distributions was illustrated previously for the 1s orbital of hydrogen. Because Ψ2
gives the probability of finding an electron in a given volume of space (such as a cubic picometer), a plot of Ψ2 versus distance
from the nucleus (r) is a plot of the probability density. The 1s orbital is spherically symmetrical, so the probability of finding a 1s
electron at any given point depends only on its distance from the nucleus. The probability density is greatest at r = 0 (at the
nucleus) and decreases steadily with increasing distance. At very large values of r, the electron probability density is very small but
not zero.
In contrast, we can calculate the radial probability (the probability of finding a 1s electron at a distance r from the nucleus) by
adding together the probabilities of an electron being at all points on a series of x spherical shells of radius r1, r2, r3,…, rx − 1, rx. In
effect, we are dividing the atom into very thin concentric shells, much like the layers of an onion (Figure 1a), and calculating the
probability of finding an electron on each spherical shell. Recall that the electron probability density is greatest at r = 0 (Figure 1b),
so the density of dots is greatest for the smallest spherical shells in part (a) in Figure 1. In contrast, the surface area of each
spherical shell is equal to 4πr2, which increases very rapidly with increasing r (Figure 1c). Because the surface area of the spherical
shells increases more rapidly with increasing r than the electron probability density decreases, the plot of radial probability has a
maximum at a particular distance (Figure 1d). Most important, when r is very small, the surface area of a spherical shell is so small
that the total probability of finding an electron close to the nucleus is very low; at the nucleus, the electron probability vanishes
(Figure 1d).

Figure 1 : Most Probable Radius for the Electron in the Ground State of the Hydrogen Atom. (a) Imagine dividing the atom’s total
volume into very thin concentric shells as shown in the onion drawing. (b) A plot of electron probability density Ψ2 versus r shows
that the electron probability density is greatest at r = 0 and falls off smoothly with increasing r. The density of the dots is therefore
greatest in the innermost shells of the onion. (c) The surface area of each shell, given by 4πr2, increases rapidly with increasing r.
(d) If we count the number of dots in each spherical shell, we obtain the total probability of finding the electron at a given value of
r. Because the surface area of each shell increases more rapidly with increasing r than the electron probability density decreases, a
plot of electron probability versus r (the radial probability) shows a peak. This peak corresponds to the most probable radius for
the electron, 52.9 pm, which is exactly the radius predicted by Bohr’s model of the hydrogen atom.
For the hydrogen atom, the peak in the radial probability plot occurs at r = 0.529 Å (52.9 pm), which is exactly the radius
calculated by Bohr for the n = 1 orbit. Thus the most probable radius obtained from quantum mechanics is identical to the radius
calculated by classical mechanics. In Bohr’s model, however, the electron was assumed to be at this distance 100% of the time,
whereas in the Schrödinger model, it is at this distance only some of the time. The difference between the two models is
attributable to the wavelike behavior of the electron and the Heisenberg uncertainty principle.

5 [Link]
Figure 2 compares the electron probability densities for the hydrogen 1s, 2s, and 3s orbitals. Note that all three are spherically
symmetrical. For the 2s and 3s orbitals, however (and for all other s orbitals as well), the electron probability density does not fall
off smoothly with increasing r. Instead, a series of minima and maxima are observed in the radial probability plots (Figure 2c). The
minima correspond to spherical nodes (regions of zero electron probability), which alternate with spherical regions of nonzero
electron probability. The existence of these nodes is a consequence of changes of wave phase in the wavefunction Ψ.

Figure 2 : Probability Densities for the 1s, 2s, and 3s Orbitals of the Hydrogen Atom. (a) The electron probability density in any
plane that contains the nucleus is shown. Note the presence of circular regions, or nodes, where the probability density is zero. (b)
Contour surfaces enclose 90% of the electron probability, which illustrates the different sizes of the 1s, 2s, and 3s orbitals. The
cutaway drawings give partial views of the internal spherical nodes. The orange color corresponds to regions of space where the
phase of the wave function is positive, and the blue color corresponds to regions of space where the phase of the wave function is
negative. (c) In these plots of electron probability as a function of distance from the nucleus (r) in all directions (radial
probability), the most probable radius increases as n increases, but the 2s and 3s orbitals have regions of significant electron
probability at small values of r.

s Orbitals (l=0)
Three things happen to s orbitals as n increases (Figure 2):
1. They become larger, extending farther from the nucleus.
2. They contain more nodes. This is similar to a standing wave that has regions of significant amplitude separated by nodes, points
with zero amplitude.
3. For a given atom, the s orbitals also become higher in energy as n increases because of their increased distance from the
nucleus.

6 [Link]
Orbitals are generally drawn as three-dimensional surfaces that enclose 90% of the electron density, as was shown for the hydrogen
1s, 2s, and 3s orbitals in part (b) in Figure 2. Although such drawings show the relative sizes of the orbitals, they do not normally
show the spherical nodes in the 2s and 3s orbitals because the spherical nodes lie inside the 90% surface. Fortunately, the positions
of the spherical nodes are not important for chemical bonding.

p Orbitals (l=1)
Only s orbitals are spherically symmetrical. As the value of l increases, the number of orbitals in a given subshell increases, and the
shapes of the orbitals become more complex. Because the 2p subshell has l = 1, with three values of ml (−1, 0, and +1), there are
three 2p orbitals.

Figure 3 : Electron Probability Distribution for a Hydrogen 2p Orbital. The nodal plane of zero electron density separates the two
lobes of the 2p orbital. As in Figure 2, the colors correspond to regions of space where the phase of the wave function is positive
(orange) and negative (blue).
The electron probability distribution for one of the hydrogen 2p orbitals is shown in Figure 3. Because this orbital has two lobes of
electron density arranged along the z axis, with an electron density of zero in the xy plane (i.e., the xy plane is a nodal plane), it is a
2p orbital. As shown in Figure 4 , the other two 2p orbitals have identical shapes, but they lie along the x axis (2p ) and y axis (
z x

2p ), respectively. Note that each p orbital has just one nodal plane. In each case, the phase of the wave function for each of the 2p
y

orbitals is positive for the lobe that points along the positive axis and negative for the lobe that points along the negative axis. It is
important to emphasize that these signs correspond to the phase of the wave that describes the electron motion, not to positive or
negative charges.

Figure 4 The Three Equivalent 2p Orbitals of the Hydrogen Atom

The surfaces shown enclose 90% of the total electron probability for the 2px, 2py, and 2pz orbitals. Each orbital is oriented along the
axis indicated by the subscript and a nodal plane that is perpendicular to that axis bisects each 2p orbital. The phase of the wave
function is positive (orange) in the region of space where x, y, or z is positive and negative (blue) where x, y, or z is negative. Just
as with the s orbitals, the size and complexity of the p orbitals for any atom increase as the principal quantum number n increases.
The shapes of the 90% probability surfaces of the 3p, 4p, and higher-energy p orbitals are, however, essentially the same as those
shown in Figure 4.

7 [Link]
d Orbitals (l=2)
Subshells with l = 2 have five d orbitals; the first principal shell to have a d subshell corresponds to n = 3. The five d orbitals have
ml values of −2, −1, 0, +1, and +2.

Figure 5 : The Five Equivalent 3d Orbitals of the Hydrogen Atom. The surfaces shown enclose 90% of the total electron
probability for the five hydrogen 3d orbitals. Four of the five 3d orbitals consist of four lobes arranged in a plane that is
intersected by two perpendicular nodal planes. These four orbitals have the same shape but different orientations. The fifth 3d
orbital, 3d , has a distinct shape even though it is mathematically equivalent to the others. The phase of the wave function for the
z
2

different lobes is indicated by color: orange for positive and blue for negative.
The hydrogen 3d orbitals, shown in Figure 5, have more complex shapes than the 2p orbitals. All five 3d orbitals contain two nodal
surfaces, as compared to one for each p orbital and zero for each s orbital. In three of the d orbitals, the lobes of electron density are
oriented between the x and y, x and z, and y and z planes; these orbitals are referred to as the 3d , \)3d_{xz}\), and 3d orbitals,
xy yz

respectively. A fourth d orbital has lobes lying along the x and y axes; this is the 3d 2
x −y orbital. The fifth 3d orbital, called the
2

3dz2 orbital, has a unique shape: it looks like a 2p orbital combined with an additional doughnut of electron probability lying in
z

the xy plane. Despite its peculiar shape, the 3d orbital is mathematically equivalent to the other four and has the same energy. In
z2

contrast to p orbitals, the phase of the wave function for d orbitals is the same for opposite pairs of lobes. As shown in Figure 5, the
phase of the wave function is positive for the two lobes of the dz orbital that lie along the z axis, whereas the phase of the wave
2

function is negative for the doughnut of electron density in the xy plane. Like the s and p orbitals, as n increases, the size of the d
orbitals increases, but the overall shapes remain similar to those depicted in Figure 5.

f Orbitals (l=3)
Principal shells with n = 4 can have subshells with l = 3 and ml values of −3, −2, −1, 0, +1, +2, and +3. These subshells consist of
seven f orbitals. Each f orbital has three nodal surfaces, so their shapes are complex. Because f orbitals are not particularly
important for our purposes, we do not discuss them further, and orbitals with higher values of l are not discussed at all.

Orbital Energies
Although we have discussed the shapes of orbitals, we have said little about their comparative energies. We begin our discussion of
orbital energies by considering atoms or ions with only a single electron (such as H or He+).
The relative energies of the atomic orbitals with n ≤ 4 for a hydrogen atom are plotted in Figure 6; note that the orbital energies
depend on only the principal quantum number n. Consequently, the energies of the 2s and 2p orbitals of hydrogen are the same; the
energies of the 3s, 3p, and 3d orbitals are the same; and so forth. Quantum mechanics predicts that in the hydrogen atom, all
orbitals with the same value of n (e.g., the three 2p orbitals) are degenerate, meaning that they have the same energy. The orbital

8 [Link]
energies obtained for hydrogen using quantum mechanics are exactly the same as the allowed energies calculated by Bohr. In
contrast to Bohr’s model, however, which allowed only one orbit for each energy level, quantum mechanics predicts that there are
4 orbitals with different electron density distributions in the n = 2 principal shell (one 2s and three 2p orbitals), 9 in the n = 3
principal shell, and 16 in the n = 4 principal [Link] different values of l and ml for the individual orbitals within a given principal
shell are not important for understanding the emission or absorption spectra of the hydrogen atom under most conditions, but they
do explain the splittings of the main lines that are observed when hydrogen atoms are placed in a magnetic field. Figure 6 shows
that the energy levels become closer and closer together as the value of n increases, as expected because of the 1/n2 dependence of
orbital energies.

Figure 6 : Orbital Energy Level Diagram for the Hydrogen Atom with a single electron. Each box corresponds to one orbital. Note
that the difference in energy between orbitals decreases rapidly with increasing values of n.
The energies of the orbitals in any species with only one electron can be calculated by a minor variation of Bohr’s equation, which
can be extended to other single-electron species by incorporating the nuclear charge Z (the number of protons in the nucleus):
2
Z
E =− Rhc (4)
2
n

In general, both energy and radius decrease as the nuclear charge increases. Thus the most stable orbitals (those with the lowest
energy) are those closest to the nucleus. For example, in the ground state of the hydrogen atom, the single electron is in the 1s
orbital, whereas in the first excited state, the atom has absorbed energy and the electron has been promoted to one of the n = 2
orbitals. In ions with only a single electron, the energy of a given orbital depends on only n, and all subshells within a principal
shell, such as the p , p , and p orbitals, are degenerate.
x y z

Summary
There is a relationship between the locations of electrons in atoms and molecules and their energies that is described by quantum
mechanics. Because of wave–particle duality, scientists must deal with the probability of an electron being at a particular point in
space. To do so required the development of quantum mechanics, which uses wavefunctions (Ψ) to describe the mathematical
relationship between the location of electrons in atoms and molecules and their energies. Wavefunctions have four important
properties:
1. the wavefunction uses three variables (Cartesian axes x, y, and z) to describe the position of an electron;
2. the probability of finding an electron at a given point is proportional to the square of the wavefunction at that point, leading to a
distribution of probabilities in space that is often portrayed as an electron density plot;
3. describing electron distributions as standing waves leads naturally to the existence of sets of quantum numbers characteristic
of each wavefunction; and

9 [Link]
 4. each spatial distribution of the electron described by a wavefunction with a given set of quantum numbers has a particular
energy.
Quantum numbers provide important information about the energy and spatial distribution of an electron. The principal quantum
number n can be any positive integer; as n increases for an atom, the average distance of the electron from the nucleus also
increases. All wavefunctions with the same value of n constitute a principal shell in which the electrons have similar average
distances from the nucleus. The azimuthal quantum number l can have integral values between 0 and n − 1; it describes the
shape of the electron distribution. wavefunctions that have the same values of both n and l constitute a subshell, corresponding to
electron distributions that usually differ in orientation rather than in shape or average distance from the nucleus. The magnetic
quantum number ml can have 2l + 1 integral values, ranging from −l to +l, and describes the orientation of the electron
distribution. Each wavefunction with a given set of values of n, l, and ml describes a particular spatial distribution of an electron in
an atom, an atomic orbital.
The four chemically important types of atomic orbital correspond to values of ℓ = 0 , 1, 2, and 3. Orbitals with ℓ = 0 are s orbitals
and are spherically symmetrical, with the greatest probability of finding the electron occurring at the nucleus. All orbitals with
values of n > 1 and ell = 0 contain one or more nodes. Orbitals with ℓ = 1 are p orbitals and contain a nodal plane that includes
the nucleus, giving rise to a dumbbell shape. Orbitals with ℓ = 2 are d orbitals and have more complex shapes with at least two
nodal surfaces. Orbitals with ℓ = 3 are f orbitals, which are still more complex.
Because its average distance from the nucleus determines the energy of an electron, each atomic orbital with a given set of quantum
numbers has a particular energy associated with it, the orbital energy.
2
Z
E =− Rhc
2
n

In atoms or ions with only a single electron, all orbitals with the same value of n have the same energy (they are degenerate), and
the energies of the principal shells increase smoothly as n increases. An atom or ion with the electron(s) in the lowest-energy
orbital(s) is said to be in its ground state, whereas an atom or ion in which one or more electrons occupy higher-energy orbitals is
said to be in an excited state.

Contributors
Modified by Joshua Halpern (Howard University)
Modified by Tom Neils (Grand Rapids Community College)

2.10 Quantum Mechanics and The Atom is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

10 [Link]
2.11 Trends of the Periodic Table
Skills to Develop
Describe and explain the observed trends in atomic size, ionization energy, and electron affinity of the elements

The elements in groups (vertical columns) of the periodic table exhibit similar chemical behavior. This similarity occurs because
the members of a group have the same number and distribution of electrons in their valence shells. However, there are also other
patterns in chemical properties on the periodic table. For example, as we move down a group, the metallic character of the atoms
increases. Oxygen, at the top of Group VIA (16), is a colorless gas; in the middle of the group, selenium is a semiconducting solid;
and, toward the bottom, polonium is a silver-grey solid that conducts electricity.
As we go across a period from left to right, we add a proton to the nucleus and an electron to the valence shell with each successive
element. As we go down the elements in a group, the number of electrons in the valence shell remains constant, but the principal
quantum number increases by one each time. An understanding of the electronic structure of the elements allows us to examine
some of the properties that govern their chemical behavior. These properties vary periodically as the electronic structure of the
elements changes. They are (1) size (radius) of atoms and ions, (2) ionization energies, (3) electron affinities, (4)
electronegativities, and (5) the number of valence electrons.

Variation in Covalent Radius

The quantum mechanical picture makes it difficult to establish a definite size of an atom. However, there are several practical ways
to define the radius of atoms and, thus, to determine their relative sizes that give roughly similar values. We will use the covalent
radius (Figure 1), which is defined as one-half the distance between the nuclei of two identical atoms when they are joined by a
covalent bond (this measurement is possible because atoms within molecules still retain much of their atomic identity).

Figure 1 : (a) The radius of an atom is defined as one-half the distance between the nuclei in a molecule consisting of two identical
atoms joined by a covalent bond. The atomic radius for the halogens increases down the group as n increases. (b) Covalent radii of
the elements are shown to scale. The general trend is that radii increase down a group and decrease across a period.

1 [Link]
We know that as we move down a group, the principal quantum number, n, increases by one for each element. Thus, the electrons
are being added to a region of space that is increasingly distant from the nucleus. Consequently, the size of the atom (and its
covalent radius) must increase as we increase the distance of the outermost electrons from the nucleus. This trend is illustrated for
the covalent radii of the halogens in Table 1 and Figure 1. The trends for the entire periodic table can be seen in Figure 2.
Table 1 : Covalent Radii of the Halogen Group Elements
N
u
c
l
e
a
Atom Covalent radius (pm) r
c
h
a
r
g
e

+
F 64
9
+
Cl 99 1
7
+
Br 114 3
5
+
I 133 5
3
+
At 148 8
5

As shown in Figure 2, as we move across a period from left to right, we generally find that each element has a smaller covalent
radius than the element preceding it. This trend can be explained with the concept of effective nuclear charge, Z . This is the pull
ef f

exerted on a specific electron by the nucleus, taking into account any electron–electron repulsions. For hydrogen, there is only one
electron and so the nuclear charge (Z) and the effective nuclear charge (Zeff) are equal. For all other atoms, the inner electrons
partially shield the outer electrons from the pull of the nucleus, and thus:
Zeff = Z − shielding (1)

Shielding is determined by the probability of another electron being between the electron of interest and the nucleus, as well as by
the electron–electron repulsions the electron of interest encounters. Core electrons are adept at shielding, while electrons in the
same valence shell do not block the nuclear attraction experienced by each other as efficiently. Thus, each time we move from one
element to the next across a period, Z increases by one, but the shielding increases only slightly. Thus, Zeff increases as we move
from left to right across a period. The stronger pull (higher effective nuclear charge) experienced by electrons on the right side of
the periodic table draws them closer to the nucleus, making the covalent radii smaller.

2 [Link]
 Figure 2 : Within each period, the trend in atomic radius decreases as Z increases; for example, from K to Kr. Within each group
(e.g., the alkali metals shown in purple), the trend is that atomic radius increases as Z increases.
Thus, as we would expect, the outermost or valence electrons are easiest to remove because they have the highest energies, are
shielded more, and are farthest from the nucleus. As a general rule, when the representative elements form cations, they do so by
the loss of the s or p electrons that are farthest from the nucleus.

Example 1 : Sorting Atomic Radii

Predict the order of increasing covalent radius for Ge, Fl, Br, Kr.
Solution
Radius increases as we move down a group, so Ge < Fl (Note: Fl is the symbol for flerovium, element 114, NOT fluorine).
Radius decreases as we move across a period, so Kr < Br < Ge. Putting the trends together, we obtain Kr < Br < Ge < Fl.

Exercise 1
Give an example of an atom whose size is smaller than fluorine.

Answer
Ne or He

Variation in Ionization Energies

The amount of energy required to remove the most loosely bound electron from a gaseous atom in its ground state is called its first
ionization energy (IE1). The first ionization energy for an element, X, is the energy required to form a cation with +1 charge:
+ −
X(g) ⟶ X (g) + e IE (2)
1

The energy required to remove the second most loosely bound electron is called the second ionization energy (IE2).
+ 2+ −
X (g) ⟶ X (g) + e IE (3)
2

The energy required to remove the third electron is the third ionization energy, and so on. Energy is always required to remove
electrons from atoms or ions, so ionization processes are endothermic and IE values are always positive. For larger atoms, the most
loosely bound electron is located farthest from the nucleus and so is easier to remove. Thus, as size (atomic radius) increases, the
ionization energy should decrease. Relating this logic to what we have just learned about radii, we would expect first ionization
energies to decrease down a group and to increase across a period.

3 [Link]
 Figure 4 : The first ionization energy of the elements in the first five periods are plotted against their atomic number.
Figure 4 graphs the relationship between the first ionization energy and the atomic number of several elements. Within a period, the
values of first ionization energy for the elements (IE1) generally increases with increasing Z. Down a group, the IE1 value generally
decreases with increasing Z. There are some systematic deviations from this trend, however we will not attempt to explain them in
this course.

Figure 5 : This version of the periodic table shows the first ionization energy of (IE: 1), in kJ/mol, of selected elements.

Example 2 : Ranking Ionization Energies

Predict the order of increasing energy for the following processes: IE1 for F, IE1 for Se, IE1 for N, IE1 for At.
Solution
Removing the highest energy electron requires less energy the farther an electron is away from the nucleus. The size of the
atoms is At > Se > N > F, so the IE trend is the reverse:
IE1(At) < IE1(Se) < IE3(N) < IE2(F).

Exercise 2
Which has the lowest value for IE1: O, Po, Pb, or Ba?

Answer

4 [Link]
 Ba

Variation in Electron Affinities

The electron affinity [EA] is the energy change for the process of adding an electron to a gaseous atom to form an anion (negative
ion).
− −
X(g) + e ⟶ X (g) EA (4)
1

This process can be either endothermic or exothermic, depending on the element. The EA of some of the elements is given in
Figure 6. You can see that many of these elements have negative values of EA, which means that energy is released when the
gaseous atom accepts an electron. However, for some elements, energy is required for the atom to become negatively charged and
the value of their EA is positive. There are good explanations for the variations in EA, but we will not discuss them in this class.
Just as with ionization energy, subsequent EA values are associated with forming ions with greater charges. The second EA is the
energy associated with adding an electron to an anion to form a –2 ion, and so on.

Figure 6 : This version of the periodic table displays the electron affinity values (in kJ/mol) for selected elements.:
The properties discussed in this section (size of atoms, ionization energies, and electron affinities) are central to understanding
chemical reactivity. For example, because fluorine has an energetically favorable EA and a large energy barrier to ionization (IE), it
is much easier to form fluorine anions than cations. Metallic properties including conductivity and malleability (the ability to be
formed into sheets) depend on having electrons that can be removed easily. Thus, metallic character increases as we move down a
group and decreases across a period in the same trend observed for atomic size because it is easier to remove an electron that is
farther away from the nucleus.
Variation in Electronegativity

The elements with the highest ionization energies are generally those with the most negative electron affinities, which are located
toward the upper right corner of the periodic table. Conversely, the elements with the lowest ionization energies are generally those
with the least negative electron affinities and are located in the lower left corner of the periodic table.
Because the tendency of an element to gain or lose electrons is so important in determining its chemistry, various methods have
been developed to quantitatively describe this tendency. The most important method uses a measurement called electronegativity,
defined as the relative ability of an atom to attract electrons to itself in a chemical compound. Elements with high
electronegativities tend to acquire electrons in chemical reactions and are found in the upper right corner of the periodic table.
Elements with low electronegativities tend to lose electrons in chemical reactions and are found in the lower left corner of the
periodic table.
Unlike ionization energy or electron affinity, the electronegativity of an atom is not a simple, fixed property that can be directly
measured in a single experiment. In fact, an atom’s electronegativity should depend to some extent on its chemical environment
because the properties of an atom are influenced by its neighbors in a chemical compound. Nevertheless, when different methods

5 [Link]
for assigning the electronegativity of an atom are compared, they all tend to assign similar relative values to a given element. For
example, all scales predict that fluorine has the highest electronegativity and cesium the lowest of the stable elements, which
suggests that all the methods are measuring the same fundamental property.

Electronegativity is defined as the ability of an atom in a particular molecule to attract

electrons to itself. The greater the value, the greater the attractiveness for electrons.
Electronegativity is a function of:
1. the atom's ionization energy (how strongly the atom holds on to its own electrons) and
2. the atom's electron affinity (how strongly the atom attracts other electrons).
Both of these are properties of the isolated atom. An element will be highly electronegative if it has a large (negative) electron
affinity and a high ionization energy (always endothermic, or positive, for neutral atoms). Thus, it will attract electrons from other
atoms and resist having its own electrons attracted away.
The Pauling Electronegativity Scale
The original electronegativity scale, developed in the 1930s by Linus Pauling (1901– 1994) was based on measurements of the
strengths of covalent bonds between different elements. Pauling arbitrarily set the electronegativity of fluorine at 4.0 (although
today it has been refined to 4.09), thereby creating a scale in which all elements have values between 0 and 4.0.

Figure 1 : A Plot of Periodic Variation of Electronegativity with Atomic Number for the First Six Rows of the Periodic Table
Periodic variations in Pauling’s electronegativity values are illustrated in Figures 1 and 2. If we ignore the inert gases and elements
for which no stable isotopes are known, we see that fluorine (χ = 3.98) is the most electronegative element and cesium is the least
electronegative nonradioactive element (χ = 0.79). Because electronegativities generally increase diagonally from the lower left to
the upper right of the periodic table, elements lying on diagonal lines running from upper left to lower right tend to have
comparable values (e.g., O and Cl and N, S, and Br). It is very important to note that the electronegativity of H is similar to that of
C.

Figure 2 : Pauling Electronegativity Values of the s-, p-, d-, and f-Block Elements. Values for most of the actinides are approximate.
Elements for which no data are available are shown in gray. Source: Data from L. Pauling, The Nature of the Chemical Bond, 3rd

6 [Link]
 ed. (1960).
Linus Pauling (1901-1994)
When he was nine, Pauling’s father died, and his mother tried to convince him to quit school to support the family. He did not
quit school, but was later denied a high school degree, and had to work several jobs to put himself through college. Pauling
would go on to become one of the most influential chemists of the century if not all time. He won two Nobel Prizes, one for
chemistry in 1954 and one for peace in 1962.

Pauling’s method is limited by the fact that many elements do not form stable covalent compounds with other elements; hence their
electronegativities cannot be measured by his method. Other definitions have since been developed that address this problem, e.g.,
the Mulliken, Allred-Rochow, and Allen electronegativity scales. The Mulliken electronegativity of an element is the average of its
first ionization energy and the absolute value of its electron affinity, showing the relationship between electronegativity and these
other periodic properties.
Electronegativity Differences between Metals and Nonmetals
An element’s electronegativity provides us with a single value that we can use to characterize the chemistry of an element.
Elements with a high electronegativity (\ ≥ 2.2 in Figure 2) have very negative affinities and large ionization potentials, so they are
generally nonmetals and electrical insulators that tend to gain electrons in chemical reactions (i.e., they are oxidants). In contrast,
elements with a low electronegativity (≤ 1.8) have electron affinities that have either positive or small negative values and small
ionization potentials, so they are generally metals and good electrical conductors that tend to lose their valence electrons in
chemical reactions (i.e., they are reductants). In between the metals and nonmetals, along the heavy diagonal line running from B
to At is a group of elements with intermediate electronegativities (~ 2.0). These are the metalloids (or semimetals), elements that
have some of the chemical properties of both nonmetals and metals. The distinction between metals and nonmetals is one of the
most fundamental we can make in categorizing the elements and predicting their chemical behavior. Figure 3 shows the strong
correlation between electronegativity values, metallic versus nonmetallic character, and location in the periodic table.

7 [Link]
 Figure 3 : Three-Dimensional Plots Demonstrating the Relationship between Electronegativity and the Metallic/Nonmetallic
Character of the Elements. (a) A plot of electrical resistivity (measured resistivity to electron flow) at or near room temperature
shows that substances with high resistivity (little to no measured electron flow) are electrical insulators, whereas substances with
low resistivity (high measured electron flow) are metals. (b) A plot of Pauling electronegativities for a like set of elements shows
that high electronegativity values (≥ about 2.2) correlate with high electrical resistivities (insulators). Low electronegativity values
(≤ about 2.2) correlate with low resistivities (metals). Because electrical resistivity is typically measured only for solids and liquids,
the gaseous elements do not appear in part (a).

Electronegativity values increase from lower left to upper right in the periodic table.

The rules for assigning oxidation states are based on the relative electronegativities of the elements; the more electronegative
element in a binary compound is assigned a negative oxidation state. As we shall see, electronegativity values are also used to
predict bond polarities, and the kinds of reactions that compounds undergo.

Example 1 : Increasing Electronegativity

On the basis of their positions in the periodic table, arrange Cl, Se, Si, and Sr in order of increasing electronegativity and
classify each as a metal, a nonmetal, or a metalloid.
Given: four elements
Asked for: order by increasing electronegativity and classification
Strategy:
A. Locate the elements in the periodic table. From their diagonal positions from lower left to upper right, predict their relative
electronegativities.
B. Arrange the elements in order of increasing electronegativity.
C. Classify each element as a metal, a nonmetal, or a metalloid according to its location about the diagonal belt of metalloids
running from B to At.
Solution:
A Electronegativity increases from lower left to upper right in the periodic table (Figure 8.4.2). Because Sr lies far to the left of
the other elements given, we can predict that it will have the lowest electronegativity. Because Cl lies above and to the right of
Se, we can predict that χCl > χSe. Because Si is located farther from the upper right corner than Se or Cl, its electronegativity
should be lower than those of Se and Cl but greater than that of Sr. B The overall order is therefore χSr < χSi < χSe < χCl.
C To classify the elements, we note that Sr lies well to the left of the diagonal belt of metalloids running from B to At; while Se
and Cl lie to the right and Si lies in the middle. We can predict that Sr is a metal, Si is a metalloid, and Se and Cl are nonmetals.

Exercise 1
On the basis of their positions in the periodic table, arrange Ge, N, O, Rb, and Zr in order of increasing electronegativity and
classify each as a metal, a nonmetal, or a metalloid.

Answer
Rb < Zr < Ge < N < O; metals (Rb, Zr); metalloid (Ge); nonmetal (N, O)

Number of Valence Electrons

One last trend that occurs on the periodic table is the trend of the number of valence electrons, which are the electrons that are
farthest from the nucleus, and thus are the electrons that have the most energy, and that are involved in chemical reactions. For the
A Group elements (IA-VIIIA), the the valence electrons are those electrons in the s and p subshells of the highest energy shell.
Conveniently, the number of valence electrons for the A Group elements is equal to the group number. Thus, Na in Group IA has 1
valence electron, whereas C, in Group IVA has 4 valence electrons.

8 [Link]
Summary
The arrangement of electrons in atoms allows us to understand many periodic trends. Covalent radius increases as we move down a
group because the electrons are located in shells that are further from the nucleus. Covalent radius mostly decreases as we move
left to right across a period because the electrons are pulled in more tightly to the nucleus. Ionization energy (IE, the energy
associated with forming a cation) decreases down a group and mostly increases across a period because it is easier to remove an
electron from a larger atom. Electron affinity (EA, the energy associated with forming an anion) has no simply-explained trends.
Electronegativity (EN) is defined as the relative ability of an atom to attract electrons to itself in a chemical compound. Fluorine
has been assigned the highest EN value and the EN values of other elements decrease the farther they are from fluorine.

Glossary

covalent radius
one-half the distance between the nuclei of two identical atoms when they are joined by a covalent bond

effective nuclear charge

charge that leads to the Coulomb force exerted by the nucleus on an electron, calculated as the nuclear charge minus shielding

electron affinity
energy required to add an electron to a gaseous atom to form an anion

ionization energy
energy required to remove an electron from a gaseous atom or ion. The associated number (e.g., second ionization energy)
corresponds to the charge of the ion produced (X2+)

isoelectronic
group of ions or atoms that have identical electron configurations

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).
Modified by Tom Neils (Grand Rapids Community College)

2.11 Trends of the Periodic Table is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

9 [Link]
2.12 Example Problems
1. Atomic Structure Problems
1. What is the difference between a gram and an atomic mass unit (a.k.a. a Dalton)?
2. What makes all barium (Ba) atoms different from all atoms of any other element?
3. Isotopes always have different densities. Why is this?
4. Write the nuclide symbol for the following particles:
a) a copper atom with 35 neutrons and 27 electrons
b) a sulfur atom with 15 neutrons and 17 electrons
5. What is the weighted average mass of potassium if the three major isotopes are K-39 with a mass of 38.96371 amu and an
abundance of 93.1%; K-40 with a mass of 39.974 amu and an abundance of 0.00118%; K-41 with a mass of 40.96184 and an
abundance of 6.88%?

Exercise 1
Answers to Q 1-5

Answer
1. A gram is a mass unit useful for the macroscopic scale. An amu is a mass unit appropriate for the atomic scale because
1.0000 amu is 1.6605 x 10-24 grams.
2. All barium atoms have 56 protons, and all atoms with 56 protons are barium atoms.
3. Isotopes differ by the number of neutrons. the neutrons exist in the nucleus of an atom, and changing the size of the
nucleus does not change the size of the atom. Thus isotopes have different masses, but their volumes are the same, meaning
they have different densities.
4. a) 64
29
Cu
2+
b) 31
16
S
1−

5. (38.96371)(.931) + (39.974)(0.0000118) + (40.96184)(0.0688) = 39.09 amu

2. The Mole
6. How many moles of sodium atoms (Na) are there in 43.6 grams of sodium atoms?
7. How many grams of argon (Ar) are there in 134 grams of argon atoms?
8. What is the mass, in grams, of 0.675 moles of radium (Ra) atoms?
9. What is the mass, in grams, of 9.64 x 1023 osmium (Os) atoms?

Exercise 2
Answers to Q 6-9

Answer
1 mole N a atoms
6. 43.6 grams N a atomsx = 1.90 grams Na atoms
22.99 grams N a atoms

23
1 mole Ar atoms 6.022x 10 Ar atoms
7. 134 grams Ar atomsx x = 2.02x1024 Ar atoms
39.85 grams Ar atoms 1 mole Ar atoms

226 grams Ra atoms

8. 0.675 moles Ra atomsx = 153 grams Ra atoms
1 mole Ra atoms

1 mole Os atoms 190.23 grams Os atoms

9. 9.64x 10 23
Os atomsx
23
x = 305 grams Os atoms.
6.022x 10 Os atoms 1 mole Os atoms

1 [Link]
3. Nuclear Reactions
10. Determine the nuclide symbol for the missing particle in the following nuclear reactions:
a) 35
16
S+
4
2
He →
18
9
F+ ?

b) 139
56
Ba →
0
−1
β+ ?

c) 90
38
Sr +
182
75
Re → 20 n+ ?
1

11. If you start with 25.00 grams of a radioactive nuclide, X, how many grams of X will remain after 3 half-lives?
12. If you start with 37.3 grams of radioactive nuclide X, how many hours will it take until there are only 10.0 grams of X? The
half-life of X is 17.1 hours.

Exercise 3
Answers to Q 10-12

Answer
10. a) 21
9
F b) 139
57
La c) 270
113
Nh

11. 25.00 → 12.50 → 6.250 → 3.125 g or (1/2)3(25.00 grams) = 3.125 grams

10.0 log(0.2681)
12. 10.0g = (1/2) n
(37.3g) ⇒ n
= (1/2 ) ⇒ = n = 1.899 half-lives. 1.899 x 17.1 hours = 32.5 hours.
37.3 log(0.5)

4. Electronic Structure
13. Which has the greater energy per photon, green light or red light?
14. What does an atomic orbital boundary surface tell you?
15. Tell the maximum number of electrons possible in:
a) a 1s orbital
b) a 5d orbital
c) a 2p subshell
d) a 4d subshell
e) shell 3
16. Compare a Ca atom and an Se atom in terms of
a) atomic size
b) ionization energy
c) electronegativity
d) number of valence electrons

Exercise 4
Answers to Q 13-16

Answer
13. Energy is directly proportional to the frequency, and green light has a higher frequency than red light, so green photons
have higher energy than red photons.
14. An atomic orbital boundary surface tells the volume of space in which an electron can be found 90% of the time.
15. a) 2 b) 2 c) 6 d) 10 e) 18
16. A Ca atom a) is larger than a Se atom b) has a lower first I.E. than a Se atom c) has a lower EN than a Se atom d) has
fewer valence electrons than a Se atom.

2 [Link]
Modified by Tom Neils (Grand Rapids Community College)

2.12 Example Problems is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

3 [Link]
 CHAPTER OVERVIEW

3: Chemical Formulas and Bonding

3.1 An Atomic-Level Perspective of Ionic and Covalent Compounds
3.2 Composition of Compounds
3.3 Chemical Bonds
3.4 Ionic Compounds: Formulas and Names
3.5 Covalently-Bonded Species: Formulas and Names
3.6 Electronegativity and Bond Polarity
3.7 Lewis Structures
3.8 Resonance and Formal Charge Revisited
3.9 Exceptions to the Octet Rule
3.10 Shapes of Molecules - VSEPR Theory and Valence Bond Theory
3.11 Practice Problems

3: Chemical Formulas and Bonding is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
3.1 An Atomic-Level Perspective of Ionic and Covalent Compounds
Skills to Develop
Define ionic and molecular (covalent) compounds
Predict the type of compound formed from elements based on their location within the periodic table
Determine formulas for simple ionic compounds

In chemical reactions, the nucleus of each atom (and thus the identity of the element) remains unchanged. Electrons, however, can
be added to atoms by transfer from other atoms, lost by transfer to other atoms, or shared with other atoms. The transfer and
sharing of electrons among atoms govern the chemistry of the elements. During the formation of some compounds, atoms gain or
lose electrons, and form electrically charged particles called ions (Figure 1).

Figure 1 : (a) A sodium atom (Na) has equal numbers of protons and electrons (11) and is uncharged. (b) A sodium cation (Na+)
has lost an electron, so it has one more proton (11) than electrons (10), giving it an overall positive charge, signified by a
superscripted plus sign.
You can use the periodic table to predict whether an atom will form an anion or a cation, and you can often predict the charge of the
resulting ion. Atoms of many main-group metals lose enough electrons to leave them with the same number of electrons as an atom
of the preceding noble gas. To illustrate, an atom of an alkali metal (group IA) loses one electron and forms a cation with a 1+
charge; an alkaline earth metal (group IIA) loses two electrons and forms a cation with a 2+ charge, and so on. For example, a
neutral calcium atom, with 20 protons and 20 electrons, readily loses two electrons. This results in a cation with 20 protons, 18
electrons, and a 2+ charge. It has the same number of electrons as atoms of the preceding noble gas, argon, and is symbolized Ca2+.
The name of a metal ion is the same as the name of the metal atom from which it forms, so Ca2+ is called a calcium ion.
When atoms of nonmetal elements form ions, they generally gain enough electrons to give them the same number of electrons as an
atom of the next noble gas in the periodic table. Atoms of group VIIA gain one electron and form anions with a 1− charge; atoms
of group VIA gain two electrons and form ions with a 2− charge, and so on. For example, the neutral bromine atom, with 35
protons and 35 electrons, can gain one electron to provide it with 36 electrons. This results in an anion with 35 protons, 36
electrons, and a 1− charge. It has the same number of electrons as atoms of the next noble gas, krypton, and is symbolized Br−. (A
discussion of the theory supporting the favored status of noble gas electron numbers (an octet of valence electrons) reflected in
these predictive rules for ion formation exists, but is not is described in this text.)
Note the usefulness of the periodic table in predicting likely ion formation and charge (Figure 2). Moving from the far left to the
right on the periodic table, main-group elements tend to form cations with a charge equal to the group number. That is, group IA
elements form 1+ ions; group IIA elements form 2+ ions, and so on. Moving from the far right to the left on the periodic table,
elements often form anions with a negative charge equal to the number of groups moved left from the noble gases. For example,
group VIIA elements (one group left of the noble gases) form 1− ions; group VIA elements (two groups left) form 2− ions, and so
on. This trend can be used as a guide in many cases, but its predictive value decreases when moving toward the center of the
periodic table. In fact, transition metals and some other metals often exhibit variable charges that are not predictable by their
location in the table. For example, copper can form ions with a 1+ or 2+ charge, and iron can form ions with a 2+ or 3+ charge.

1 [Link]
 Figure 2 : Some elements exhibit a regular pattern of ionic charge when they form ions.

Example 1 : Composition of Ions

An ion found in some compounds used as antiperspirants contains 13 protons and 10 electrons. What is its symbol?
Solution
Because the number of protons remains unchanged when an atom forms an ion, the atomic number of the element must be 13.
Knowing this lets us use the periodic table to identify the element as Al (aluminum). The Al atom has lost three electrons and
thus has three more positive charges (13) than it has electrons (10). This is the aluminum cation, Al3+.

Exercise 1
Give the symbol and name for the ion with 34 protons and 36 electrons.

Answer
Se2−, the selenide ion

Example 2 : Formation of Ions

Magnesium and nitrogen react to form an ionic compound. Predict which forms an anion, which forms a cation, and the charges
of each ion. Write the symbol for each ion and name them.
Solution
Magnesium’s position in the periodic table (group IIA) tells us that it is a metal. Metals form positive ions (cations). A
magnesium atom must lose two electrons to have the same number electrons as an atom of the previous noble gas, neon. Thus, a
magnesium atom will form a cation with two fewer electrons than protons and a charge of 2+. The symbol for the ion is Mg2+,
and it is called a magnesium ion.
Nitrogen’s position in the periodic table (group VA) reveals that it is a nonmetal. Nonmetals form negative ions (anions). A
nitrogen atom must gain three electrons to have the same number of electrons as an atom of the following noble gas, neon. Thus,
a nitrogen atom will form an anion with three more electrons than protons and a charge of 3−. The symbol for the ion is N3−,
and it is called a nitride ion.

Exercise 2

2 [Link]
 Aluminum and chlorine react to form an ionic compound. Predict which forms an anion, which forms a cation, and the charges
of each ion. Write the symbol for each ion and name them.

Answer
Al will form a cation with a charge of 3+: Al3+, an aluminum ion. Chlorine will form an anion with a charge of 1−: Cl−, a
chloride ion.

The ions that we have discussed so far are called monatomic ions, that is, they are ions formed from only one atom. We also find
many polyatomic ions. These ions, which act as discrete units, are a group of covalently-bonded atoms with an overall charge.
Some of the more important polyatomic ions are listed in Table 1. Oxyanions are polyatomic ions that contain one or more oxygen
atoms. At this point in your study of chemistry, you should memorize the names, formulas, and charges of the most common
polyatomic ions. Because you will use them repeatedly, they will soon become familiar.
Table 1 : Common Polyatomic Ions
Name Formula Related Acid Formula

ammonium NH
+
4

hydronium H O
3
+

oxide O
2 −
hydroxide OH
−

peroxide O
2 −
2

hydroxide OH
−
water H O
2

acetate CH COO
3
−
acetic acid CH COOH
3

cyanide CN
−
hydrocyanic acid HCN

cyanate OCN
−
cyanic acid HOCN

carbonate CO
2 −
3
hydrogen carbonate HCO
−
3

hydrogen carbonate HCO

−
3
carbonic acid H CO
2 3

nitrate NO
−
3
nitric acid HNO
3

nitrite NO
−
2
nitrous acid HNO
2

sulfate SO
2 −
4
hydrogen sulfate HSO
−
4

hydrogen sulfate HSO

−
4
sulfuric acid H SO
2 4

sulfite SO
2 −
3
hydrogen sulfite HSO
−
3

hydrogen sulfite HSO

−
3
sulfurous acid H SO
2 3

phosphate PO
3 −
4
hydrogen phosphate HPO
2 −
4

hydrogen phosphate HPO

2 −
4
dihydrogen phospahte H PO
2
−
4

dihydrogen phosphate H PO
2
−
4
phosphoric acid H PO
3 4

perchlorate ClO
−
4
perchloric acid HClO
4

chlorate ClO
−
3
chloric acid HClO
3

chlorite ClO
−
2
chlorous acid HClO
2

hypochlorite ClO
−
hypochlorous acid HClO

chromate CrO
2 −
4
chromic acid H CrO
2 4

dichromate Cr O
2
2 −
7
dichromic acid H Cr O
2 2 7

permanganate MnO
−
4
permanganic acid HMnO
4

Note that there is a system for naming some polyatomic ions; -ate and -ite are suffixes designating polyatomic ions containing
more or fewer oxygen atoms. Per- (short for “hyper”) and hypo- (meaning “under”) are prefixes meaning more oxygen atoms than

3 [Link]
-ate and fewer oxygen atoms than -ite, respectively. For example, perchlorate is ClO , chlorate is ClO , chlorite is ClO and
−

4
−

3
−

hypochlorite is ClO−. Unfortunately, the number of oxygen atoms corresponding to a given suffix or prefix is not consistent; for
example, nitrate is NO while sulfate is SO . This will be covered in more detail in the module on nomenclature.
−
3
2 −

The nature of the attractive forces that hold atoms or ions together within a compound is the basis for classifying chemical bonding.
When electrons are transferred and ions form, ionic bonds result. Ionic bonds are electrostatic forces of attraction, that is, the
attractive forces experienced between objects of opposite electrical charge (in this case, cations and anions). When electrons are
“shared” and molecules form, covalent bonds result. Covalent bonds are the attractive forces between the positively charged nuclei
of the bonded atoms and one or more pairs of electrons that are located between the atoms. Compounds are classified as ionic or
molecular (covalent) on the basis of the bonds present in them.

Ionic Compounds
When an element composed of atoms that readily lose electrons (a metal) reacts with an element composed of atoms that readily
gain electrons (a nonmetal), a transfer of electrons usually occurs, producing ions. The compound formed by this transfer is
stabilized by the electrostatic attractions (ionic bonds) between the ions of opposite charge present in the compound. For example,
when each sodium atom in a sample of sodium metal (group 1) gives up one electron to form a sodium cation, Na+, and each
chlorine atom in a sample of chlorine gas (group 17) accepts one electron to form a chloride anion, Cl−, the resulting compound,
NaCl, is composed of sodium ions and chloride ions in the ratio of one Na+ ion for each Cl− ion. Similarly, each calcium atom
(group 2) can give up two electrons and transfer one to each of two chlorine atoms to form CaCl2, which is composed of Ca2+ and
Cl− ions in the ratio of one Ca2+ ion to two Cl− ions.
A compound that contains ions and is held together by ionic bonds is called an ionic compound. The periodic table can help us
recognize many of the compounds that are ionic: When a metal is combined with one or more nonmetals, the compound is usually
ionic. This guideline works well for predicting ionic compound formation for most of the compounds typically encountered in an
introductory chemistry course. However, it is not always true (for example, aluminum chloride, AlCl3, is not ionically-bonded as a
pure compound, but does form ions when dissolved in water).
You can often recognize ionic compounds because of their properties. Ionic compounds are solids that typically melt at high
temperatures and boil at even higher temperatures. For example, sodium chloride melts at 801 °C and boils at 1413 °C. (As a
comparison, the molecular compound water melts at 0 °C and boils at 100 °C.) In solid form, an ionic compound is not electrically
conductive because its ions are unable to flow (“electricity” is the flow of charged particles). When molten, however, it can conduct
electricity because its ions are able to move freely through the liquid (Figure 3).

Figure 3 : Sodium chloride melts at 801 °C and conducts electricity when molten. (credit: modification of work by Mark Blaser and
Matt Evans)
In every ionic compound, the total number of positive charges of the cations equals the total number of negative charges of the
anions. Thus, ionic compounds are electrically neutral overall, even though they contain positive and negative ions. We can use this
observation to help us write the formula of an ionic compound. The formula of an ionic compound must have a ratio of ions such
that the numbers of positive and negative charges are equal.

Example 3 : Predicting the Formula of an Ionic Compound

4 [Link]
 The gemstone sapphire (Figure 4) is mostly a compound of aluminum and oxygen that contains aluminum cations, Al3+, and
oxygen anions, O2−. What is the formula of this compound?

Figure 4 : Although pure aluminum oxide is colorless, trace amounts of iron and titanium give blue sapphire its characteristic
color. (credit: modification of work by Stanislav Doronenko)
Solution Because the ionic compound must be electrically neutral, it must have the same number of positive and negative
charges. Two aluminum ions, each with a charge of 3+, would give us six positive charges, and three oxide ions, each with a
charge of 2−, would give us six negative charges. The formula would be Al2O3.

Exercise 3
Predict the formula of the ionic compound formed between the sodium cation, Na+, and the sulfide anion, S2−.

Answer
Na2S

Many ionic compounds contain polyatomic ions (Table 1) as the cation, the anion, or both. As with simple ionic compounds, these
compounds must also be electrically neutral, so their formulas can be predicted by treating the polyatomic ions as discrete units.
We use parentheses in a formula to indicate a group of atoms that behave as a unit. For example, the formula for calcium
phosphate, one of the minerals in our bones, is Ca3(PO4)2. This formula indicates that there are three calcium ions (Ca2+) for every
two phosphate (PO ) groups. The PO
3 −

4
3 −

4
groups are discrete units, each consisting of one phosphorus atom and four oxygen
atoms, and having an overall charge of 3−. The compound is electrically neutral, and its formula shows a total count of three Ca,
two P, and eight O atoms.

Example 4 : Predicting the Formula of a Compound with a Polyatomic Anion

Baking powder contains calcium dihydrogen phosphate, an ionic compound composed of the ions Ca2+ and H PO
2
−

4
. What is
the formula of this compound?
Solution
The positive and negative charges must balance, and this ionic compound must be electrically neutral. Thus, we must have two
negative charges to balance the 2+ charge of the calcium ion. This requires a ratio of one Ca2+ ion to two H PO ions. We
2
−

designate this by enclosing the formula for the dihydrogen phosphate ion in parentheses and adding a subscript 2. The formula is
Ca(H2PO4)2.

Exercise 4
Predict the formula of the ionic compound formed between the lithium ion and the peroxide ion, O
2−
2
(Hint: Use the periodic
table to predict the sign and the charge on the lithium ion.)

Answer
Li2O2

Because an ionic compound is not made up of single, discrete molecules, it cannot be properly symbolized using a molecular
formula. Instead, ionic compounds must be symbolized by a formula indicating the relative numbers of its constituent ions. For
compounds containing only monatomic ions (such as NaCl) and for many compounds containing polyatomic ions (such as CaSO4),
these formulas are just the empirical formulas introduced earlier in this chapter. However, the formulas for some ionic compounds
containing polyatomic ions are not empirical formulas. For example, the ionic compound sodium oxalate is comprised of Na+ and

5 [Link]
C O
2
2−

4
ions combined in a 2:1 ratio, and its formula is written as Na2C2O4. The subscripts in this formula are not the smallest-
possible whole numbers, as each can be divided by 2 to yield the empirical formula, NaCO2. This is not the accepted formula for
sodium oxalate, however, as it does not accurately represent the compound’s polyatomic anion, C O .2
2−
4

Molecular Compounds
Many compounds do not contain ions but instead consist solely of discrete, neutral molecules. These molecular compounds
(covalent compounds) result when atoms share, rather than transfer (gain or lose), electrons. Covalent bonding is an important and
extensive concept in chemistry, and it will be treated in considerable detail in a later chapter of this text. We can often identify
molecular compounds on the basis of their physical properties. Under normal conditions, molecular compounds often exist as
gases, low-boiling liquids, and low-melting solids, although many important exceptions exist.
Whereas ionic compounds are usually formed when a metal and a nonmetal combine, covalent compounds are usually formed by a
combination of nonmetals. Thus, the periodic table can help us recognize many of the compounds that are covalent. While we can
use the positions of a compound’s elements in the periodic table to predict whether it is ionic or covalent at this point in our study
of chemistry, you should be aware that this is a very simplistic approach that does not account for a number of interesting
exceptions. Shades of gray exist between ionic and molecular compounds, and you’ll learn more about those later.

Example 5 : Predicting the Type of Bonding in Compounds

Predict whether the following compounds are ionic or molecular:
a. KI, the compound used as a source of iodine in table salt
b. H2O2, the bleach and disinfectant hydrogen peroxide
c. CHCl3, the anesthetic chloroform
d. Li2CO3, a source of lithium in antidepressants
Solution
a. Potassium (group IA) is a metal, and iodine (group VIIA) is a nonmetal; KI is predicted to be ionic.
b. Hydrogen (group IA) is a nonmetal, and oxygen (group VIA) is a nonmetal; H2O2 is predicted to be molecular.
c. Carbon (group IVA) is a nonmetal, hydrogen (group IA) is a nonmetal, and chlorine (group VIIA) is a nonmetal; CHCl3 is
predicted to be molecular.
d. Lithium (group IA) is a metal, and carbonate is a polyatomic ion; Li2CO3 is predicted to be ionic.

Exercise 5
Using the periodic table, predict whether the following compounds are ionic or covalent:
a. SO2
b. CaF2
c. N2H4
d. Al2(SO4)3

Answer a
molecular
Answer b
ionic
Answer c
molecular
Answer d
ionic

6 [Link]
Summary
Metals (particularly those in groups IA and IIA) tend to lose the number of electrons that would leave them with the same number
of electrons as in the preceding noble gas in the periodic table. By this means, a positively charged ion is formed. Similarly,
nonmetals (especially those in groups VIA and VIIA, and, to a lesser extent, those in Group VA) can gain the number of electrons
needed to provide atoms with the same number of electrons as in the next noble gas in the periodic table. Thus, nonmetals tend to
form negative ions. Positively charged ions are called cations, and negatively charged ions are called anions. Ions can be either
monatomic (containing only one atom) or polyatomic (containing more than one atom).
Compounds that contain ions are called ionic compounds. Ionic compounds generally form from metals and nonmetals.
Compounds that do not contain ions, but instead consist of atoms bonded tightly together in molecules (uncharged groups of atoms
that behave as a single unit), are called covalent compounds. Covalent compounds usually form from two or more nonmetals.

Glossary
covalent bond
attractive force between the nuclei of a molecule’s atoms and pairs of electrons between the atoms

covalent compound
(also, molecular compound) composed of molecules formed by atoms of two or more different elements covalently bonded
together

ionic bond
electrostatic forces of attraction between the oppositely charged ions of an ionic compound

ionic compound
compound composed of cations and anions combined in ratios, yielding an electrically neutral substance

molecular compound
(also, covalent compound) composed of molecules formed by atoms of two or more different elements covalently bonded
together

monatomic ion
ion composed of a single atom

polyatomic ion
ion composed of more than one atom

oxyanion
polyatomic anion composed of a central atom bonded to oxygen atoms

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).
Modified by Tom Neils (Grand Rapids Community College)

3.1 An Atomic-Level Perspective of Ionic and Covalent Compounds is shared under a CC BY-NC-SA 4.0 license and was authored, remixed,
and/or curated by LibreTexts.

7 [Link]
3.2 Composition of Compounds
Skills to Develop
To understand the definition and difference between empirical formulas and molecular formulas
To understand how combustion analysis can be used to identify molecular formulas

Chemistry is the experimental and theoretical study of materials at both the macroscopic and microscopic levels. Understanding the relationship between
properties and structures/bonding is a major aspect of these theoretical and experimental studies. A chemical formula is a format used to express the structure of
compounds. The formula tells which elements and how many of each element are present in a compound. Formulas are written using the elemental symbol of
each atom and a subscript to denote the number of elements.
Molecular formulas tell you how many atoms of each element are in a compound, and empirical formulas tell you the simplest or most reduced ratio of
elements in a compound. If a compound's molecular formula cannot be reduced any more, then the empirical formula is the same as the molecular formula.
Once the molar mass of the compound is known, the molecular formula can be calculated from the empirical formula.

Formulas on the Atomic and the Molar Level

A chemical formula tells us the relative ratios of different atoms in a compound. The ratios hold true on the molar level as well as the atomic level. Thus, H2O
is composed of two atoms of hydrogen and 1 atom of oxygen. One molecule of water has a mass of 18.02 amus. Likewise, 1.000 mole of H2O molecules is
composed of 2.000 moles of hydrogen and 1.000 mole of oxygen. The mass of 1.000 mole of water molecules has a mass of 18.02 grams.

Example 1 : Acetone
An acetone molecule has the chemical formula of C3H6O.
Questions:
a) Is C3H6O an empirical formula, a molecular formula, or both?
b) How many H atoms are in one acetone molecule?
c) How many total atoms are in one acetone molecule?
d) What is the mass, in amus, of one acetone molecule?
e) What is the mass, in grams, of 1.000 mole of acetone molecules?
f) How many H atoms are in 1.000 mole of acetone molecules?
g) How many total atoms are in 1.000 mole of acetone molecules?
Solutions:
a) The formula is both an empirical formula (because it is the simplest ratio of elements) and also a molecular formula (because the formula tells the actual
number of atoms of each element in one acetone molecule).
b) There are 6 H atoms in one acetone molecule.
c) There are 10 total atoms (6 H + 3 C + O) in one acetone molecule.
1.008 amus 12.01 amus 16.00 amus
d) The mass of one acetone molecule: 6 H atoms × + 3 C atoms × + 1 O atom × = 58.08amus
H atom C atom O atom

e) The mass of 1.000 mole of acetone molecules:

1.008 grams 12.01 grams
6 moles H atoms × + 3 moles C atoms × + 1 mole O atoms (1)
1.000 moles H atoms 1.000 moles C atoms

16.00 grams
× = 58.08grams
1.000 mole O atoms

f) H atoms in 1.00 mole of acetone molecules:

23
6 moles H atoms 6.022x 10 H atoms
24
1.000 mole acetone molecules × × = 3.613x 10 H (2)
1.000 mole acetone molecules 1.000 moles H atoms

atoms

g) Total atoms in 1.000 moles of acetone molecules:

23
10 moles atoms 6.022x 10 atoms
24
1.000 mole acetone molecules × × = 6.022x 10 atoms (3)
1.000 mole acetone molecules 1.000 mole atoms

Exercise 1
An certain molecule has the chemical formula of C8H8O4
Questions:
a) Is C8H8O4 an empirical formula, a molecular formula, or both?
b) How many H atoms are in one C8H8O4 molecule?

1 [Link]
 c) How many total atoms are in one C8H8O4 molecule?
d) What is the mass, in amus, of one C8H8O4 molecule?
e) What is the mass, in grams, of 1.000 mole of C8H8O4 molecules?
f) How many H atoms are in 1.000 mole of C8H8O4 molecules?
g) How many total atoms are in 1.000 mole of C8H8O4 molecules?

Answer
a) The formula is a molecular formula, because it is not the simplest ratio of elements. The empirical formula is C2H2O1
b) There are 8 H atoms in one acetone molecule.
c) There are 20 total atoms (8 H + 8 C + 4 O) in one C8H8O4 molecule.
1.008 amus 12.01 amus 16.00 amus
d) The mass of one C8H8O4 molecule: 8 H atoms × + 8 C atoms × + 4 O atom × = 168.1amus
H atom C atom O atom

e) The mass of 1.000 mole of C8H8O4 molecules:

1.008 grams 12.01 grams 16.00 grams
8 moles H atoms × + 8 moles C atoms × + 4 mole O atoms × (4)
1.000 moles H atoms 1.000 moles C atoms 1.000 mole O atoms

= 168.1grams

f) H atoms in 1.00 mole of C8H8O4 molecules:

23
8 moles H atoms 6.022x 10 H atoms 24
1.000 mole C8 H8 O4 molecules × × = 4.818x 10 H atoms (5)
1.000 mole C8 H8 O4 molecules 1.000 moles H atoms

g) Total atoms in 1.000 moles of C8H8O4 molecules:

23
20 moles atoms 6.022x 10 atoms 25
1.000 mole C8 H8 O4 molecules × × = 1.204x 10 atoms (6)
1.000 mole C8 H8 O4 molecules 1.000 mole atoms

Structural Formulas
There are several ways to write and draw chemical formulas for covalently-bonded compounds, depending on how much information about the structure is
needed.

Condensed Structural Formula

Condensed structural formulas show a bit more information about the bonding order of atoms in a molecule than a simple molecular formula. A condensed
structural formula is written in a single line to save space and make it more convenient and faster to write out. Condensed structural formulas are also helpful
when showing that a group of atoms is connected to a single atom in a compound. When this happens, parenthesis are used around the group of atoms to show
they are together.
Ex. Condensed Structural Formula for ethanol: CH3CH2OH (molecular Formula: C2H6O).
Condensed Structural Formula for dimethyl ether: (CH3)2O (molecular formula: C2H6O).

Expanded Structural Formula

A structural formula displays the atoms of the molecule in the order they are bonded. It also depicts how the atoms are bonded to one another, for example
single, double, and triple covalent bond. Covalent bonds are shown using lines. The number of dashes indicate whether the bond is a single, double, or triple
covalent bond. Structural formulas are helpful because they explain the properties and structure of the compound which condensed formulas cannot always
represent.
Structural Formula for CH3CH2OH, ethanol

Line-Angle Formula
Because organic compounds can be complex, line-angle formulas are used to write carbon and hydrogen atoms more efficiently by omitting the symbol of H
atoms attached to C atoms, and by replacing the C element symbols with the intersection of lines. Thus, a carbon atom is present wherever one line intersects
another line. Hydrogen atoms are assumed to complete each of carbon's four bonds. All other atoms that are connected to carbon atoms are written out. Line
angle formulas help show structure and order of the atoms in a compound making the advantages and disadvantages similar to structural formulas.
Line-Angle Formula for Ethanol:

2 [Link]
Isomers
Understanding how atoms in a molecules are arranged and how they are bonded together is very important in giving the molecule its identity. Isomers are
compounds in which two molecules have the same number of atoms, and thus the same molecular formula, but have completely different physical and chemical
properties because of differences in structural formula.

Methylpropane and butane have the same molecular formula of C4H10, but are structurally different (methylpropane on the left, butane on the right).

Polymers
A polymer is formed when small molecules of identical structure, monomers, combine into a large cluster. The monomers are joined together by covalent
bonds. When monomers repeat and bind, they form a polymer. While they can be comprised of natural or synthetic molecules, polymers often include plastics
and rubber. When a molecule has more than one of these polymers, parenthesis are used to show that all the elements within the polymer are multiplied by the
subscript outside of the parenthesis. The subscript (shown as n in the example below) denotes the number of monomers present in the macromolecule (or
polymer).

Ethylene becomes the polymer polyethylene.

Contributors
Mike Blaber (Florida State University)
Modified by Tom Neils (Grand Rapids Community College)

3.2 Composition of Compounds is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

3 [Link]
3.3 Chemical Bonds
Skills to Develop
To quantitatively describe the energetic factors involved in the formation of an ionic bond.

Chemical bonds form when electrons can be simultaneously close to two or more nuclei, but beyond this, there is no simple, easily
understood theory that would not only explain why atoms bind together to form molecules, but would also predict the three-
dimensional structures of the resulting compounds as well as the energies and other properties of the bonds themselves.
Unfortunately, no one theory exists that accomplishes these goals in a satisfactory way for all of the many categories of compounds
that are known. Moreover, it seems likely that if such a theory does ever come into being, it will be far from simple.
When we are faced with a scientific problem of this complexity, experience has shown that it is often more useful to concentrate
instead on developing models. A scientific model is something like a theory in that it should be able to explain observed
phenomena and to make useful predictions. But whereas a theory can be discredited by a single contradictory case, a model can be
useful even if it does not encompass all instances of the phenomena it attempts to explain. We do not even require that a model be a
credible representation of reality; all we ask is that be able to explain the behavior of those cases to which it is applicable in terms
that are consistent with the model itself. An example of a model that you may already know about is the kinetic molecular theory of
gases. Despite its name, this is really a model (at least at the level that beginning students use it) because it does not even try to
explain the observed behavior of real gases. Nevertheless, it serves as a tool for developing our understanding of gases, and as a
starting point for more elaborate [Link] the extraordinary variety of ways in which atoms combine into aggregates, it
should come as no surprise that a number of useful bonding models have been developed. Most of them apply only to certain
classes of compounds, or attempt to explain only a restricted range of phenomena. In this section we will provide brief descriptions
of some of the bonding models; the more important of these will be treated in much more detail in later parts of this chapter.

Ionic Bonding
Ever since the discovery early in the 19th century that solutions of salts and other electrolytes conduct electric current, there has
been general agreement that the forces that hold atoms together must be electrical in nature. Electrolytic solutions contain ions
having opposite electrical charges, opposite charges attract, so perhaps the substances from which these ions come consist of
positive and negatively charged atoms held together by electrostatic attraction.
It turns out that this is not true generally, but a model built on this assumption does a fairly good job of explaining a rather small
but important class of compounds that are called ionic solids. The most well known example of such a compound is sodium
chloride, which consists of two interpenetrating lattices of Na+ and Cl– ions arranged in such as way that every ion of one type is
surrounded (in three dimensional space) by six ions of opposite charge. The main limitation of this model is that it applies really
well only to the small class of solids composed of Group 1 and 2 elements with highly electronegative elements such as the
halogens.
According to the ionic electrostatic model, solids such as NaCl consist of positive and negative ions arranged in a crystal lattice.
Each ion is attracted to neighboring ions of opposite charge, and is repelled by ions of like charge; this combination of attractions
and repulsions, acting in all directions, causes the ion to be tightly fixed in its own location in the crystal lattice.
Ions are atoms or molecules which are electrically charged. Cations are positively charged and anions carry a negative charge.
Ions form when atoms gain or lose electrons. Since electrons are negatively charged, an atom that loses one or more electrons will
become positively charged; an atom that gains one or more electrons becomes negatively charged. Ionic bonding is the attraction
between positively- and negatively-charged ions. These oppositely charged ions attract each other to form ionic networks (or
lattices). Electrostatics explains why this happens: opposite charges attract and like charges repel. When many ions attract each
other, they form large, ordered, crystal lattices in which each ion is surrounded by ions of the opposite charge. Generally, when
metals react with non-metals, electrons are transferred from the metals to the non-metals. The metals form positively-charged ions
and the non-metals form negatively-charged ions.
Ionic bonds form when metals and non-metals chemically react. By definition, a metal is relatively stable if it loses electrons to
form a complete valence shell and becomes positively charged. Likewise, a non-metal becomes stable by gaining electrons to
complete its valence shell and become negatively charged. When metals and non-metals react, the metals lose electrons by
transferring them to the non-metals, which gain them. Consequently, ions are formed, which instantly attract each other—ionic
bonding.

1 [Link]
 Example 1 : Sodium Chloride
For example, in the reaction of Na (sodium) and Cl (chlorine), each Cl atom takes one electron from a Na atom. Therefore each
Na becomes a Na+ cation and each Cl atom becomes a Cl- anion. Due to their opposite charges, they attract each other to form
an ionic lattice. The formula (ratio of positive to negative ions) in the lattice is NaCl.

2N a(s) + C l2(g) → 2N aC l(s) (1)

These ions are arranged in solid NaCl in a regular three-dimensional arrangement (or lattice):

NaCl lattice. (left) 3-D structure and (right) simple 2D slice through lattes. Images used with permission from Wikipedia and
Mike Blaber.
The chlorine has a high affinity for electrons, and the sodium has a low ionization potential. Thus the chlorine gains an electron
from the sodium atom. This can be represented using electron-dot symbols (here we will consider one chlorine atom, rather than
Cl2):

The arrow indicates the transfer of the electron from sodium to chlorine to form the Na+ metal ion and the Cl- chloride ion. Each
ion now has an octet of electrons in its valence shell.

Covalent Bonding
Formation of an ionic bond by complete transfer of an electron from one atom to another is possible only for a fairly restricted set
of elements. Covalent bonding, in which neither atom loses complete control over its valence electrons, is much more common. In
a covalent bond the electrons occupy a region of space between the two nuclei and are said to be shared by them. This model
originated with the theory developed by G.N. Lewis in 1916, and it remains the most widely-used model of chemical bonding. The
essential element s of this model can best be understood by examining the simplest possible molecule. This is the hydrogen
molecule ion H2+, which consists of two nuclei and one electron. First, however, think what would happen if we tried to make the
even simpler molecule H22+. Since this would consist only of two protons whose electrostatic charges would repel each other at all
distances, it is clear that such a molecule cannot exist; something more than two nuclei are required for bonding to occur.
In the hydrogen molecule ion H2+ we have a third particle, an electron. The effect of this electron will depend on its location with
respect to the two nuclei. If the electron is in the space between the two nuclei, it will attract both protons toward itself, and thus
toward each other. If the total attraction energy exceeds the internuclear repulsion, there will be a net bonding effect and the
molecule will be stable. If, on the other hand, the electron is off to one side, it will attract both nuclei, but it will attract the closer
one much more strongly, owing to the inverse-square nature of Coulomb's law. As a consequence, the electron will now help the
electrostatic repulsion to push the two nuclei apart.
We see, then, that the electron is an essential component of a chemical bond, but that it must be in the right place: between the two
nuclei. Coulomb's law can be used to calculate the forces experienced by the two nuclei for various positions of the electron, but
we have been vague in our language about the actual nature of the chemical bonds themselves. We know that a covalent bond
involves the ‘sharing’ of a pair of electrons between two atoms - but how does this happen, and how does it lead to the formation of
a bond holding the two atoms together?
The valence bond theory is introduced to describe bonding in covalent molecules. In this model, bonds are considered to form
from the overlapping of two atomic orbitals on different atoms, each orbital containing a single electron. In looking at simple
inorganic molecules such as H2 or HF, our present understanding of s and p atomic orbitals will suffice. To explain the bonding in
more complex molecules, however, we will need to introduce the concept of hybrid orbitals.

2 [Link]
Example: The H2 molecule
The simplest case to consider is the hydrogen molecule, H2. When we say that the two electrons from each of the hydrogen atoms
are shared to form a covalent bond between the two atoms, what we mean in valence bond theory terms is that the two spherical 1s
orbitals overlap, allowing the two electrons to form a pair within the two overlapping orbitals. In simple terms, we can say that both
electrons now spend more time between the two nuclei and thus hold the atoms together. As we will see, the situation is not quite
so simple as that, because the electron pair must still obey quantum mechanics - that is, the two electrons must now occupy a
shared orbital space. This will be the essential principle of valence bond theory.

These two electrons are now attracted to the positive charge of both of the hydrogen nuclei, with the result that they serve as a sort
of ‘chemical glue’ holding the two nuclei together.
How far apart are the two nuclei? That is a very important issue to consider. If they are too far apart, their respective 1s orbitals
cannot overlap, and thus no covalent bond can form - they are still just two separate hydrogen atoms. As they move closer and
closer together, orbital overlap begins to occur, and a bond begins to form. This lowers the potential energy of the system, as new,
attractive positive-negative electrostatic interactions become possible between the nucleus of one atom and the electron of the
second. However, something else is happening at the same time: as the atoms get closer, the repulsive positive-positive interaction
between the two nuclei also begins to increase.

At first this repulsion is more than offset by the attraction between nuclei and electrons, but at a certain point, as the nuclei get even
closer, the repulsive forces begin to overcome the attractive forces, and the potential energy of the system rises quickly. When the
two nuclei are ‘too close’, we have a very unstable, high-energy situation. There is a defined optimal distance between the nuclei in
which the potential energy is at a minimum, meaning that the combined attractive and repulsive forces add up to the greatest
overall attractive force. This optimal internuclear distance is the bond length. For the H2 molecule, this distance is 74 x 10-12
meters, or 0.74 Å (Å means angstrom, or 10-10 meters). Likewise, the difference in potential energy between the lowest state (at the
optimal internuclear distance) and the state where the two atoms are completely separated is called the bond energy. For the
hydrogen molecule, this energy is equal to about 104 kcal/mol.
Every covalent bond in a given molecule has a characteristic length and strength. In general, carbon-carbon single bonds are about
1.5 Å long (Å means angstrom, or 10-10 meters) while carbon-carbon double bonds are about 1.3 Å, carbon-oxygen double bonds
are about 1.2 Å, and carbon-hydrogen bonds are in the range of 1.0 – 1.1 Å. Most covalent bonds range in strength from just under
100 kcal/mole (for a carbon-hydrogen bond in ethane, for example) up to nearly 200 kcal/mole.

Orbital Overlap: A Second Look

You learned that as two hydrogen atoms approach each other from an infinite distance, the energy of the system reaches a
minimum. This region of minimum energy in the energy diagram corresponds to the formation of a covalent bond between the two
atoms at an H–H distance of 74 pm. According to quantum mechanics, bonds form between atoms because their atomic orbitals
overlap, with each region of overlap accommodating a maximum of two electrons with opposite spin, in accordance with the Pauli
principle. In this case, a bond forms between the two hydrogen atoms when the singly occupied 1s atomic orbital of one hydrogen
atom overlaps with the singly occupied 1s atomic orbital of a second hydrogen atom. Electron density between the nuclei is
increased because of this orbital overlap and results in a localized electron-pair bond. When the orbitals of two atoms overlap along

3 [Link]
the line between the two atomic nuclei (the internuclear axis), the bond is designated as a sigma (σ ) bond. The formation of a
sigma bond between two H atoms is shown here:

Overlap of Two Singly Occupied Hydrogen 1s Atomic Orbitals Produces an H–H Bond in H2. The formation of H2 from two
hydrogen atoms, each with a single electron in a 1s orbital, occurs as the electrons are shared to form an electron-pair bond, as
indicated schematically by the gray spheres and black arrows. The orange electron density distributions show that the formation of
an H2 molecule increases the electron density in the region between the two positively charged nuclei.
All orbitals other than s orbitals are able to form a second type of covalent bond, based on their ability to overlap, simultaneously,
both above and below the internuclear axis of the two bonding atoms. This type of overlap is called a pi (pi) bond.
There are two basic assumptions for covalent bonding theory:
1. The strength of a covalent bond is proportional to the amount of overlap between atomic orbitals; that is, the greater the overlap,
the more stable the bond. Sigma bonds are generally stronger than pi bonds because the overlap is greater in sigma bonds than
in pi bonds.
2. An atom can use different combinations of atomic orbitals to maximize the overlap of orbitals used by bonded atoms.
(Described later when we discuss hybrid orbitals.)

Sigma Bond Overlapping

The figure below shows a sigma bond formed by the overlap of two s atomic orbitals, two p atomic orbitals, and an s and an p
orbital. Notice that bonding overlap occurs when the interacting atomic orbitals have the correct orientation (are "pointing at" each
other).

Maximum overlap occurs between orbitals with the same spatial orientation and similar energies.

4 [Link]
Three Different Ways to Form an Electron-Pair Bond. An electron-pair bond can be formed by the overlap of any of the following
combinations of two singly occupied atomic orbitals: two s atomic orbitals (a), an s and an p atomic orbital (b), and two p atomic
orbitals (c).

Pi Bond Overlapping
The figure below shows a pi bond formed by the overlap of two p atomic orbitals, and a p and a d orbital. Notice that bonding
overlap occurs when the interacting atomic orbitals have the correct orientation (are "parallel" with each other).
A pi bond (π bond) is a type of covalent bond that results from the side-by-side overlap of two p orbitals, as illustrated in the figure
below. In a π bond, the regions of orbital overlap lie above and below the internuclear axis. Along the axis itself, there is a node,
that is, a plane with no probability of finding an electron.

Formation of π Molecular Orbitals from npx and npy Atomic Orbitals on Adjacent Atoms.

Metallic Bonding
Metals have several qualities that are unique, such as the ability to conduct electricity, a low ionization energy, and a low
electronegativity (so they will give up electrons easily, i.e., they are cations). Metallic bonding is sort of like covalent bonding,
because it involves sharing electrons. The simplest model of metallic bonding is the "sea of electrons" model, which imagines that
the atoms sit in a sea of valence electrons that are delocalized over all the atoms. Because there are not specific bonds between
individual atoms, metals are more flexible. The atoms can move around and the electron sea will keep holding them together. Some
metals are very hard and have very high melting points, while others are soft and have low melting points. This depends roughly on
the number of valence electrons that form the sea.
A False Dichotomy: The Ionic vs. Colvalent
The covalent-ionic continuum described above is certainly an improvement over the old covalent -versus - ionic dichotomy that
existed only in the textbook and classroom, but it is still only a one-dimensional view of a multidimensional world, and thus a
view that hides more than it reveals. The main thing missing is any allowance for the type of bonding that occurs between more
pairs of elements than any other: metallic bonding. Intermetallic compounds are rarely even mentioned in introductory courses,
but since most of the elements are metals, there are a lot of them, and many play an important role in metallurgy. In metallic
bonding, the valence electrons lose their association with individual atoms; they form what amounts to a mobile "electron fluid"
that fills the space between the crystal lattice positions occupied by the atoms, (now essentially positive ions.) The more readily
this electron delocalization occurs, the more "metallic" the element.

Thus instead of the one-dimension chart shown above, we can construct a triangular diagram whose corners represent the three
extremes of "pure" covalent, ionic, and metallic bonding.

5 [Link]
Summary
The covalent bond is formed when two atoms are able to share electrons:

whereas the ionic bond is formed when the "sharing" is so unequal that an electron from atom A is completely lost to atom B,
resulting in a pair of ions:

The two extremes of electron sharing represented by the covalent and ionic models appear to be generally consistent with the
observed properties of molecular and ionic solids and liquids. But does this mean that there are really two kinds of chemical bonds,
ionic and covalent?

Contributors
Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook
Modified by Tom Neils (Grand Rapids Community College)

3.3 Chemical Bonds is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

6 [Link]
3.4 Ionic Compounds: Formulas and Names

Skills to Develop
Derive names for common types of inorganic compounds using a systematic approach

Nomenclature, a collection of rules for naming things, is important in science and in many other situations. This module describes
an approach that is used to name simple ionic and molecular compounds, such as NaCl, CaCO3, and N2O4. The simplest of these
are binary compounds, those containing only two elements, but we will also consider how to name ionic compounds containing
polyatomic ions, and one specific, very important class of compounds known as acids (subsequent chapters in this text will focus
on these compounds in great detail). We will limit our attention here to inorganic compounds, compounds that are composed
principally of elements other than carbon, and will follow the nomenclature guidelines proposed by IUPAC. The rules for organic
compounds, in which carbon is the principle element, will be treated in a later chapter on organic chemistry.

Ionic Compounds
To name an inorganic compound, we need to consider the answers to several questions. First, is the compound ionic or molecular?
If the compound is ionic, does the metal form ions of only one type (fixed charge) or more than one type (variable charge)? Are the
ions monatomic or polyatomic? If the compound is molecular, does it contain hydrogen? If so, does it also contain oxygen? From
the answers we derive, we place the compound in an appropriate category and then name it accordingly.

Compounds Containing Only Monatomic Ions

The name of a binary compound containing monatomic ions consists of the name of the cation (the name of the metal) followed by
the name of the anion (the name of the nonmetallic element with its ending replaced by the suffix –ide). Some examples are given
in Table 3.4I onicC ompounds. 2.
Table 3.4I onicC ompounds. 1 : Names of Some Ionic Compounds
NaCl, sodium chloride Na2O, sodium oxide

KBr, potassium bromide CdS, cadmium sulfide

CaI2, calcium iodide Mg3N2, magnesium nitride

CsF, cesium fluoride Ca3P2, calcium phosphide

LiCl, lithium chloride Al4C3, aluminum carbide

Compounds Containing Polyatomic Ions

Compounds containing polyatomic ions are named similarly to those containing only monatomic ions, except there is no need to
change to an –ide ending, since the suffix is already present in the name of the anion. Examples are shown in Table
3.4I onicC ompounds. 2.

Table 3.4I onicC ompounds. 2 : Names of Some Polyatomic Ionic Compounds

KC2H3O2, potassium acetate (NH4)Cl, ammonium chloride

NaHCO3, sodium bicarbonate CaSO4, calcium sulfate

Al2(CO3)3, aluminum carbonate Mg3(PO4)2, magnesium phosphate

Ionic Compounds in Your Cabinets

Every day you encounter and use a large number of ionic compounds. Some of these compounds, where they are found, and
what they are used for are listed in Table. Look at the label or ingredients list on the various products that you use during the
next few days, and see if you run into any of those in this table, or find other ionic compounds that you could now name or write
as a formula.

Ionic Compound Use

NaCl, sodium chloride ordinary table salt

3.4 Ionic Compounds.1 [Link]

 KI, potassium iodide added to “iodized” salt for thyroid health

NaF, sodium fluoride ingredient in toothpaste

NaHCO3, sodium bicarbonate baking soda; used in cooking (and as antacid)

Na2CO3, sodium carbonate washing soda; used in cleaning agents

NaOCl, sodium hypochlorite active ingredient in household bleach

CaCO3 calcium carbonate ingredient in antacids

Mg(OH)2, magnesium hydroxide ingredient in antacids

Al(OH)3, aluminum hydroxide ingredient in antacids

NaOH, sodium hydroxide lye; used as drain cleaner

K3PO4, potassium phosphate food additive (many purposes)

MgSO4, magnesium sulfate added to purified water

Na2HPO4, sodium hydrogen phosphate anti-caking agent; used in powdered products

Na2SO3, sodium sulfite preservative

Compounds Containing a Metal Ion with a Variable Charge

Most of the transition metals can form two or more cations with different charges. Compounds of these metals with nonmetals are
named with the same method as compounds in the first category, except the charge of the metal ion is specified by a Roman
numeral in parentheses after the name of the metal. The charge of the metal ion is determined from the formula of the compound
and the charge of the anion. For example, consider binary ionic compounds of iron and chlorine. Iron typically exhibits a charge of
either 2+ or 3+ (see [link]), and the two corresponding compound formulas are FeCl2 and FeCl3. The simplest name, “iron
chloride,” will, in this case, be ambiguous, as it does not distinguish between these two compounds. In cases like this, the charge of
the metal ion is included as a Roman numeral in parentheses immediately following the metal name. These two compounds are
then unambiguously named iron(II) chloride and iron(III) chloride, respectively. Other examples are provided in Table
3.4I onicC ompounds. 3.

Table 3.4I onicC ompounds. 3 : Names of Some Transition Metal Ionic Compounds
Transition Metal Ionic Compound Name

FeCl3 iron(III) chloride

Hg2O mercury(I) oxide

HgO mercury(II) oxide

Cu3(PO4)2 copper(II) phosphate

Out-of-date nomenclature used the suffixes –ic and –ous to designate metals with higher and lower charges, respectively: Iron(III)
chloride, FeCl3, was previously called ferric chloride, and iron(II) chloride, FeCl2, was known as ferrous chloride. Though this
naming convention has been largely abandoned by the scientific community, it remains in use by some segments of industry. For
example, you may see the words stannous fluoride on a tube of toothpaste. This represents the formula SnF2, which is more
properly named tin(II) fluoride. The other fluoride of tin is SnF4, which was previously called stannic fluoride but is now named
tin(IV) fluoride.

Example 3.4I onicCompounds. 1: Naming Ionic Compounds

Name the following ionic compounds, which contain a metal that can have more than one ionic charge:
a. Fe2S3
b. CuSe
c. GaN
d. CrCl3
e. Ti2(SO4)3

3.4 Ionic Compounds.2 [Link]

 Solution
The anions in these compounds have a fixed negative charge (S2−, Se2− , N3−, Cl−, and SO ), and the compounds must be
2−

neutral. Because the total number of positive charges in each compound must equal the total number of negative charges, the
positive ions must be Fe3+, Cu2+, Ga3+, Cr4+, and Ti3+. These charges are used in the names of the metal ions:
a. iron(III) sulfide
b. copper(II) selenide
c. gallium(III) nitride
d. chromium(III) chloride
e. titanium(III) sulfate

Exercise 3.4I onicCompounds. 1

Write the formulas of the following ionic compounds:
1. (a) chromium(III) phosphide
2. (b) mercury(II) sulfide
3. (c) manganese(II) phosphate
4. (d) copper(I) oxide
5. (e) chromium(VI) fluoride
Answer:
(a) CrP; (b) HgS; (c) Mn3(PO4)2; (d) Cu2O; (e) CrF6

Summary
Chemists use nomenclature rules to clearly name compounds. Ionic and molecular compounds are named using somewhat-different
methods. Binary ionic compounds typically consist of a metal and a nonmetal. The name of the metal is written first, followed by
the name of the nonmetal with its ending changed to –ide. For example, K2O is called potassium oxide. If the metal can form ions
with different charges, a Roman numeral in parentheses follows the name of the metal to specify its charge. Thus, FeCl2 is iron(II)
chloride and FeCl3 is iron(III) chloride. Some compounds contain polyatomic ions; the names of common polyatomic ions should
be memorized.

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).
Modified by Tom Neils (Grand Rapids Community College)

3.4 Ionic Compounds: Formulas and Names is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

3.4 Ionic Compounds.3 [Link]

3.5 Covalently-Bonded Species: Formulas and Names
Skills to Develop
Derive names for common types of inorganic compounds using a systematic approach

The bonding characteristics of inorganic molecular compounds are different from ionic compounds, and they are named using a
different system as well. The charges of cations and anions dictate their ratios in ionic compounds, so specifying the names of the ions
provides sufficient information to determine chemical formulas. However, because covalent bonding allows for significant variation in
the combination ratios of the atoms in a molecule, the names for molecular compounds must explicitly identify these ratios.

Compounds Composed of Two Elements

When two nonmetallic elements form a molecular compound, several combination ratios are often possible. For example, carbon and
oxygen can form the compounds CO and CO2. Since these are different substances with different properties, they cannot both have the
same name (they cannot both be called carbon oxide). To deal with this situation, we use a naming method that is somewhat similar to
that used for ionic compounds, but with added prefixes to specify the numbers of atoms of each element. The name of the more metallic
element (the one farther to the left and/or bottom of the periodic table) is first, followed by the name of the more nonmetallic element
(the one farther to the right and/or top) with its ending changed to the suffix –ide. The numbers of atoms of each element are designated
by the Greek prefixes shown in Table 3.5C ovalently − BondedSpecies. 3 .
Table 3.5C ovalently − BondedSpecies. 3 : Nomenclature Prefixes
N Prefix Number P
u r
m e
b f
e i
r x

1 mono- 6 h
( e
s x
o a
m -
e
t
i
m
e
s
o
m
i
t
t
e
d
)

2 di- 7 h
e
p
t
a
-

3 tri- 8 o
c
t
a
-

3.5 Covalently-Bonded Species.1 [Link]

 N Prefix Number P
u r
m e
b f
e i
r x

4 tetra- 9 n
o
n
a
-

5 penta- 10 d
e
c
a
-

When only one atom of the first element is present, the prefix mono- is usually deleted from that part. Thus, CO is named carbon
monoxide, and CO2 is called carbon dioxide. When two vowels are adjacent, the a in the Greek prefix is usually dropped. Some other
examples are shown in Table 3.5C ovalently − BondedSpecies. 4 .
Table 3.5C ovalently − BondedSpecies. 4 : Names of Some Molecular Compounds Composed of Two Elements
C Name Compound N
o a
m m
p e
o
u
n
d

S sulfur dioxide BCl3 b

O o
2 r
o
n
t
r
i
c
h
l
o
r
i
d
e

3.5 Covalently-Bonded Species.2 [Link]

C Name Compound N
o a
m m
p e
o
u
n
d

S sulfur trioxide SF6 s

O u
3 l
f
u
r
h
e
x
a
f
l
u
o
r
i
d
e

N nitrogen dioxide PF5 p

O h
2 o
s
p
h
o
r
u
s
p
e
n
t
a
f
l
u
o
r
i
d
e

3.5 Covalently-Bonded Species.3 [Link]

 C Name Compound N
o a
m m
p e
o
u
n
d

N dinitrogen tetroxide P4O10 t

2 e
O t
4 r
a
p
h
o
s
p
h
o
r
u
s
d
e
c
a
o
x
i
d
e

N dinitrogen pentoxide IF7 i

2 o
O d
5 i
n
e
h
e
p
t
a
f
l
u
o
r
i
d
e

There are a few common names that you will encounter as you continue your study of chemistry. For example, although NO is often
called nitric oxide, its proper name is nitrogen monoxide. Similarly, N2O is known as nitrous oxide even though our rules would specify
the name dinitrogen monoxide. You should commit to memory the common names of compounds as you encounter them.

Example 3.5Covalently − BondedSpecies. 2 : Naming Covalent Compounds

Name the following covalent compounds:
a. SF6
b. N2O3
c. Cl2O7
d. P4O6

3.5 Covalently-Bonded Species.4 [Link]

 Solution
Because these compounds consist solely of nonmetals, we use prefixes to designate the number of atoms of each element:
a. sulfur hexafluoride
b. dinitrogen trioxide
c. dichlorine heptoxide
d. tetraphosphorus hexoxide

Exercise 3.5Covalently − BondedSpecies. 2

Write the formulas for the following compounds:
a. phosphorus pentachloride
b. dinitrogen monoxide
c. iodine heptafluoride
d. carbon tetrachloride
Answer:
(a) PCl5; (b) N2O; (c) IF7; (d) CCl4

Binary Compounds of Hydrogen

Covalently-bonded compounds that consist of only H atoms and one atom of one other element are named as if they are ionically-
bonded. Specifically, the number of atoms is not indicated in the name. Thus, HI is named hydrogen iodide, and H2S is named
hydrogen sulfide. Be aware that the systematic name is not dihydrogen monoxide.

Binary Acids
Some compounds containing hydrogen are members of an important class of substances known as acids. The chemistry of these
compounds is explored in more detail in later chapters of this text, but for now, it will suffice to note that many acids release hydrogen
ions, H+, when dissolved in water. To denote this distinct chemical property, a mixture of water with an acid is given a name derived
from the compound’s name. If the compound is a binary acid (comprised of hydrogen and one other nonmetallic element):
1. The word “hydrogen” is changed to the prefix hydro-
2. The other nonmetallic element name is modified by adding the suffix -ic
3. The word “acid” is added as a second word
For example, when the gas HCl (hydrogen chloride) is dissolved in water, the solution is called hydrochloric acid. Several other
examples of this nomenclature are shown in Table 3.5C ovalently − BondedSpecies. 5 .
Table 3.5C ovalently − BondedSpecies. 5 : Names of Some Simple Acids
Name of Gas Name of Acid

HF(g), hydrogen fluoride HF(aq), hydrofluoric acid

HCl(g), hydrogen chloride HCl(aq), hydrochloric acid

HBr(g), hydrogen bromide HBr(aq), hydrobromic acid

HI(g), hydrogen iodide HI(aq), hydroiodic acid

H2S(g), hydrogen sulfide H2S(aq), hydrosulfuric acid

Oxyacids
Many compounds containing three or more elements (such as organic compounds or coordination compounds) are subject to
specialized nomenclature rules that you will learn later. However, we will briefly discuss the important compounds known as oxyacids,
compounds that contain hydrogen, oxygen, and at least one other element, and are bonded in such a way as to impart acidic properties

3.5 Covalently-Bonded Species.5 [Link]

to the compound (you will learn the details of this in a later chapter). Typical oxyacids consist of hydrogen combined with a
polyatomic, oxygen-containing ion. To name oxyacids:
1. Omit “hydrogen”
2. Start with the root name of the anion
3. Replace –ate with –ic, or –ite with –ous
4. Add “acid”
For example, consider H2CO3 (which you might be tempted to call “hydrogen carbonate”). To name this correctly, “hydrogen” is
omitted; the –ate of carbonate is replace with –ic; and acid is added—so its name is carbonic acid. Other examples are given in Table
3.5C ovalently − BondedSpecies. 6 . There are some exceptions to the general naming method (e.g., H2SO4 is called sulfuric acid,

not sulfic acid, and H2SO3 is sulfurous, not sulfous, acid).

Table 3.5C ovalently − BondedSpecies. 6 : Names of Common Oxyacids
Formula Anion Name Acid Name

HC2H3O2 acetate acetic acid

HNO3 nitrate nitric acid

HNO2 nitrite nitrous acid

HClO4 perchlorate perchloric acid

H2CO3 carbonate carbonic acid

H2SO4 sulfate sulfuric acid

H2SO3 sulfite sulfurous acid

H3PO4 phosphate phosphoric acid

Summary
Chemists use nomenclature rules to clearly name compounds. Ionic and molecular compounds are named using somewhat-different
methods. Binary ionic compounds typically consist of a metal and a nonmetal. The name of the metal is written first, followed by the
name of the nonmetal with its ending changed to –ide. For example, K2O is called potassium oxide. If the metal can form ions with
different charges, a Roman numeral in parentheses follows the name of the metal to specify its charge. Thus, FeCl2 is iron(II) chloride
and FeCl3 is iron(III) chloride. Some compounds contain polyatomic ions; the names of common polyatomic ions should be
memorized. Molecular compounds can form compounds with different ratios of their elements, so prefixes are used to specify the
numbers of atoms of each element in a molecule of the compound. Examples include SF6, sulfur hexafluoride, and N2O4, dinitrogen
tetroxide. Acids are an important class of compounds containing hydrogen and having special nomenclature rules. Binary acids are
named using the prefix hydro-, changing the –ide suffix to –ic, and adding “acid;” HCl is hydrochloric acid. Oxyacids are named by
changing the ending of the anion to –ic, and adding “acid;” H2CO3 is carbonic acid.

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley (Stephen
F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed under a Creative
Commons Attribution License 4.0 license. Download for free at [Link]
Modified by Tom Neils (Grand Rapids Community College)

3.5 Covalently-Bonded Species: Formulas and Names is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

3.5 Covalently-Bonded Species.6 [Link]

3.6 Electronegativity and Bond Polarity
Skills to Develop
To define electronegativity and bond polarity
To calculate the percent ionic character of a covalent polar bond

The electron pairs shared between two atoms are not necessarily shared equally. For example, whereas the bonding electron pair is
shared equally in the covalent bond in C l , in N aC l the one valence electron is stripped from the Na atom and is incorporated into
2

the electronic structure of the Cl atom - and the compound is most accurately described as consisting of individual N a and C l
+ −

ions (ionic bonding). For most covalent substances, their bond character falls between these two extremes. As demonstrated below,
the bond polarity is a useful concept for describing the sharing of electrons between atoms within a covalent bond:
A nonpolar covalent bond is one in which the electrons are shared equally or nearly equally between two atoms.
A polar covalent bond is one in which one atom has a greater attraction for the electrons than the other atom. If this relative
attraction is great enough, then the bond is an ionic bond.

Percent Ionic Character of a Covalent polar Bond

The two idealized extremes of chemical bonding: (1) ionic bonding—in which one or more electrons are transferred completely
from one atom to another, and the resulting ions are held together by purely electrostatic forces—and (2) covalent bonding, in
which electrons are shared equally between two atoms. Most compounds, however, have polar covalent bonds, which means that
electrons are shared unequally between the bonded atoms. Figure 4 compares the electron distribution in a polar covalent bond with
those in an ideally covalent and an ideally ionic bond. Recall that a lowercase Greek delta (δ ) is used to indicate that a bonded atom
possesses a partial positive charge, indicated by δ , or a partial negative charge, indicated by δ , and a bond between two atoms
+ −

that possess partial charges is a polar bond.

Figure 4 : The Electron Distribution in a Nonpolar Covalent Bond, a Polar Covalent Bond, and an Ionic Bond Using Lewis
Electron Structures. In a purely covalent bond (a), the bonding electrons are shared equally between the atoms. In a purely ionic
bond (c), an electron has been transferred completely from one atom to the other. A polar covalent bond (b) is intermediate
between the two extremes: the bonding electrons are shared unequally between the two atoms, and the electron distribution is
asymmetrical with the electron density being greater around the more electronegative atom. Electron-rich (negatively charged)
regions are shown in blue; electron-poor (positively charged) regions are shown in red.
One method for calculating the percent ionic character of a bond is to use the following equation:
E Nhigher − E Nlower
% ionic character = × 100
ENhigher

≥ 50% means the bond is ionic

> 5% but < 50% means the bond is polar covalent

1 [Link]
 ≤ 5% means the bond is pure (non-polar) covalent
Table of Pauling Electronegativities

Example 1
What is the % ionic character of a P-S bond?
Solution
Add text here.

Exercise 1
Add exercises text here.

Answer
Add texts here. Do not delete this text first.

Bond Polarity
The polarity of a bond—the extent to which it is polar—is determined largely by the relative electronegativities of the bonded
atoms. Electronegativity (χ) was defined as the ability of an atom in a molecule or an ion to attract electrons to itself. Thus there is
a direct correlation between electronegativity and bond polarity. A bond is nonpolar if the bonded atoms have equal
electronegativities. If the electronegativities of the bonded atoms are not equal, however, the bond is polarized toward the more
electronegative atom. A bond in which the electronegativity of B (χB) is greater than the electronegativity of A (χA), for example, is
indicated with the partial negative charge on the more electronegative atom:

less electronegative more electronegative

A − B (1)
+ −
δ δ

One way of estimating the ionic character of a bond—that is, the magnitude of the charge separation in a polar covalent bond—is
to calculate the difference in electronegativity between the two atoms: Δχ = χB − χA.
To predict the polarity of the bonds in Cl2, HCl, and NaCl, for example, we look at the electronegativities of the relevant atoms: χCl
= 3.16, χH = 2.20, and χNa = 0.93. Cl2 must be nonpolar because the electronegativity difference (Δχ) is zero; hence the two
chlorine atoms share the bonding electrons equally. In NaCl, Δχ is 2.23. This high value is typical of an ionic compound (Δχ ≥
≈1.5) and means that the valence electron of sodium has been completely transferred to chlorine to form Na+ and Cl− ions. In HCl,
however, Δχ is only 0.96. The bonding electrons are more strongly attracted to the more electronegative chlorine atom, and so the
charge distribution is
+ −
δ δ
(2)
H − Cl

Remember that electronegativities are difficult to measure precisely and different definitions produce slightly different numbers. In
practice, the polarity of a bond is usually estimated rather than calculated.

Bond polarity and ionic character increase with an increasing difference in electronegativity.

2 [Link]
As with bond energies, the electronegativity of an atom depends to some extent on its chemical environment. It is therefore
unlikely that the reported electronegativities of a chlorine atom in NaCl, Cl2, ClF5, and HClO4 would be exactly the same.

Dipole Moments
The asymmetrical charge distribution in a polar substance such as HCl produces a dipole moment where Qr in meters (m). is
abbreviated by the Greek letter mu (µ). The dipole moment is defined as the product of the partial charge Q on the bonded atoms
and the distance r between the partial charges.
When a molecule with a dipole moment is placed in an electric field, it tends to orient itself with the electric field because of its
asymmetrical charge distribution (Figure 4).

Figure 5 : Molecules That Possess a Dipole Moment Partially Align Themselves with an Applied Electric Field. In the absence of a
field (a), the HCl molecules are randomly oriented. When an electric field is applied (b), the molecules tend to align themselves
with the field, such that the positive end of the molecular dipole points toward the negative terminal and vice versa.
The measured dipole moment of HCl indicates that the H–Cl bond has approximately 18% ionic character (0.1811 × 100), or 82%
covalent character. Instead of writing HCl as
+ −
δ δ
(3)
H − Cl

we can therefore indicate the charge separation quantitatively as

+ −
0.18δ 0.18δ
(4)
H − Cl

Our calculated results are in agreement with the electronegativity difference between hydrogen and chlorine χH = 2.20; χCl = 3.16,
χCl − χH = 0.96), a value well within the range for polar covalent bonds. We indicate the dipole moment by writing an arrow above
the molecule. Mathematically, dipole moments are vectors, and they possess both a magnitude and a direction. The dipole moment
of a molecule is the vector sum of the dipoles of the individual bonds. In HCl, for example, the dipole moment is indicated as
follows:

The arrow shows the direction of electron flow by pointing toward the more electronegative atom.
The charge on the atoms of many substances in the gas phase can be calculated using measured dipole moments and bond
distances. Figure 6 shows a plot of the percent ionic character versus the difference in electronegativity of the bonded atoms for
several substances. According to the graph, the bonding in species such as NaCl(g) and CsF(g) is substantially less than 100% ionic
in character. As the gas condenses into a solid, however, dipole–dipole interactions between polarized species increase the charge
separations. In the crystal, therefore, an electron is transferred from the metal to the nonmetal, and these substances behave like
classic ionic compounds. The data in Figure 6 show that diatomic species with an electronegativity difference of less than 1.5 are
less than 50% ionic in character, which is consistent with our earlier description of these species as containing polar covalent
bonds. The use of dipole moments to determine the ionic character of a polar bond is illustrated in Example 2.

3 [Link]
Figure 6 : A Plot of the Percent Ionic Character of a Bond as Determined from Measured Dipole Moments versus the Difference in
Electronegativity of the Bonded [Link] the gas phase, even CsF, which has the largest possible difference in electronegativity
between atoms, is not 100% ionic. Solid CsF, however, is best viewed as 100% ionic because of the additional electrostatic
interactions in the lattice.

Summary
Bond polarity and ionic character increase with an increasing difference in electronegativity. The electronegativity (χ) of an
element is the relative ability of an atom to attract electrons to itself in a chemical compound and increases diagonally from the
lower left of the periodic table to the upper right. The Pauling electronegativity scale is based on measurements of the strengths of
covalent bonds between different atoms, whereas the Mulliken electronegativity of an element is the average of its first ionization
energy and the absolute value of its electron affinity. Elements with a high electronegativity are generally nonmetals and electrical
insulators and tend to behave as oxidants in chemical reactions. Conversely, elements with a low electronegativity are generally
metals and good electrical conductors and tend to behave as reductants in chemical reactions.
Compounds with polar covalent bonds have electrons that are shared unequally between the bonded atoms. The polarity of such a
bond is determined largely by the relative electronegativites of the bonded atoms. The asymmetrical charge distribution in a polar
substance produces a dipole moment, which is the product of the partial charges on the bonded atoms and the distance between
them.

Modified by Tom Neils (Grand Rapids Community College)

3.6 Electronegativity and Bond Polarity is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

4 [Link]
3.7 Lewis Structures
Skills to Develop
To use Lewis dot symbols to explain the stoichiometry of a compound

We begin our discussion of the relationship between structure and bonding in covalent compounds by describing the interaction
between two identical neutral atoms—for example, the H2 molecule, which contains a purely covalent bond. Each hydrogen atom
in H2 contains one electron and one proton, with the electron attracted to the proton by electrostatic forces. As the two hydrogen
atoms are brought together, additional interactions must be considered (Figure 1):
The electrons in the two atoms repel each other because they have the same charge (E > 0).
Similarly, the protons in adjacent atoms repel each other (E > 0).
The electron in one atom is attracted to the oppositely charged proton in the other atom and vice versa (E < 0). Recall that it is
impossible to specify precisely the position of the electron in either hydrogen atom. Hence the quantum mechanical probability
distributions must be used.

Figure 1 : Attractive and Repulsive Interactions between Electrons and Nuclei in the Hydrogen Molecule. Electron–electron and
proton–proton interactions are repulsive; electron–proton interactions are attractive. At the observed bond distance, the repulsive
and attractive interactions are balanced.
A plot of the potential energy of the system as a function of the internuclear distance (Figure 2) shows that the system becomes
more stable (the energy of the system decreases) as two hydrogen atoms move toward each other from r = ∞, until the energy
reaches a minimum at r = r0 (the observed internuclear distance in H2 is 74 pm). Thus at intermediate distances, proton–electron
attractive interactions dominate, but as the distance becomes very short, electron–electron and proton–proton repulsive interactions
cause the energy of the system to increase rapidly. Notice the similarity between Figures 1 and 2, which described a system
containing two oppositely charged ions. The shapes of the energy versus distance curves in the two figures are similar because they
both result from attractive and repulsive forces between charged entities.

Figure 2 : A Plot of Potential Energy versus Internuclear Distance for the Interaction between Two Gaseous Hydrogen Atoms.
At long distances, both attractive and repulsive interactions are small. As the distance between the atoms decreases, the attractive
electron–proton interactions dominate, and the energy of the system decreases. At the observed bond distance, the repulsive
electron–electron and proton–proton interactions just balance the attractive interactions, preventing a further decrease in the

1 [Link]
internuclear distance. At very short internuclear distances, the repulsive interactions dominate, making the system less stable than
the isolated atoms.

Using Lewis Dot Symbols to Describe Covalent Bonding

It is usually easier to figure out a problem if you can draw a picture, either mental or real, of what is happening. This is often done
in physics and mathematics, and it is especially helpful when looking at the bonding, structure, physical properties, and reactivity
of compounds.
The most common picture, or model, of elements and compounds used is the Lewis Dot Structure. These pictures show you the
type(s) of atom(s) involved, their position in the molecule, and where their valence electrons are situated.
To draw structures of substances you need to know:
1. the electronegativities of the elements so that you can decide if the atoms form ionic bonds or covalent bonds.
2. the number of valence electrons so that you can determine what ions will likely form (if the bonding will be ionic) or
how many electrons will need to be shared in bonds (if the bonding will be covalent.)
GENERAL TERMS FOR LEWIS DOT STRUCTURES:

1. Dot • one dot represents one valence electron (found on odd-electron particles)
2. Pair of Dots •• a pair of dots represents a nonbonding (lone) pair of electrons that are not involved in a covalent bond and
"belong to" only one atom
3. Dash each dash represents two electrons that are shared between two atoms as a covalent bond.

One dash — a single bond; one set of two electrons shared; also a sigma (σ) bond

Two dashes = a double bond; two sets of two electrons shared; one sigma (σ) and one pi (π) bond
Three dashes a triple bond: three sets of two electrons shared; one sigma and two pi (π) bonds

The valence electron configurations of the constituent atoms of a covalent compound are important factors in determining its
structure, stoichiometry, and properties. For example, chlorine, with seven valence electrons, is one electron short of an octet. If
two chlorine atoms share their unpaired electrons by making a covalent bond and forming Cl2, they can each complete their
valence shell:

Each chlorine atom now has an octet. The electron pair being shared by the atoms is called a bonding pair; the other three pairs of
electrons on each chlorine atom are called lone pairs. Lone pairs are not involved in covalent bonding.
We can illustrate the formation of a water molecule from two hydrogen atoms and an oxygen atom using Lewis dot symbols:

The structure on the right is the Lewis electron structure, or Lewis structure, for H2O. With two bonding pairs and two lone pairs,
the oxygen atom has now completed its octet. Moreover, by sharing a bonding pair with oxygen, each hydrogen atom now has a
full valence shell of two electrons. Chemists usually indicate a bonding pair by a single line, as shown here for our two examples:

In CHM 120, you should always use lines to represent bonds. The use of dots will be reserved for non-bonding (lone)
electron pairs.
The following procedure can be used to construct Lewis electron structures for more complex molecules and ions:
Skills to Develop

2 [Link]
 THE EASY METHOD PROCEDURE TO DETERMINE A LEWIS DOT STRUCTURE
In this process, the basic concept of this method is that all valence electrons present will be taken away from the
individual atoms and pooled together. They will first be doled out to form the requisite number of bonds. The remaining
valence electrons will then be added to individual atoms as lone pairs to complete the octet of each atom.
1. Calculate the total number of valence electrons required for each atom to have an octet, or eight valence electrons. The
major exception to this rule is that hydrogen wants only two (2) valence electrons. The other two most commonly-
occurring exceptions are Be (4) and B (6) valence electrons.
Thus, the process for step one is 2 x (# of H atoms) + 8 x (# of most other atoms) = valence electrons needed
2. Calculate the total number of valence electrons in the given species.
If you have a polyatomic anion, you must add the number of '-' charges because there are extra valence electrons.
If you have a polyatomic cation, you must subtract the number of '+' charges because there are missing valence
electrons.
3. Subtract result 2 from result 1. This is the number of valence electrons lacking for each atom to have its own octet. This
number of electrons will have to be shared in bonds.
4. Divide result 3 by two, because there are two electrons per bond. This is the number of covalent bonds you must use!
5. Connect the atoms in the formula together with the number of bonds from result 4. Helpful hints:
i) H atoms form only one bond.
ii) The first atom in the formula is usually the central atom to which the other atoms bond
iii) If the particle has only three atoms, and each atom is of a different element, the atom in the middle of the formula is
usually in the middle of the structure.
iv) species are as symmetrical as possible when there are several central atoms
v) For neutral species:
Group IV atoms usually form four bonds
Group V atoms usually form three bonds
Group VI atoms usually form two bonds
Group VII atoms usually form one bond
6. Add in electrons as non-bonding pairs or lone pairs (groups of two), so that each atom has eight electrons around it.
7. Count the total number of electrons in the structure. The number should be equal to the number of electrons in result 2.
CAUTIONS:
1. Never put a lone pair on an H atom.
2. The only common substances that have a lone pair on a C atom are CO and CN-. Other than those two particles, you
should not put a lone pair on a C atom.

Now let’s apply this procedure to some particular compounds, beginning with one we have already discussed.

The central atom is usually the least electronegative element in the molecule or ion; hydrogen and the halogens are usually
terminal.

The H O Molecule
2

1. (1 O atom) x (8) + (2 H atoms) x (2) = 12 valence electrons needed

2. (1 O atom) x (6) + (2 H atoms) x (1) = 8 valence electrons present.
3. 12-8 = 4 electrons short, thus 4 electrons must be shared
4. 4 shared electrons/ 2 electrons per bond = 2 bonds
5. Connect the each of the two H atoms to the O atom with one single bond each.

3 [Link]
 6. Add the remaining 4 electrons to the oxygen (as two lone pairs) to give the following structure:

This is the Lewis structure we drew earlier. Because it gives oxygen an octet and each hydrogen two electrons, we do not need to
use step 6.

The OCl Ion

−

1. (1 O atom) x (8) + (1 Cl atom) x (8) = 16 valence electrons needed

2. (1 O atom) x (6) + (1 Cl atom) x (7) + 1 = 14 valence electrons present.
3. 16 - 14 = 2 electrons short, thus 2 electrons must be shared
4. 2 shared electrons/ 2 electrons per bond = 1 bond
5. Connect the two atoms with one single bond .
6. Add the remaining 12 electrons as lone pairs, with 3 pairs on the O atom and 3 pairs on the Cl atom, giving the following
structure:

Each atom now has an octet of electrons. The Lewis electron structure is drawn within brackets as is customary for an ion, with the
overall charge indicated outside the brackets, and the bonding pair of electrons is indicated by a solid line. OCl− is the hypochlorite
ion, the active ingredient in chlorine laundry bleach and swimming pool disinfectant.

The C H O Molecule
2

1. (1 O atom) x (8) + (1 C atom) x (8) + (2 H atoms) x (2) = 20 valence electrons needed

2. (1 O atom) x (6) + (1 C atom) x (4) + (2 H atoms) x (1) = 12 valence electrons present.
3. 20 - 12 = 8 electrons short, thus 8 electrons must be shared
4. 8 shared electrons/ 2 electrons per bond = 4 bonds
5. Because carbon is less electronegative than oxygen and hydrogen is normally terminal, C must be the central atom. Connect the
two H atoms and the O atom to the C atom with with one single bond each, giving the structure:

6. There is still one more bond that you must use in the structure. At this point, the C atom has only three bonds and the O atom has
only one bond. Thus, putting one more bond between the C and the O, creating a double bond, will satisfy all bonding
requirements.
7. Add the remaining 4 electrons as two lone pairs on the O atom, giving the following structure:

Both the oxygen and the carbon now have an octet of electrons, so this is an acceptable Lewis electron structure. The O has two
bonding pairs and two lone pairs, and C has four bonding pairs. This is the structure of formaldehyde, which is used in embalming
fluid.
An alternative structure can be drawn with one H bonded to O. Formal charges, discussed later in this section, suggest that such a
structure is less stable than that shown previously.

Example 1
Write the Lewis electron structure for each species.
a. NCl3
b. S22−
c. NOCl
Given: chemical species
Asked for: Lewis electron structures

4 [Link]
Strategy:
Use the six-step procedure to write the Lewis electron structure for each species.
Solution:
a. NCl3 Determine number of bonds needed
1. (1 N atom) x (8) + (3 Cl atoms) x (8) = 32 valence electrons needed
2. (1 N atom) x (5) + (3 Cl atoms) x (7) = 26 valence electrons present.
3. 32 - 26 = 6 electrons short, thus 6 electrons must be shared
4. 6 shared electrons/ 2 electrons per bond = 3 bonds
5. Nitrogen is less electronegative than chlorine, and halogen atoms are usually terminal, so nitrogen is the central atom.
Connect the three Cl atoms with the central N atom with three single bonds.
6. You have used 6 electrons. Add the remaining 20 electrons on to the structure as lone pairs, to ensure that each atom has
an octet (1 lone pair for N, and 3 lone pairs for each Cl.)

Nitrogen trichloride is an unstable oily liquid once used to bleach flour; this use is now prohibited in the United States.

b. S22- ion Determine number of bonds needed

1. (2 S atoms) x (8) = 16 valence electrons needed
2. (2 S atoms) x (6) + 2 = 14 valence electrons present.
3. 16-14 = 2 electrons short, thus 2 electrons must be shared
4. 2 shared electrons/ 2 electrons per bond = 1 bond
5. Connect the each of the two S atoms with one single bond each.
6. You have used two electrons. Add the remaining 12 electrons to the S atoms (as three lone pairs per S atom) to give the
following structure:

c. NOCl Determine number of bonds needed

1. (1 N atom) x (8) + (1 O atom) x (8) + (1 Cl atom) x (8) = 24 valence electrons needed
2. (1 N atom) x (5) + (1 O atom) x (6) + (1 Cl atom) x (7)= 18 valence electrons present.
3. 24-18 = 6 electrons short, thus 6 electrons must be shared
4. 6 shared electrons/ 2 electrons per bond = 3 bonds
5. Because nitrogen is less electronegative than oxygen or chlorine, it is the central atom. Also, this molecule falls into
the category of a particle that has only three atoms, and each atom is of a different element, so the atom in the middle
of the formula is usually in the middle of the structure. Placing one bonding pair of electrons between each pair of
bonded atoms uses 4 electrons and gives the following:

5 [Link]
 6. There is still one more bond that you must use in the structure. At this point, the N atom has only two bonds and the O
atom has only one bond. Thus, putting one more bond between the N and the O, creating a double bond, will satisfy all
bonding requirements. The Cl, as a halogen, is stable with just one bond.
7. You have used 6 electrons. Add the remaining 12 electrons as two lone pairs on the O atom, one lone pair on the N
atom, and three lone pairs ion the Cl atom giving the following structure:

All atoms now have octet configurations. This is the Lewis electron structure of nitrosyl chloride, a highly corrosive, reddish-
orange gas.

Exercise 1
Write Lewis electron structures for CO2 and SCl2, a vile-smelling, unstable red liquid that is used in the manufacture of rubber.
Answer:

1.

2.

Using Lewis Electron Structures to Explain Stoichiometry

Lewis dot symbols provide a simple rationalization of why elements form compounds with the observed stoichiometries. In the
Lewis model, the number of bonds formed by an element in a neutral compound is the same as the number of unpaired electrons it
must share with other atoms to complete its octet of electrons. For the elements of Group VIIA (the halogens), this number is one;
for the elements of Group VIA (the chalcogens), it is two; for Group VA elements, three; and for Group IVA elements four. These
requirements are illustrated by the following Lewis structures for the hydrides of the lightest members of each group:

6 [Link]
Elements may form multiple bonds to complete an octet. In ethylene, for example, each carbon contributes two electrons to the
double bond, giving each carbon an octet (two electrons/bond × four bonds = eight electrons). Neutral structures with fewer or
more bonds exist, but they are unusual and violate the octet rule.

Lewis structures explain why the elements of groups IVA–VIIA form neutral compounds with four, three, two, and one bonded
atom(s), respectively.

Allotropes of an element can have very different physical and chemical properties because of different three-dimensional
arrangements of the atoms; the number of bonds formed by the component atoms, however, is always the same. Diamond is a hard,
transparent solid; graphite is a soft, black solid; and the fullerenes have open cage structures. Despite these differences, the carbon
atoms in all three allotropes form four bonds, in accordance with the octet rule.
Elemental phosphorus also exists in three forms: white phosphorus, a toxic, waxy substance that initially glows and then
spontaneously ignites on contact with air; red phosphorus, an amorphous substance that is used commercially in safety matches,
fireworks, and smoke bombs; and black phosphorus, an unreactive crystalline solid with a texture similar to graphite (Figure 3).
Nonetheless, the phosphorus atoms in all three forms obey the octet rule and form three bonds per phosphorus atom.

Figure 3 : The Three Allotropes of Phosphorus: White, Red, and Black. ll three forms contain only phosphorus atoms, but they
differ in the arrangement and connectivity of their atoms. White phosphorus contains P4 tetrahedra, red phosphorus is a network of
linked P8 and P9 units, and black phosphorus forms sheets of six-membered rings. As a result, their physical and chemical
properties differ dramatically.

Formal Charges
It is sometimes possible to write more than one Lewis structure for a substance that does not violate the octet rule, as we saw for
CH2O, but not every Lewis structure may be equally reasonable. In these situations, we can choose the most stable Lewis structure
by considering the formal charge assigned to the atoms. A formal charge is the difference between the number of valence electrons
in the free atom and the number assigned to it in the Lewis electron structure. The formal charge is a way of computing the charge
distribution within a Lewis structure; the sum of the formal charges on the atoms within a molecule or an ion must equal the overall
charge on the molecule or ion. A formal charge does not represent a true charge on an atom in a covalent bond but is simply used to
predict the most likely structure when a compound has more than one valid Lewis structure.
To calculate formal charges, we assign electrons in the molecule to individual atoms according to these rules:

7 [Link]
 Nonbonding electrons are assigned to the atom on which they are located.
Bonding electrons are divided equally between the bonded atoms.
For each atom, we then compute a formal charge:
−
bonding e
− −
f ormal charge = valence e − (non − bonding e + )
2
(atom in Lewis structure)
(f ree atom) (atom in Lewis structure)

To illustrate this method, let’s calculate the formal charge on the atoms in ammonia (NH3) whose Lewis electron structure is as
follows:

A neutral nitrogen atom has five valence electrons (it is in group VA). From its Lewis electron structure, the nitrogen atom in
ammonia has one lone pair and shares three bonding pairs with hydrogen atoms, so nitrogen itself is assigned a total of five
electrons [2 nonbonding e− + (6 bonding e−/2)]. Substituting into Equation 1, we obtain
−
− −
6 bonding e
f ormal charge (N ) = 5 valence e − (2 non − bonding e + ) =0 (1)
2

A neutral hydrogen atom has one valence electron. Each hydrogen atom in the molecule shares one pair of bonding electrons and is
therefore assigned one electron [0 nonbonding e− + (2 bonding e−/2)]. Using Equation 1 to calculate the formal charge on
hydrogen, we obtain
−
− −
2 bonding e
f ormal charge (H ) = 1 valence e − (0 non − bonding e + ) =0 (2)
2

The hydrogen atoms in ammonia have the same number of electrons as neutral hydrogen atoms, and so their formal charge is also
zero. Adding together the formal charges should give us the overall charge on the molecule or ion. In this example, the nitrogen and
each hydrogen has a formal charge of zero. When summed the overall charge is zero, which is consistent with the overall charge on
the NH3 molecule.

An atom, molecule, or ion has a formal charge of zero if it has the number of bonds that is typical for that species.

A second way to assign electrons is to draw the Lewis dot structure and then draw a circle around each atom in the structure. The
circle should be drawn so that every bond is cut in half, and so that lone pairs on an atom are included in the circle. The electrons in
the circle around the atom are the electrons that are assigned to that atom:

The formal charge is calculated by subtracting the number of assigned electrons (in the circle) from the number of valence
electrons.
Typically, the structure with the most zero formal charges on the atoms is the more stable Lewis structure. In cases where there are
positive or negative formal charges on various atoms, stable structures generally have negative formal charges on the more
electronegative atoms and positive formal charges on the less electronegative atoms. The next example further demonstrates how to
calculate formal charges.

Example 2 : The Ammonium Ion

Calculate the formal charges on each atom in the NH4+ ion.
Given: chemical species
Asked for: formal charges

8 [Link]
 Strategy:
Identify the number of valence electrons in each atom in the NH4+ ion. Use the Lewis electron structure of NH4+ to identify the
number of bonding and nonbonding electrons associated with each atom and then use Equation 1 to calculate the formal charge
on each atom.
Solution:
The Lewis electron structure for the NH4+ ion is as follows:

The nitrogen atom shares four bonding pairs of electrons, and a neutral nitrogen atom has five valence electrons. Using Equation
??? , the formal charge on the nitrogen atom is therefore

8
f ormal charge (N ) = 5 − (0 + ) =0 (3)
2

Each hydrogen atom in has one bonding pair. The formal charge on each hydrogen atom is therefore
2
f ormal charge (H ) = 1 − (0 + ) =0 (4)
2

The formal charges on the atoms in the NH4+ ion are thus

Adding together the formal charges on the atoms should give us the total charge on the molecule or ion. In this case, the sum of
the formal charges is 0 + 1 + 0 + 0 + 0 = +1.

Exercise 2
Write the formal charges on all atoms in BH4−.
Answer:

If an atom in a molecule or ion has the number of bonds that is typical for that atom (e.g., four bonds for carbon), its formal
charge is zero.

Using Formal Charges to Distinguish Viable Lewis Structures

As an example of how formal charges can be used to determine the most stable Lewis structure for a substance, we can compare
two possible structures for CO2. Both structures conform to the rules for Lewis electron structures.

CO2
1. (1 C atom) x (8) + (2 O atoms) x (8)= 24 valence electrons needed
2. (1 C atom) x (4) + (2 O atoms) x (6) = 16 valence electrons present.
3. 24 - 16 = 8 electrons short, thus 8 electrons must be shared
4. 8 shared electrons/ 2 electrons per bond = 4 bonds

9 [Link]
 5. Carbon is less electronegative than oxygen, so carbon is the central atom. Connect the two O atoms with the central C atom
with one single bond each. You have two more bonds that need to be added to the structure. These two bonds could be added in
three different ways:

6. You have used 8 electrons. Add the remaining 8 electrons on to the O atoms as lone pairs to ensure that each atom has an octet:

All three Lewis structures give all three atoms an octet. How do we decide between these three possibilities? First, recognize that
the left form and the right form are equivalent; that is they each have one singly-bonded O atom and one triply-bonded O atom. The
middle structure is not equivalent to either of the side structures. The formal charges for the two non-equivalent Lewis structures of
CO2 are as follows:

Both Lewis structures have a net formal charge of zero, but the structure on the right has a +1 charge on the more electronegative
atom (O). Thus the symmetrical Lewis structure on the left is predicted to be more stable, and it is, in fact, the structure observed
experimentally. Remember, though, that formal charges do not represent the actual charges on atoms in a molecule or ion. They are
used simply as a bookkeeping method for predicting the most stable Lewis structure for a compound.

The Lewis structure with the set of formal charges closest to zero is usually (but not always) the most stable.

Example 3 : The Thiocyanate Ion

The thiocyanate ion (SCN−), which is used in printing and as a corrosion inhibitor against acidic gases, has at least two possible
Lewis electron structures. Draw two possible structures, assign formal charges on all atoms in both, and decide which is the
preferred arrangement of electrons.
Given: chemical species
Asked for: Lewis electron structures, formal charges, and preferred arrangement
Strategy:
A. Use the step-by-step procedure to write two plausible Lewis electron structures for SCN−.
B. Calculate the formal charge on each atom.
C. Predict which structure is preferred based on the formal charge on each atom and its electronegativity relative to the other
atoms present.
Solution:
A Possible Lewis structures for the SCN− ion are as follows:

B We must calculate the formal charges on each atom to identify the more stable structure. If we begin with carbon, we notice
that the carbon atom in each of these structures shares four bonding pairs, the number of bonds typical for carbon, so it has a
formal charge of zero. Continuing with sulfur, we observe that in (a) the sulfur atom shares one bonding pair and has three lone
pairs and has a total of six valence electrons. The formal charge on the sulfur atom is therefore
6 − (6 +
2
) = −1.5 − (4 +
2
4
) = −1
2
In (c), nitrogen has a formal charge of −2.
C Which structure is preferred? Structure (b) is preferred because the negative charge is on the more electronegative atom (N),
and it has lower formal charges on each atom as compared to structure (c): 0, −1 versus +1, −2.

Exercise 1 : The Fulminate Ion

10 [Link]
 Salts containing the fulminate ion (CNO−) are used in explosive detonators. Draw three Lewis electron structures for CNO− and
use formal charges to predict which is more stable. (Note: N is the central atom.)
Answer:

The second structure is predicted to be more stable.

Summary
Lewis dot symbols provide a simple rationalization of why elements form compounds with the observed stoichiometries. In Lewis
electron structures, we encounter bonding pairs, which are shared by two atoms, and lone pairs, which are not shared between
atoms. Lewis structures are an attempt to rationalize why certain stoichiometries are commonly observed for the elements of
particular families. Neutral compounds of group IVA elements typically contain four bonds around each atom (a double bond
counts as two, a triple bond as three), whereas neutral compounds of group VA elements typically contain three bonds. In cases
where it is possible to write more than one Lewis electron structure with octets around all the nonhydrogen atoms of a compound,
the formal charge on each atom in alternative structures must be considered to decide which of the valid structures can be
excluded and which is the most reasonable. The formal charge is the difference between the number of valence electrons of the free
atom and the number of electrons assigned to it in the compound, where bonding electrons are divided equally between the bonded
atoms. The Lewis structure with the lowest formal charges on the atoms is almost always the most stable one.

Contributors
Modified by Joshua Halpern (Howard University)
Modified by Tom Neils (Grand Rapids Community College)

3.7 Lewis Structures is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

11 [Link]
3.8 Resonance and Formal Charge Revisited
Skills to Develop
To understand the concept of resonance.

Resonance structures are a set of two or more Lewis Structures that collectively describe the electronic bonding a single polyatomic
species including fractional bonds and fractional charges. Resonance structure are capable of describing delocalized electrons that
cannot be expressed by a single Lewis formula with an integer number of covalent bonds. When drawing resonance structures, you
are allowed to move only lone pairs of electrons and pi bonds. You cannot move any atoms, and you cannot make any new sigma
bonds or remove any existing sigma bonds.

Sometimes one Lewis Structure is not Enough

Sometimes, even when formal charges are considered, the bonding in some molecules or ions cannot be described by a single
Lewis structure. Resonance is a way of describing delocalized electrons within certain molecules or polyatomic ions where the
bonding cannot be expressed by a single Lewis formula. A molecule or ion with such delocalized electrons is represented by
several contributing structures (also called resonance structures or canonical forms). Such is the case for ozone (O ), an allotrope
3

of oxygen with a V-shaped structure and an O–O–O angle of 117.5°.

Ozone (O ) 3

First we calculate the number of bonds needed

1. (3 O atoms) x (8) = 24 valence electrons needed
2. (3 O atoms) x (6) = 18 valence electrons present.
3. 24 - 18 = 6 electrons short, thus 6 electrons must be shared
4. 6 shared electrons/ 2 electrons per bond = 3 bonds
5. Connect the three atoms with one single bond. A three-membered ring is not impossible, but not very likely.
We know that ozone has a V-shaped structure from the information given above, so one O atom is central:

6. There is still one more bond to add. You could place that bond on either side, and then add the remaining 12 electrons as lone
pairs, with 3 pairs on the singly-bonded O atom, 2 pairs on the doubly-bonded O atom, and one pair on the central O atom
giving the following structures:

Which is correct? In fact, neither is correct. Both predict one O–O single bond and one O=O double bond. As you will learn, if the
bonds were of different types (one single and one double, for example), they would have different lengths. It turns out, however,
that both O–O bond distances are identical, 127.2 pm, which is shorter than a typical O–O single bond (148 pm) and longer than
the O=O double bond in O2 (120.7 pm).
Equivalent Lewis dot structures, such as those of ozone, are called resonance structures. The position of the atoms is the same in
the various resonance structures of a compound, but the position of the electrons is different. Double-headed arrows link the
different resonance structures of a compound:

The double-headed arrow indicates that the actual electronic structure is an average of those shown, not that the molecule oscillates
between the two structures.

1 [Link]
 When it is possible to write more than one equivalent resonance structure for a molecule
or ion, the actual structure is the average of the resonance structures.
The Carbonate (CO 2−
3
) Ion
Like ozone, the electronic structure of the carbonate ion cannot be described by a single Lewis electron structure. Unlike O3,
though, the actual structure of CO32− is an average of three resonance structures.
First we calculate the number of bonds needed
1. (3 O atoms) x (8) + (1 C atom) x (8) = 32 valence electrons needed
2. (3 O atoms) x (6) + (1 C atom) x (4) + 2 = 24 valence electrons present.
3. 32 - 24 = 8 electrons short, thus 8 electrons must be shared
4. 8 shared electrons/ 2 electrons per bond = 4 bonds
5. The C atom is the least electronegative element, so it is in the center. Connect the three O atoms to the C atom with one single
bond per O atom.

6. There is still one more bond to add. You can place that bond as a pi bond to any one of the O atoms, and then add the remaining
16 electrons as lone pairs, with 3 pairs on the singly-bonded O atoms, and 2 pairs on the doubly-bonded O atom, giving the
following three structures:

As with ozone, none of these structures describes the bonding exactly. Each predicts one carbon–oxygen double bond and two
carbon–oxygen single bonds, but experimentally all C–O bond lengths are identical. We can write resonance structures (in this
case, three of them) for the carbonate ion:

The actual structure is an average of these three resonance structures.

Example 1 : Benzene
Benzene is a common organic solvent that was previously used in gasoline; it is no longer used for this purpose, however,
because it is now known to be a carcinogen. The benzene molecule (C H ) consists of a regular hexagon of carbon atoms, each
6 6

of which is also bonded to a hydrogen atom. Use resonance structures to describe the bonding in benzene.
Given: molecular formula and molecular geometry
Asked for: resonance structures
Strategy:
A. Calculate the number of bonds needed for the molecule
B. Draw the resonance structures for benzene.
Solution:
1. (6 C atoms) x (8) + (6 H atoms) x (2) = 60 valence electrons needed
2. (6 C atoms) x (4) + (6 H atoms) x (1) = 30 valence electrons present.
3. 60 - 30 = 30 electrons short, thus 30 electrons must be shared
4. 30 shared electrons/ 2 electrons per bond = 15 bonds

2 [Link]
 5. If we place a single bonding electron pair between each pair of carbon atoms and between each carbon and a hydrogen atom,
we obtain the following:

This structure has 12 bonds, so there are still 3 bonds to add. The only option is to place a pi bond between every other C atom.
But there are 2 ways to do this:

Each structure has alternating double and single bonds, but experimentation shows that each carbon–carbon bond in benzene is
identical, with bond lengths (139.9 pm) intermediate between those typically found for a C–C single bond (154 pm) and a C=C
double bond (134 pm). We can describe the bonding in benzene using the two resonance structures, but the actual electronic
structure is an average of the two. The existence of multiple resonance structures for aromatic hydrocarbons like benzene is
often indicated by drawing either a circle or dashed lines inside the hexagon:

Exercise 1 : Nitrate Ion

The sodium salt of nitrite is used to relieve muscle spasms. Draw two resonance structures for the nitrite ion (NO2−).

Answer

Resonance structures are particularly common in oxoanions of the p-block elements, such as sulfate and phosphate, and in
aromatic hydrocarbons, such as benzene and naphthalene.

Warning
If several reasonable resonance forms for a molecule exists, the "actual electronic structure" of the molecule will probably be
intermediate between all the forms that you can draw. The classic example is benzene in Example 1. Once would expect the
double bonds to be shorter than the single bonds, but if once overlays the two structures, you see that one structure has a single
bond where the other structure has a double bond. The best measurements that we can make of benzene do not show two bond
lengths - instead, they show that the bond length is intermediate between the two resonance structures.
Resonance structures is mechanism that allows us to use all of possible resonance structures to try to predict what the actual
form of the molecule would be. Single bonds, double bonds, triple bonds, +1 charges, -1 charges, these are our limitations in
explaining the structures, and the true forms can be in between - a carbon-carbon bond could be mostly single bond with a little
bit of double bond character and a partial negative charge, for example.

3 [Link]
Summary
Some molecules have two or more chemically equivalent Lewis electron structures, called resonance structures. Resonance is a
mental exercise and method within the Valence Bond Theory of bonding that describes the delocalization of electrons within
molecules. These structures are written with a double-headed arrow between them, indicating that none of the Lewis structures
accurately describes the bonding but that the actual structure is an average of the individual resonance structures. Resonance
structures are used when one Lewis structure for a single molecule cannot fully describe the bonding that takes place between
neighboring atoms relative to the empirical data for the actual bond lengths between those atoms. The net sum of valid resonance
structures is defined as a resonance hybrid, which represents the overall delocalization of electrons within the molecule. A
molecule that has several resonance structures is more stable than one with fewer. Some resonance structures are more favorable
than others.

Modified by Tom Neils (Grand Rapids Community College)

3.8 Resonance and Formal Charge Revisited is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

4 [Link]
3.9 Exceptions to the Octet Rule
Skills to Develop
To assign a Lewis dot symbol to elements not having an octet of electrons in their compounds.

Three cases can be constructed that do not follow the octet rule, and as such, they are known as the exceptions to the octet rule.
Following the Octet Rule for Lewis Dot Structures leads to the most accurate depictions of stable molecular and atomic structures
and because of this we always want to use the octet rule when drawing Lewis Dot Structures. However, it is hard to imagine that
one rule could be followed by all molecules. There is always an exception, and in this case, three exceptions:
1. When there are an odd number of valence electrons
2. When there are too few valence electrons
3. When there are too many valence electrons

Exception 1: Species with Odd Numbers of Electrons

The first exception to the Octet Rule is when there are an odd number of valence electrons. An example of this would be nitrogen
monoxide also called nitric oxide (NO.
1. (1 O atom) x (8) + (1 N atom) x (8) = 16 valence electrons needed
2. (1 O atom) x (6) + (1 N atom) x (5) = 11 valence electrons present.
3. 16 - 11 = 5 electrons short, thus 5 electrons must be shared
4. 5 shared electrons/ 2 electrons per bond = 2.5 bonds How can you have a half of a bond? You can't according to Lewis dot
structure rules. Instead, draw a structure with two bonds (essentially ignoring the 1/2 bond).
5. The two bonds have to be placed between the N and O atoms.
N=O
6. You have used up 4 of the 11 electrons. Add in the remaining seven as 3 lone pairs and one unpaired electron. But where should
the lone pairs and the one unpaired electron go? The unpaired electron is usually placed in the Lewis Dot Structure so that each
element in the structure will have the lowest formal charge possible. Oxygen normally has six valence electrons. If we give the O
atom two lone pairs of electrons, and it participates in two bonds (a double bond) with nitrogen, the O atom will have a formal
charge of 0. Nitrogen normally has five valence electrons. If the N atom participates in two bonds with oxygen and is assigned one
lone pair along with one single electron, the formal charge on the N atom will be 0. The O atom will have an octet of valence
electrons, but the N atom will have only seven valence electrons. That is acceptable because this molecule is an odd-elctron particle
and one atom in the molecule must have fewer than eight valence electrons.

Figure : The proper Lewis structure for NO molecule

Free Radicals
There are actually very few stable molecules with odd numbers of electrons that exist, since that unpaired electron is willing to
react with other unpaired electrons. Most odd electron species, which we call free radicals, are highly reactive. Because of their
instability, free radicals bond to atoms in which they can take an electron from in order to become stable, making them very
chemically reactive. Radicals are found as both reactants and products, but generally react to form more stable molecules as
soon as they can. In order to emphasize the existence of the unpaired electron, radicals are denoted with a dot in front of their
chemical symbol as with ⋅OH , the hydroxyl radical. An example of a radical you may by familiar with already is the gaseous
chlorine atom, denoted ⋅C l.

Exception 2: Incomplete Octets - Carbocations

The second exception to the octet rule is when there are too few valence electrons on one atom, which results in an incomplete
octet. Species with incomplete octets are pretty rare and generally are only found in some beryllium, aluminum, and boron
compounds including the boron hydrides. But they are also found in organic chemistry as reaction intermediates - species that are
formed in one step of a reaction, but then used up in some following step. Let's take a look at one such carbocation, CH3CH2CH2+:
1. (3 C atoms) x (8) + (7 H atoms) x (2) = 38 valence electrons needed

1 [Link]
 2. (3 C atoms) x (4) + (7 H atoms) x (1) -1 = 18 valence electrons present.
3. 38 - 18 = 20 electrons short, thus 20 electrons must be shared
4. 20 shared electrons/ 2 electrons per bond = 10 bonds But, how can you have 10 bonds if you have only 18 electrons present?
You can't . Instead, draw a structure with 9 bonds (subtract one bond from the number of bonds that you calculated.)
5. You can draw single bonds between the C and H atoms, using up all 18 electrons, as shown here:

The problem with this structure is that C atom on the right has an incomplete octet; it only has six electrons around it. Hydrogen
atoms can naturally only have only 2 electrons in their outermost shell (their version of an octet), and as such there are no spare
electrons to form a double bond with carbon. A carbocation such as this is commonly a transitory species, formed temporarily in
reactions that involve multiple steps.

Example 1 : N F 3

Draw the Lewis structure for (CH3)3C+

SOLUTION
1. (4 C atoms) x (8) + (9 H atoms) x (2) = 50 valence electrons needed
2. (4 C atoms) x (4) + (9 H atoms) x (1) -1 = 24 valence electrons present.
3. 50 - 24 = 26 electrons short, thus 26 electrons must be shared
4. 26 shared electrons/ 2 electrons per bond = 13 bonds But, how can you have 13 bonds if you have only 24 electrons present?
You can't . Instead, draw a structure with 12 bonds (subtract one bond from the number of bonds that you calculated.)
5. You can draw single bonds between the C and H atoms, using up all 24 electrons, as shown here:

Exception 3: Expanded Valence Shells

Compounds containing expanded valence shell atoms occur when the central atom in a Lewis structure has more than eight
electrons in its valence shell. In expanded octets, the central atom can have ten, twelve, or even fourteen valence electrons.
Particles with expanded octets involve a nonmetal central atom from the third row or below, and a highly electronegative terminal
atom. We will not work with any of these particles, but it is important to note that two common polyatomic ions, SO42- and PO43-,
can be drawn, in their most stable resonance form, with the S and P atoms as expanded valence shell atoms:

Summary
Following the Octet Rule for Lewis Dot Structures leads to the most accurate depictions of stable molecular and atomic structures
and because of this we always want to use the octet rule when drawing Lewis Dot Structures. There are three exceptions: (1) When
there are an odd number of valence electrons, (2) When there are too few valence electrons, and (3) when there are too many
valence electrons

References
1. Petrucci, Ralph H.; Harwood, William S.; Herring, F. G.; Madura, Jeffrey D. General Chemistry: Principles & Modern
Applications. 9th Ed. New Jersey. Pearson Education, Inc. 2007.

2 [Link]
 2. Moore, John W.; Stanitski, Conrad L.; Jurs, Peter C. Chemistry; The Molecular Science. 2nd Ed. 2004.

Contributors
Mike Blaber (Florida State University)
Modified by Tom Neils (Grand Rapids Community College)

3.9 Exceptions to the Octet Rule is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

3 [Link]
3.10 Shapes of Molecules - VSEPR Theory and Valence Bond Theory
VSEPR Theory
Valence Shell Electron Pair Repulsion Theory uses the basic idea that electron pairs are mutually repulsed to predict the
arrangement of electron pairs around a central atom (an atom that has at least two other atoms bonded directly to it). The key to
correctly applying VSEPR Theory is to start with a correct Lewis dot structure. From a correct Lewis dot structure, it is a
straightforward process to determine the shape of a molecule or polyatomic ion by determining the arrangement of electron pairs
around every central atom in the molecule or polyatomic ion.
The step-by-step process to determine the shape around each central atom is
1. Draw the Lewis dot structure.
2. Apply the following analysis to each separate, central atom (where a central atom is an atom with two or more other atoms
bonded directly to it.)
a) Find the number of "things attached" to the central atom, where a "thing attached" is either an atom or a non-bonding
electron pair.
(Actually, you are counting the number of hybrid orbitals on the central atom, but that is the next theory to be
discussed.)
It is important to remember that you are not counting bonds!
b) Find the Electron Group Arrangement (EGA) in the table below

# of Things Attached Electron Group Arrangement Ideal Bond Angle Hybridization of Central Atom

2 line (linear shape) 180 sp

trigonal plane( trigonal planar

3 120 sp2
shape)

4 tetrahedron (tetrahedral shape) 109.5 sp3

c) Find the Molecular Geometry (MG) of the particle, determined by counting up the number of atoms and the number of
lone pairs and using this table:

#
o
M
f
o
l
l
o
e
n
c
B
e
ou
E
p
xnl
a
ad
Hybridization of Central Atom i
# of atoms attached ar
m
(see Valence Bond Theory) r
pnG
s
lge
a
elo
t
em
t
e
a
t
c
r
h
y
e
d

sp hybridized central atom:

1 [Link]
 l
C1
i
2 O80
n
20
e

sp2 hybridized central atom:

t
r
i
g
o
B 1n
3 F2a0
30 l
p
l
a
n
e

b
<
S
1e
2 O1
2n
2
0t

sp3 hybridized central atom:

t
e
t
1r
C 0a
4 H 9h0
4.e
5d
r
o
n

t
r
i
g
o
<
n
1
Na
0
3 Hl1
9
3p
.
y
5
r
a
m
i
d

<
1b
H
0e
2 22
9n
O
.t
5

2 [Link]
 Example 1
Determine the Electron Group Arrangement and Molecular Geometry about the central atom(s) in a) OF2 and b) CH3CN.
Solution

a) The Lewis dot structure of OF2 is (leaving off the lone pairs on the non-central F atoms.)
There are 2 atoms and 2 lone pairs attached to the central O atom, for a total of 4 "things attached."
From the two tables above, we can see that the O atom must have an EGA of a tetrahedron, and its MG is bent.
b) The Lewis dot structure of CH3CN is

There are 4 atoms and 0 lone pairs attached to the central C atom on the left, for a total of 4 "things attached."
From the two tables above, we can see that this C atom must have an EGA of a tetrahedron, and its MG is also a tetrahedron.
There are 2 atoms and 0 lone pairs attached to the central C atom on the right, for a total of 2 "things attached."
From the two tables above, we can see that this C atom must have an EGA of a line, and its MG is also a line.

Exercise 1
Determine the Electron Group Arrangement and Molecular Geometry about the central atom(s) in a) PF3 and b) CH2NH.

Answer

a) The Lewis dot structure of PF3 is (leaving off the lone pairs on the non-central F atoms.)
There are 3 atoms and 1 lone pair attached to the central P atom, for a total of 4 "things attached."
From the two tables above, we can see that the P atom must have an EGA of a tetrahedron, and its MG is a trigonal pyramid.
b)The Lewis dot structure of CH2NH is

There are 3 atoms and 0 lone pairs attached to the central C atom on the left, for a total of 3 "things attached."
From the two tables above, we can see that this C atom must have an EGA of a trigonal plane, and its MG is also a trigonal
plane.
There are 2 atoms and 1 lone pair attached to the central N atom on the right, for a total of 3 "things attached."
From the two tables above, we can see that this N atom must have an EGA of a trigonal plane, and its MG is bent.

Valence Bond Theory

The localized valence bond theory uses a process called hybridization, in which atomic orbitals are combined mathematically to
produce sets of equivalent orbitals that are properly oriented to form bonds to create the common electron group arrangements.
These new orbital combinations are called hybrid atomic orbitals because they are produced by combining (hybridizing) two or
more atomic orbitals from the same atom.
Hybridizing One s Orbital and Three p Orbitals
Carbon atoms typically form four covalent bonds, and have electron group arrangement of a tetrahedron because there are four
"things attached" to the central C atom. We can explain the tetrahedral shape by proposing that the 2s orbital and the three 2p
orbitals on a carbon atom mix together to give a set of four degenerate sp3 (“s-p-three”) hybrid orbitals, each containing a single
electron.

3 [Link]
The large lobes of the hybridized orbitals are oriented toward the vertices of a tetrahedron, with 109.5° angles between them
(Figure 1). Like all the hybridized orbitals discussed earlier, the sp3 hybrid atomic orbitals are predicted to be equal in energy.
Thus, methane (CH4) is a tetrahedral molecule with four equivalent C-H bonds.

Figure 1 : Formation of sp3 Hybrid Orbitals. Combining one ns and three np atomic orbitals results in four sp3 hybrid orbitals
oriented at 109.5° to one another in a tetrahedral arrangement.
An sp3 hybrid orbital looks a bit like half of a p orbital, and the four sp3 hybrid orbitals arrange themselves in space so that they are
as far apart as possible. You can picture the nucleus as being at the centre of a tetrahedron (a triangularly based pyramid) with the
orbitals pointing to the corners. For clarity, the nucleus is drawn far larger than it really is.

What happens when the bonds are formed?

Remember that hydrogen's electron is in a 1s orbital - a spherically symmetric region of space surrounding the nucleus where there
is some fixed chance (say 95%) of finding the electron. When a covalent bond is formed, the atomic orbitals (the orbitals in the
individual atoms) merge to produce a new molecular orbital which contains the electron pair which creates the bond.

Four molecular orbitals are formed, looking rather like the original sp3 hybrids, but with a hydrogen nucleus embedded in each
lobe.
Hybrid orbital theory can be applied to molecules of ammonia (NH3) , which has three atoms and one lone pair attached to the
central N atom. This means that the N atom is sp3 hybridized. Three sp3 orbitals form bonds with three H atoms, while the fourth
orbital accommodates the lone pair of electrons. Similarly, H2O has an sp3 hybridized oxygen atom that uses two sp3 orbitals to
bond to two H atoms, and two orbitals to accommodate the two lone pairs predicted by the VSEPR model. Such descriptions
explain the approximately tetrahedral distribution of electron pairs on the central atom in NH3 and H2O.
Hybridizing One s Orbital and Two p Orbitals
Ethene, C2H4, is a molecule in which all of the atoms lie in a plane, with 120o bond angles between all of the atoms:

To explain this structure, we can generate three equivalent hybrid orbitals on each C atom by combining the 2s orbital of the carbon
and two of the three degenerate 2p orbitals. This mixing results in each C atom possessing a set of three equivalent hybrid orbitals
with one electron each. The hybrid orbitals are degenerate and are oriented at 120° angles to each other (Figure 2). Because the
hybrid atomic orbitals are formed from one s and two p orbitals, carbon is said to be sp2 hybridized (pronounced “s-p-two” or “s-p-
squared”).

4 [Link]
 Figure 2 : Formation of sp2 Hybrid Orbitals. Combining one ns and two np atomic orbitals gives three equivalent sp2 hybrid
orbitals in a trigonal planar arrangement; that is, oriented at 120° to one another.
Two of the sp2 hybrid atomic orbitals on each C atom can can overlap with the s orbitals on two H atoms. The third hybrid orbital
on each C atom can overlap to form a sigma bond between the two C atoms. Both C atoms have one 2p orbital that has yet to be
used for bonding. When the C atoms form a sigma bond and are pulled close together, a pi bond can also form between the two C
atoms because the p-orbitals can overlap above and below the internuclear axis. The result to form a trigonal planar structure.

The entire bonding process looks like this (with the sp2 hybrid orbitals in bright green and the
unhybridized p orbitals in red):

The two carbon atoms and four hydrogen atoms would look like this before they joined together:

The various atomic orbitals which are pointing towards each other now merge to give molecular orbitals, each containing a bonding
pair of electrons. These are sigma bonds - just like those formed by end-to-end overlap of atomic orbitals in, say, ethane.

The p orbitals on each carbon are not pointing towards each other, and so we'll leave those for a moment. In the diagram, the black
dots represent the nuclei of the atoms. Notice that the p orbitals are so close that they are overlapping sideways.

This sideways overlap also creates a π bond.

For clarity, the sigma bonds are shown using lines - each line representing one pair of shared electrons. The various sorts of line
show the directions the bonds point in. An ordinary line represents a bond in the plane of the screen (or the paper if you've printed
it), a broken line is a bond going back away from you, and a wedge shows a bond coming out towards you.
Be clear about what a π bond is. It is a region of space in which you can find the two electrons which make up the bond. Those two
electrons can live anywhere within that space. It would be quite misleading to think of one living in the top and the other in the
bottom.
Hybridizing One s Orbital and One p Orbital
Ethyne, C2H2, is a molecule in which all of the atoms lie in a straight line:

5 [Link]
To explain this structure, we can generate two equivalent hybrid orbitals on each C atom by combining the 2s orbital of carbon and
any one of the three degenerate 2p orbitals.
By taking the sum and the difference of C 2s and 2pz atomic orbitals, for example, we produce two new orbitals with major and
minor lobes oriented along the z-axes, as shown in Figure 3.

Figure 3 : The Formation of sp Hybrid Orbitals. Taking the sum and difference of an ns and an np atomic orbital where n = 2 gives
two equivalent sp hybrid orbitals oriented at 180° to each other.
The nucleus resides just inside the minor lobe of each orbital. In this case, the new orbitals are called sp hybrids because they are
formed from one s and one p orbital.
One sp hybrid orbital on each C atom can now form a sigma bond with one of the H atoms. The other sp hybrid orbital on each C
atom can overlap to form a sigma bond between the two C atoms. Both C atoms have two 2p orbitals that have yet to be used for
bonding. These orbitals are perpendicular to each other on each C atom, but when the C atoms form a sigma bond and are pulled
close together, two pi bonds can also form between the two C atoms because one set of p-orbitals can overlap above and below the
internuclear axis, and the other set of p orbitals can overlap in front of and behind the internuclear axis.

The entire bonding process looks like this (with the sp hybrid orbitals in bright green and the
unhybridized p orbitals in red):

Notice that the two green lobes are two different hybrid orbitals - arranged as far apart from
each other as possible. Do not confuse them with the shape of a p orbital. The two carbon
atoms and two hydrogen atoms would look like this before they joined together:

The various atomic orbitals which are pointing towards each other now merge to give molecular
orbitals, each containing a bonding pair of electrons. These are sigma bonds - just like those
formed by end-to-end overlap of atomic orbitals in, say, ethane. The sigma bonds are shown as
orange in the next diagram. The various p orbitals (now shown in slightly different reds to avoid
confusion) are now close enough together that they overlap sideways.

6 [Link]
Sideways overlap between the two sets of p orbitals produces two pi bonds - each similar to
the pi bond found in, say, ethene. These pi bonds are at 90° to each other - one above and
below the molecule, and the other in front of and behind the molecule. Notice the different
shades of red for the two different pi bonds.

Example 1
Use the VSEPR model to predict the number of electron pairs and molecular geometry in each compound and then describe the
hybridization and bonding of all atoms except hydrogen.
a. H2S
b. CHCl3
Given: two chemical compounds
Asked for: number of electron pairs and molecular geometry, hybridization, and bonding
Strategy:
A. Using the VSEPR approach to determine the number of electron pairs and the molecular geometry of the molecule.
B. From the valence electron configuration of the central atom, predict the number and type of hybrid orbitals that can be
produced. Fill these hybrid orbitals with the total number of valence electrons around the central atom and describe the
hybridization.
Solution:
1. A H2S has four electron pairs around the sulfur atom with two bonded atoms, so the VSEPR model predicts a molecular
geometry that is bent, or V shaped. B Sulfur hybridizes its 3s and 3p orbitals, to produce four sp3 hybrids. If the six valence
electrons are placed in these orbitals, two have electron pairs and two are singly occupied. The two sp3 hybrid orbitals that
are singly occupied are used to form S–H bonds, whereas the other two have lone pairs of electrons. Together, the four sp3
hybrid orbitals produce an approximately tetrahedral arrangement of electron pairs, which agrees with the molecular
geometry predicted by the VSEPR model.
2. A The CHCl3 molecule has four valence electrons around the central atom. In the VSEPR model, the carbon atom has four
electron pairs, and the molecular geometry is tetrahedral. B Carbon hybrides its 2s and 2p orbitals, to form four sp3
hybridized orbitals that are equal in energy. Eight electrons around the central atom (four from C, one from H, and one from
each of the three Cl atoms) fill three sp3 hybrid orbitals to form C–Cl bonds, and one forms a C–H bond. Similarly, the Cl
atoms, with seven electrons each in their 3s and 3p valence subshells, can be viewed as sp3 hybridized. Each Cl atom uses a
singly occupied sp3 hybrid orbital to form a C–Cl bond and three hybrid orbitals to accommodate lone pairs.

Exercise 1
Use the VSEPR model to predict the number of electron pairs and molecular geometry in each compound and then describe the
hybridization and bonding of all atoms except hydrogen.
a. the BF4− ion

7 [Link]
 b. hydrazine (H2N–NH2)

Answer a
B is sp3 hybridized; F is also sp3 hybridized so it can accommodate one B–F bond and three lone pairs. The molecular
geometry is tetrahedral.
Answer b
Each N atom is sp3 hybridized and uses one sp3 hybrid orbital to form the N–N bond, two to form N–H bonds, and one to
accommodate a lone pair. The molecular geometry about each N is trigonal pyramidal.

The number of hybrid orbitals used by the central atom is the same as the number of electron pairs around the central atom, and
thu sthe same as the number of "things attached" to the central atom.

Hybridization Using d Orbitals

Hybridization is not restricted to the ns and np atomic orbitals, but we will not discuss the formation of the hybrid orbitals
involving d orbitals.

Summary
Hybridization increases the overlap of bonding orbitals and explains the molecular geometries of many species whose geometry
cannot be explained using a VSEPR approach. The localized bonding model (called valence bond theory) assumes that covalent
bonds are formed when atomic orbitals overlap and that the strength of a covalent bond is proportional to the amount of overlap. It
also assumes that atoms use combinations of atomic orbitals (hybrids) to maximize the overlap with adjacent atoms. The
combination of one s and one p orbital gives rise to two equivalent sp hybrids oriented at 180°, whereas the combination of one s
and two or three p orbitals produces three equivalent sp2 hybrids or four equivalent sp3 hybrids, respectively. The spatial
orientation of the hybrid atomic orbitals is consistent with the geometries predicted using the VSEPR model.

Contributors
Jim Clark ([Link])
Modified by Tom Neils (Grand Rapids Community College)

3.10 Shapes of Molecules - VSEPR Theory and Valence Bond Theory is shared under a CC BY-NC-SA 4.0 license and was authored, remixed,
and/or curated by LibreTexts.

8 [Link]
3.11 Practice Problems
Chemical Formulas
1. For the following molecules; write the chemical formula, determine how many atoms are present in one molecule/formula unit,
determine the molar mass, determine the number of moles in 1.00 gram, and the number of grams in exactly 5.00 x 10-2 moles.
a) carbon dioxide
b) iron (II) chloride
c) dinitrogen pentoxide
d) iron (III) sulfate

Exercise 1
Answers to Q1

Answer

Atoms per Grams in 5.00 x 10-2

Formula Molar Mass Moles in 1.00 g
Molecule/Formula Unit moles

CO2 3 44.01 2.27 x 10-2 2.20

FeCl2 3 126.75 7.89 x 10-3 6.34

N2O5 7 108.02 9.26 x 10-3 5.40

Fe2(SO4)3 17 399.88 2.50 x 10-3 20.0

2. Name the following compounds, determine the molar mass, determine how many O atoms are present in one molecule/formula
unit, determine the grams of oxygen in 1.00 mole of the compound, and determine how many moles of O atoms in 8.35 grams of
the compound.
a) K2CO3
b) Ca(NO3)2
c) Cu2SO4
d) N2O

Exercise 2
Answers to Q2

Answer

Atoms O per
Name Molar mass Grams of O in 1.00 mole Moles of O in 8.35 grams
Molecule/Formula Unit

potassium carbonate 138.205 3 48.0 1.81 x 10-1

calcium nitrate 164.088 6 96.0 3.05 x 10-1

copper(I) sulfate 223.25 4 64.0 1.50 x 10-1

dinitrogen monoxide 44.013 1 16.0 1.90 x 10-1

3. Give the chemical formula (including the charge!) for the following ions. Also, write out the chemical formula for the compound
each anion would form with K+ and with Ca2+.
a) sulfate
b) sulfite

1 [Link]
c) nitrate
d) chloride
e) nitride
f) acetate
g) carbonate

Exercise 3
Answers to Q3

Answer
a) SO42-; K2SO4; CaSO4
b) SO32-; K2SO3; CaSO3
c) NO3-; KNO3; Ca(NO3)2
d) Cl-; KCl; CaCl2
e) N3-; K3N; Ca3N2
f) C2H3O2-; KC2H3O2; Ca(C2H3O2)2
g) CO32-; K2CO3; CaCO3

Lewis Dot Structures

4. For the compounds i) SiS2, ii) PI3, iii) SCl2, and iv) CH2PH a) draw the Lewis dot structure, b) determine the hybridization of
the central atom(s), c) determine the EGA around the central atom(s), d) determine the MG around the central atom(s), e)
determine the bond angles in the molecule, f) determine if the molecule is polar or non-polar

Exercise 4
Answers to Lewis dot questions

Answer
i) a) b) sp c) line d) line e) 180o f) nonpolar

ii) a) b) sp3 c) tetrahedron d) trigonal pyramid e) <109.5o f) polar

iii) a) b) sp3 c) tetrahedron d) bent e) <109.5o f) polar

iv) a) b) C sp2 and N sp2 c) C and N trigonal plane d) C trigonal plane; N bent e) <120o f) polar

Modified by Tom Neils (Grand Rapids Community College)

3.11 Practice Problems is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

2 [Link]
 CHAPTER OVERVIEW

4: Intermolecular Forces, Phases, and Solutions

4.1 Water in Zero Gravity - an Introduction to Intermolecular Forces
4.2 Intermolecular Forces
4.3 Application of IMFs: Evaporation, Vapor Pressure, and Boiling Points
4.4: Intermolecular Forces in Action: Surface Tension, Viscosity, and Capillary Action
4.5: Solids, Liquids, and Gases: A Molecular Comparison
4.6 Phase Changes
4.7: Pressure: The Result of Particle Collisions
4.8: Gases
4.9 Solutions - What Mixes Together and Why
4.10 Factors Affecting Solubility
4.11 Suspensions and Colloids
4.12 Practice Problems
Intermolecular Forces

4: Intermolecular Forces, Phases, and Solutions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

1
4.1 Water in Zero Gravity - an Introduction to Intermolecular Forces
Here on Earth, we all live in a state of gravity. Not only us, but everything around us, including water, is being pulled towards the
center of the planet by gravity. True, it is nice that our dogs don't float off into space, but when a child drops their ice cream (which
is full of water, by the way) they don't have to know about gravity to be upset.

4K Video of Colorful Liquid in Space

Floating Water in Zero Gravity: Once again, astronauts on the International Space Station dissolved an effervescent tablet in a
floating ball of water, and captured images using a camera capable of recording four times the resolution of normal high-definition
cameras. The higher resolution images and higher frame rate videos can reveal more information when used on science
investigations, giving researchers a valuable new tool aboard the space station. This footage is one of the first of its kind. The
cameras are being evaluated for capturing science data and vehicle operations by engineers at NASA's Marshall Space Flight
Center in Huntsville, Alabama.
If you go far enough out in space, for instance, onto the International Space Station, gravity becomes negligible, and the laws of
physics act differently than here on Earth. Just how might water act in a place of zero gravity? This video above from NASA gives
you a good idea of how different water behaves when the effects if gravity are counteracted.
Actually, on the International Space Station, there is plenty of gravity—according to NASA scientists, the pull of Earth's gravity on
the space station and its occupants is substantial: about 90 percent of the force at the Earth's surface. But since the space station is
continuously falling around our planet, the astronauts and objects on board are in a kind of free-fall, too, and feel nearly weightless.
Water on the space station behaves as if in a zero-gravity environment.
This unique picture shows not only a water drop but also an air bubble inside of the water drop. Notice they both behave the
same....according to the laws of physics in space. They both form spheres. This makes sense, as without gravity to tug downward,
the forces governing the objects are all the same. So, the water drop (and air bubble) form themselves so they occupy a shape
having the least amount of surface area, which is a sphere. On Earth, gravity distorts the shape, but not in space.
Consider what would happen on Earth: The air bubble, lighter than water, would race upward to burst through the surface of the
droplet. In space, the air bubble doesn't rise because it is no lighter than the water around it—there's no buoyancy. The droplet
doesn't fall from the leaf because there's no force to pull it off. It's stuck there by molecular adhesion.
Sticky water. No buoyancy. These are some of the factors space-farers must take into account when they plan their space gardens.
If water is sprayed onto the base of the plant will it trickle down to the roots? More likely it will stick to the stem or adhere to the
material in which the plant grows. As humans spend more time and go farther out in space in the future, the physics of "space
water" will need to be well understood.

Reference
The Physics of Space Gardens, NASA.

4.1 Water in Zero Gravity - an Introduction to Intermolecular Forces is shared under a Public Domain license and was authored, remixed, and/or
curated by LibreTexts.

1 [Link]
4.2 Intermolecular Forces
Skills to Develop
To describe the six types of intermolecular forces

In contrast to intramolecular forces, such as the covalent bonds that hold atoms together within molecules and polyatomic ions,
intermolecular forces exist bewteen separate particles holding them next to each other, leading to the existence of the liquid and
solid phases. Intermolecular forces are generally much weaker than bonds. For example, it requires 927 kJ to overcome the
intramolecular forces and break both O–H bonds in 1 mol of water, but it takes only about 41 kJ to overcome the intermolecular
attractions and convert 1 mol of liquid water to water vapor at 100°C. (Despite this seemingly low value, the intermolecular forces
in liquid water are among the strongest such forces known!) Given the large difference in the strengths of intra- and intermolecular
forces, changes between the solid, liquid, and gaseous states almost invariably occur for molecular substances without breaking
covalent bonds.

The properties of liquids are intermediate between those of gases and solids but are more
similar to solids.
Intermolecular forces determine bulk properties such as the melting points of solids and the boiling points of liquids. Liquids boil
when the molecules have enough thermal energy to overcome the intermolecular attractive forces that hold them together, thereby
forming bubbles of vapor within the liquid. Similarly, solids melt when the molecules acquire enough thermal energy to overcome
the intermolecular forces that lock them into place in the solid.
Intermolecular forces are electrostatic in nature; that is, they arise from the interaction between positively and negatively charged
species. Like covalent and ionic bonds, intermolecular interactions are the sum of both attractive and repulsive components.
Because electrostatic interactions fall off rapidly with increasing distance between molecules, intermolecular interactions are most
important for solids and liquids, where the molecules are close together. These interactions become important for gases only at very
high pressures, where they are responsible for the observed deviations from the ideal gas law at high pressures.
In this section, we first consider three kinds of intermolecular interactions that are the only types that can occur in pure substances
(although they can also occur in mixtures): London forces, dipole/dipole forces, and hydrogen bonding. We will then discuss the
three additional types of intermolecular electrostatic interaction that only occur in mixtures: ion–induced dipole interactions,
dipole-induced dipole interactions, and ion–dipole interactions. See Figure 1 .

Figure 1 : The six intermolecular forces

London Dispersion Forces

Many nonpolar molecules, such as bromine, benzene, and hexane, are liquids at room temperature, and others, such as iodine and
naphthalene, are solids. Even the noble gases can be liquefied or solidified at low temperatures, high pressures, or both (Table 1).
What kind of attractive forces can exist between nonpolar molecules or atoms? This question was answered by Fritz London
(1900–1954), a German physicist who later worked in the United States. In 1930, London proposed that temporary fluctuations in

1 [Link]
the electron distributions within atoms and nonpolar molecules could result in the formation of short-lived instantaneous dipole
moments, which produce attractive forces called London dispersion forces between otherwise nonpolar substances. (London forces
also are exerted by polar molecules because these molecules can also experience temporary fluctuations in their electron
distributions.)

Table 1 : Normal Melting and Boiling Points of Some Elements and Nonpolar Compounds
Substance Molar Mass (g/mol) Melting Point (°C) Boiling Point (°C)

Ar 40 −189.4 −185.9

Xe 131 −111.8 −108.1

N2 28 −210 −195.8

O2 32 −218.8 −183.0

F2 38 −219.7 −188.1

I2 254 113.7 184.4

CH4 16 −182.5 −161.5

Consider a pair of adjacent He atoms, for example. On average, the two electrons in each He atom are uniformly distributed around
the nucleus. Because the electrons are in constant motion, however, their distribution in one atom is likely to be asymmetrical at
any given instant, resulting in an instantaneous dipole moment. As shown in part (a) in Figure 3, the instantaneous dipole moment
on one atom can interact with the electrons in an adjacent atom, pulling them toward the positive end of the instantaneous dipole or
repelling them from the negative end. The net effect is that the first atom causes the temporary formation of a dipole, called an
induced dipole, in the second. Interactions between these temporary dipoles cause atoms to be attracted to one another. These
attractive interactions are weak and fall off rapidly with increasing distance. London was able to show with quantum mechanics
that the attractive energy between molecules due to temporary dipole–induced dipole interactions falls off as 1/r6. Doubling the
distance therefore decreases the attractive energy by 26, or 64-fold.

2 [Link]
 Figure 2 : Instantaneous Dipole Moments. The formation of an instantaneous dipole moment on one He atom (a) or an H2
molecule (b) results in the formation of an induced dipole on an adjacent atom or molecule.
Instantaneous dipole–induced dipole interactions between nonpolar molecules can produce intermolecular attractions just as they
produce interatomic attractions in monatomic substances like Xe. This effect, illustrated for two H2 molecules in part (b) in Figure
2 , tends to become more pronounced as atomic and molecular masses increase (Table 1 ). For example, Xe boils at −108.1°C,

whereas He boils at −269°C. The reason for this trend is that the strength of London dispersion forces is related to the ease with
which the electron distribution in a given atom can be perturbed. In small atoms such as He, the two 1s electrons are held close to
the nucleus in a very small volume, and electron–electron repulsions are strong enough to prevent significant asymmetry in their
distribution. In larger atoms such as Xe, however, the outer electrons are much less strongly attracted to the nucleus because of
filled intervening shells. As a result, it is relatively easy to temporarily deform the electron distribution to generate an instantaneous
or induced dipole. The ease of deformation of the electron distribution in an atom or molecule is called its polarizability. Because
the electron distribution is more easily perturbed in large, heavy species than in small, light species, we say that heavier substances
tend to be much more polarizable than lighter ones.

For similar substances, London dispersion forces get stronger with increasing molecular
size.
The polarizability of a substance also determines how it interacts with ions and species that possess permanent dipoles. Thus
London dispersion forces are responsible for the general trend toward higher boiling points with increased molecular mass and
greater surface area in a homologous series of compounds, such as the alkanes (part (a) in Figure 3). The strengths of London
dispersion forces also depend significantly on molecular shape because shape determines how much of one molecule can interact
with its neighboring molecules at any given time. For example, part (b) in Figure 3 shows 2,2-dimethylpropane (neopentane) and
n-pentane, both of which have the empirical formula C5H12. Neopentane is almost spherical, with a small surface area for
intermolecular interactions, whereas n-pentane has an extended conformation that enables it to come into close contact with other
n-pentane molecules. As a result, the boiling point of neopentane (9.5°C) is more than 25°C lower than the boiling point of n-
pentane (36.1°C).

Figure 3 : Mass and Surface Area Affect the Strength of London Dispersion Forces. (a) In this series of four simple alkanes, larger
molecules have stronger London forces between them than smaller molecules and consequently higher boiling points. (b) Linear n-
pentane molecules have a larger surface area and stronger intermolecular forces than spherical neopentane molecules. As a result,
neopentane is a gas at room temperature, whereas n-pentane is a volatile liquid.
All molecules, whether polar or nonpolar, are attracted to one another by London dispersion forces in addition to any other
attractive forces that may be present. In general, however, dipole–dipole interactions in small polar molecules are significantly
stronger than London dispersion forces, so the former predominate.

Example 1
Arrange n-butane, propane, 2-methylpropane [isobutene, (CH3)2CHCH3], and n-pentane in order of increasing boiling points.
Given: compounds
Asked for: order of increasing boiling points

3 [Link]
 Strategy:
Determine the intermolecular forces in the compounds and then arrange the compounds according to the strength of those
forces. The substance with the weakest forces will have the lowest boiling point.
Solution:
The four compounds are alkanes and nonpolar, so London dispersion forces are the only important intermolecular forces. These
forces are generally stronger with increasing molecular mass, so propane should have the lowest boiling point and n-pentane
should have the highest, with the two butane isomers falling in between. Of the two butane isomers, 2-methylpropane is more
compact, and n-butane has the more extended shape. Consequently, we expect intermolecular interactions for n-butane to be
stronger due to its larger surface area, resulting in a higher boiling point. The overall order is thus as follows, with actual boiling
points in parentheses: propane (−42.1°C) < 2-methylpropane (−11.7°C) < n-butane (−0.5°C) < n-pentane (36.1°C).

Exercise 1
Arrange GeH4, SiCl4, SiH4, CH4, and GeCl4 in order of decreasing boiling points.

Answer
GeCl4 (87°C) > SiCl4 (57.6°C) > GeH4 (−88.5°C) > SiH4 (−111.8°C) > CH4 (−161°C)

Dipole–Dipole Interactions
Polar covalent bonds behave as if the bonded atoms have localized fractional charges that are equal but opposite (i.e., the two
bonded atoms generate a dipole). If the structure of a molecule is such that the individual bond dipoles do not cancel one another,
then the molecule has a net dipole moment. Molecules with net dipole moments tend to align themselves so that the positive end of
one dipole is near the negative end of another and vice versa, as shown in Figure 4a.

Figure 4 : Attractive and Repulsive Dipole–Dipole Interactions. (a and b) Molecular orientations in which the positive end of one
dipole (δ+) is near the negative end of another (δ−) (and vice versa) produce attractive interactions. (c and d) Molecular
orientations that juxtapose the positive or negative ends of the dipoles on adjacent molecules produce repulsive interactions.
These arrangements are more stable than arrangements in which two positive or two negative ends are adjacent (Figure 4c). Hence
dipole–dipole interactions, such as those in Figure 4b, are attractive intermolecular interactions, whereas those in Figure 4d are
repulsive intermolecular interactions. Because molecules in a liquid move freely and continuously, molecules always experience
both attractive and repulsive dipole–dipole interactions simultaneously, as shown in Figure 5. On average, however, the attractive
interactions dominate.

4 [Link]
 Figure 5 : Both Attractive and Repulsive Dipole–Dipole Interactions Occur in a Liquid Sample with Many Molecules
Because each end of a dipole possesses only a fraction of the charge of an electron, dipole–dipole interactions are substantially
weaker than the interactions between two ions, each of which has a charge of at least ±1, or between a dipole and an ion, in which
one of the species has at least a full positive or negative charge. In addition, the attractive interaction between dipoles falls off
much more rapidly with increasing distance than do the ion–ion interactions. Recall that the attractive energy between two ions is
proportional to 1/r, where r is the distance between the ions. Doubling the distance (r → 2r) decreases the attractive energy by one-
half. In contrast, the energy of the interaction of two dipoles is proportional to 1/r3, so doubling the distance between the dipoles
decreases the strength of the interaction by 23, or 8-fold. Thus a substance such as HCl, which is partially held together by dipole–
dipole interactions, is a gas at room temperature and 1 atm pressure, whereas NaCl, which is held together by interionic
interactions, is a high-melting-point solid. Within a series of compounds of similar molar mass, the strength of the intermolecular
interactions increases as the dipole moment of the molecules increases, as shown in Table 2.
Table 2 : Relationships between the Dipole Moment and the Boiling Point for Organic Compounds of Similar Molar Mass
Compound Molar Mass (g/mol) Dipole Moment (D) Boiling Point (K)

C3H6 (cyclopropane) 42 0 240

CH3OCH3 (dimethyl ether) 46 1.30 248

CH3CN (acetonitrile) 41 3.9 355

The attractive energy between two ions is proportional to 1/r, whereas the attractive
energy between two dipoles is proportional to 1/r6.
Example 2
Arrange ethyl methyl ether (CH3OCH2CH3), 2-methylpropane [isobutane, (CH3)2CHCH3], and acetone (CH3COCH3) in order
of increasing boiling points. Their structures are as follows:

5 [Link]
 Given: compounds
Asked for: order of increasing boiling points
Strategy:
Compare the molar masses and the polarities of the compounds. Compounds with higher molar masses and that are polar will
have the highest boiling points.
Solution:
The three compounds have essentially the same molar mass (58–60 g/mol), so we must look at differences in polarity to predict
the strength of the intermolecular dipole–dipole interactions and thus the boiling points of the compounds.
The first compound, 2-methylpropane, contains only C–H bonds, which are not very polar because C and H have similar
electronegativities. It should therefore have a very small (but nonzero) dipole moment and a very low boiling point.
Ethyl methyl ether has a structure similar to H2O; it contains two polar C–O single bonds oriented at about a 109° angle to each
other, in addition to relatively nonpolar C–H bonds. As a result, the C–O bond dipoles partially reinforce one another and
generate a significant dipole moment that should give a moderately high boiling point.
Acetone contains a polar C=O double bond oriented at about 120° to two methyl groups with nonpolar C–H bonds. The C–O
bond dipole therefore corresponds to the molecular dipole, which should result in both a rather large dipole moment and a high
boiling point.
Thus we predict the following order of boiling points:
2-methylpropane < ethyl methyl ether < acetone.
This result is in good agreement with the actual data: 2-methylpropane, boiling point = −11.7°C, and the dipole moment (μ) =
0.13 D; methyl ethyl ether, boiling point = 7.4°C and μ = 1.17 D; acetone, boiling point = 56.1°C and μ = 2.88 D.

Exercise 2
Arrange carbon tetrafluoride (CF4), ethyl methyl sulfide (CH3SC2H5), dimethyl sulfoxide [(CH3)2S=O], and 2-methylbutane
[isopentane, (CH3)2CHCH2CH3] in order of decreasing boiling points.

Answer
dimethyl sulfoxide (boiling point = 189.9°C) > ethyl methyl sulfide (boiling point = 67°C) > 2-methylbutane (boiling point =
27.8°C) > carbon tetrafluoride (boiling point = −128°C)

Hydrogen Bonds
Molecules with hydrogen atoms bonded to electronegative atoms such as O, N, and F (and to a much lesser extent Cl and S) tend to
exhibit unusually strong intermolecular interactions. These result in much higher boiling points than are observed for substances in
which London dispersion forces dominate, as illustrated for the covalent hydrides of elements of groups 14–17 in Figure 6.
Methane and its heavier congeners in group 14 form a series whose boiling points increase smoothly with increasing molar mass.
This is the expected trend in nonpolar molecules, for which London dispersion forces are the exclusive intermolecular forces. In
contrast, the hydrides of the lightest members of groups 15–17 have boiling points that are more than 100°C greater than predicted
on the basis of their molar masses. The effect is most dramatic for water: if we extend the straight line connecting the points for

6 [Link]
H2Te and H2Se to the line for period 2, we obtain an estimated boiling point of −130°C for water! Imagine the implications for life
on Earth if water boiled at −130°C rather than 100°C.

Figure 6 : The Effects of Hydrogen Bonding on Boiling Points. These plots of the boiling points of the covalent hydrides of the
elements of groups 14–17 show that the boiling points of the lightest members of each series for which hydrogen bonding is
possible (HF, NH3, and H2O) are anomalously high for compounds with such low molecular masses.
Why do strong intermolecular forces produce such anomalously high boiling points and other unusual properties, such as high
enthalpies of vaporization and high melting points? The answer lies in the highly polar nature of the bonds between hydrogen and
very electronegative elements such as O, N, and F. The large difference in electronegativity results in a large partial positive charge
on hydrogen and a correspondingly large partial negative charge on the O, N, or F atom. Consequently, H–O, H–N, and H–F bonds
have very large bond dipoles that can interact strongly with one another. Because a hydrogen atom is so small, these dipoles can
also approach one another more closely than most other dipoles. The combination of large bond dipoles and short dipole–dipole
distances results in very strong dipole–dipole interactions called hydrogen bonds, as shown for ice in Figure 7. A hydrogen bond is
usually indicated by a dotted line between the hydrogen atom attached to O, N, or F and the O, N, orF atom that has the lone pair of
electrons. Because each water molecule contains two hydrogen atoms and two lone pairs, a tetrahedral arrangement maximizes the
number of hydrogen bonds that can be formed. In the structure of ice, each oxygen atom is surrounded by a distorted tetrahedron of
hydrogen atoms that form bridges to the oxygen atoms of adjacent water molecules. The bridging hydrogen atoms are not
equidistant from the two oxygen atoms they connect, however. Instead, each hydrogen atom is 101 pm from one oxygen and 174
pm from the other. In contrast, each oxygen atom is bonded to two H atoms at the shorter distance and two at the longer distance,
corresponding to two O–H covalent bonds and two O⋅⋅⋅H hydrogen bonds from adjacent water molecules, respectively. The
resulting open, cagelike structure of ice means that the solid is actually slightly less dense than the liquid, which explains why ice
floats on water rather than sinks.

7 [Link]
 Figure 7 : The Hydrogen-Bonded Structure of Ice.
Each water molecule accepts two hydrogen bonds from two other water molecules and donates two hydrogen atoms to form
hydrogen bonds with two more water molecules, producing an open, cagelike structure. The structure of liquid water is very
similar, but in the liquid, the hydrogen bonds are continually broken and formed because of rapid molecular motion.
Because ice is less dense than liquid water, rivers, lakes, and oceans freeze from the top down. In fact, the ice forms a protective
surface layer that insulates the rest of the water, allowing fish and other organisms to survive in the lower levels of a frozen lake or
sea. If ice were denser than the liquid, the ice formed at the surface in cold weather would sink as fast as it formed. Bodies of water
would freeze from the bottom up, which would be lethal for most aquatic creatures. The expansion of water when freezing also
explains why automobile or boat engines must be protected by “antifreeze” and why unprotected pipes in houses break if they are
allowed to freeze.

Example 3
Considering CH3OH, C2H6, Xe, and (CH3)3N, which can form hydrogen bonds as a pure substance? Draw the hydrogen-bonded
structures.
Given: compounds
Asked for: formation of hydrogen bonds and structure
Strategy:
A. Identify the compounds with a hydrogen atom attached to O, N, or F.
Solution:
A Of the species listed, xenon (Xe), ethane (C2H6), and trimethylamine [(CH3)3N] do not contain a hydrogen atom attached to
O, N, or F; hence they cannot form hydrogen bonds as a pure substance. The one compound that can form hydrogen bonds,
methanol (CH3OH), contains both a hydrogen atom attached to O and two lone pairs of electrons on O; methanol can thus form
hydrogen bonds. The hydrogen-bonded structure of methanol is as follows:

8 [Link]
 Exercise 3
Considering CH3CO2H, (CH3)3N, NH3, and CH3F, which can form hydrogen bonds as a pure substance? Draw the hydrogen-
bonded structures.

Answer:
CH3CO2H and NH3;

Although hydrogen bonds are significantly weaker than covalent bonds, with typical dissociation energies of only 15–25 kJ/mol,
they have a significant influence on the physical properties of a compound. Compounds such as HF can form only two hydrogen
bonds at a time as can, on average, pure liquid NH3. Consequently, even though their molecular masses are similar to that of water,
their boiling points are significantly lower than the boiling point of water, which forms four hydrogen bonds at a time.

Example 4 : Buckyballs
Arrange C60 (buckminsterfullerene, which has a cage structure), He, Ar, and N2O in order of increasing boiling points.
Given: compounds
Asked for: order of increasing boiling points
Strategy:
Identify the intermolecular forces in each compound and then arrange the compounds according to the strength of those forces.
The substance with the weakest forces will have the lowest boiling point.
Solution:
To predict the relative boiling points of the compounds, we must consider their polarity (for dipole–dipole interactions), their
ability to form hydrogen bonds, and their molar mass (for London dispersion forces). Helium is nonpolar and by far the lightest,
so it should have the lowest boiling point. Argon and N2O have very similar molar masses (40 and 44 g/mol, respectively), but
N2O is polar while Ar is not. Consequently, N2O should have a higher boiling point. A C60 molecule is nonpolar, but its molar
mass is 720 g/mol, much greater than that of Ar or N2O. Because the boiling points of nonpolar substances increase rapidly with
molecular mass, C60 should boil at a higher temperature than the other nonionic substances. The predicted order is thus as
follows, with actual boiling points in parentheses:
He (−269°C) < Ar (−185.7°C) < N2O (−88.5°C) < C60 (>280°C).

Exercise 4
Arrange 2,4-dimethylheptane, Ne, CS2, and Cl2 in order of decreasing boiling points.

Answer:
2,4-dimethylheptane (132.9°C) > CS2 (46.6°C) > Cl2 (−34.6°C) > Ne (−246°C)

Example 5 :

9 [Link]
 Identify the most significant intermolecular force in each substance.
a. C3H8
b. CH3OH
c. H2S
Solution
a. Although C–H bonds are polar, they are only minimally polar. The most significant intermolecular force for this substance
would be dispersion forces.
b. This molecule has an H atom bonded to an O atom, so it will experience hydrogen bonding.
c. Although this molecule does not experience hydrogen bonding, the Lewis electron dot diagram and VSEPR indicate that it is
bent, so it has a permanent dipole. The most significant force in this substance is dipole-dipole interaction.

Exercise 5
Identify the most significant intermolecular force in each substance.
a. HF
b. HCl

Answer a
hydrogen bonding
Answer b
dipole-dipole interactions

Intermolecular Forces in Mixtures

When you have mixtures, you can have a combination of ions, polar molecules, and nonpolar molecules. If the mixture contains all
nonpolar molecules, then the only IMFs in that mixture will be London forces. An example of such a mixture would be hexane
(C6H14) and benzene (C6H6):
If the mixture contains only polar molecules, then there will be London forces, dipole/dipole forces, and possibly hydrogen
bonding. For example, in a mixture of acetone and diethyl ether, the polar ether and acetone molecules would exert London forces
and dipole/dipole forces:
In a mixture of acetone and methanol, there would be London forces, dipole/dipole forces, and hydrogen bonding between the
acetone and methanol molecules:
If the mixture contains different types of particles, these particles will form electrostatic interactions, but they will involve one or
more of the following IMFs.

Dipole/Induced Dipole Forces

In a mixture of polar and nonpolar molecules, there will be London forces, but also dipole/induced dipole forces. These forces are
created when the polar molecules get close enough to the nonpolar molecules to distort the electron clouds of the nonpolar
molecules and create temporarily induced dipoles. These forces are usually quite weak, but their strength depends on the number of
valence electrons and on the polarity of the polar molecule. In a solution of ethanol and hexane (yes, they do form a solution) there
would be London forces and dipole induced dipole forces as the ethanol molecules induce dipoles in the benzene molecules:

Ion/Induced Dipole Forces

In a mixture of ions and nonpolar molecules, there will be London forces, but also ion/induced dipole forces. These forces are
created when the ions get close enough to the nonpolar molecules to distort the electron clouds of the nonpolar molecules and
create temporarily induced dipoles. These forces are usually quite weak, but their strength depends on the number of valence
electrons and on the charge on the ion. These are not common forces, because ions and nonpolar molecules do not mix well,

10 [Link]
however, in biochemical systems these interactions can be common. In blood, Fe2+ ions in hemoglobin complexes induce dipoles
in oxygen molecules to create ion/induced dipole forces so that O2 molecules can be carried through the bloodstream:

Ion/dipole Forces
In a mixture of ions and polar molecules, there will be London forces, but also ion/dipole forces. These forces are by far the
strongest intermolecular forces, and their strength can often surpass the strength of some weak covalent bonds. These forces form
when ions and polar molecules get close to each other. Ions are most strongly attracted to water molecules, because of the high
polarity of the water molecules, but other small, very polar molecules such as methanol (CH3OH), ethanol (CH3CH2OH), and
dimethylsulfoxide (DMSO, (CH3)2SO) can also dissolve ions and form ion/dipole forces. In a solution of sodium chloride and
water there would be London forces and ion/dipole forces as the water molecules surround the sodium and the chloride ions:

Summary
Intermolecular forces are electrostatic in nature. Separate molecules are held close to other molecules by intermolecular
interactions, which are weaker than the intramolecular interactions that hold the atoms together within molecules and polyatomic
ions. Transitions between the solid and liquid or the liquid and gas phases are due to changes in intermolecular interactions, but do
not affect intramolecular interactions. The six types of intermolecular interactions are London dispersion forces, dipole–dipole
interactions, hydrogen bonding, dipole/induced dipole forces, ion/induced dipole forces, and ion/dipole forces. London dispersion
forces are due to the formation of instantaneous dipole moments in polar or nonpolar molecules as a result of short-lived
fluctuations of electron charge distribution, which in turn cause the temporary formation of an induced dipole in adjacent
molecules. their energy falls off as 1/r6. Larger atoms tend to be more polarizable than smaller ones because their outer electrons
are less tightly bound and are therefore more easily perturbed. Dipole–dipole interactions arise from the electrostatic interactions
of the positive and negative ends of molecules with permanent dipole moments; their strength is proportional to the magnitude of
the dipole moment and to 1/r3, where r is the distance between dipoles. Hydrogen bonds are especially strong dipole–dipole
interactions between molecules that have hydrogen bonded to a highly electronegative atom, such as O, N, or F. The resulting
partially positively charged H atom on one molecule can interact strongly with a lone pair of electrons of a partially negatively
charged O, N, or F atom on adjacent molecules. Because of strong O⋅⋅⋅H hydrogen bonding between water molecules, water has an
unusually high boiling point, and ice has an open, cagelike structure that is less dense than liquid water. Dipole/induced dipole
forces occur only in mixtures of polar and nonpolar substances, and the forces are generally weak. Ion/induced dipole forces are
less common than dipole/induced dipole forces, simply because ions and nonpolar molecules do not mix well. Ion/dipole forces
are the strongest intermolecular forces, and they allow many ionic compounds to dissolve in water.

Modified by Tom Neils (Grand Rapids Community College)

4.2 Intermolecular Forces is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

11 [Link]
4.3 Application of IMFs: Evaporation, Vapor Pressure, and Boiling Points
Skills to Develop
To know how and why the vapor pressure of a liquid varies with temperature.
To understand that the equilibrium vapor pressure of a liquid depends on the temperature and the intermolecular forces
present.
To understand that the relationship between pressure, enthalpy of vaporization, and temperature is given by the Clausius-
Clapeyron equation.

Nearly all of us have heated a pan of water with the lid in place and shortly thereafter heard the sounds of the lid rattling and hot
water spilling onto the stovetop. When a liquid is heated, its molecules obtain sufficient kinetic energy to overcome the forces
holding them in the liquid and they escape into the gaseous phase. By doing so, they generate a population of molecules in the
vapor phase above the liquid that produces a pressure—the vapor pressure of the liquid. In the situation we described, enough
pressure was generated to move the lid, which allowed the vapor to escape. If the vapor is contained in a sealed vessel, however,
such as an unvented flask, and the vapor pressure becomes too high, the flask will explode (as many students have unfortunately
discovered). In this section, we describe vapor pressure in more detail and explain how to quantitatively determine the vapor
pressure of a liquid.

Evaporation and Condensation

Because the molecules of a liquid are in constant motion, we can plot the fraction of molecules with a given kinetic energy (KE)
against their kinetic energy to obtain the kinetic energy distribution of the molecules in the liquid (Figure
4.3Applicationof I M F s. 1), just as we did for a gas. As for gases, increasing the temperature increases both the average kinetic

energy of the particles in a liquid and the range of kinetic energy of the individual molecules. If we assume that a minimum amount
of energy (E ) is needed to overcome the intermolecular attractive forces that hold a liquid together, then some fraction of
0

molecules in the liquid always has a kinetic energy greater than E . The fraction of molecules with a kinetic energy greater than
0

this minimum value increases with increasing temperature. Any molecule with a kinetic energy greater than E has enough energy
0

to overcome the forces holding it in the liquid and escape into the vapor phase. Before it can do so, however, a molecule must also
be at the surface of the liquid, where it is physically possible for it to leave the liquid surface; that is, only molecules at the surface
can undergo evaporation (or vaporization), where molecules gain sufficient energy to enter a gaseous state above a liquid’s surface,
thereby creating a vapor pressure.

Figure 4.3Applicationof I M F s. 1 : The Distribution of the Kinetic Energies of the Molecules of a Liquid at Two
Temperatures. Just as with gases, increasing the temperature shifts the peak to a higher energy and broadens the curve. Only
molecules with a kinetic energy greater than E0 can escape from the liquid to enter the vapor phase, and the proportion of
molecules with KE > E0 is greater at the higher temperature.
To understand the causes of vapor pressure, consider the apparatus shown in Figure 4.3Applicationof I M F s. 2. When a liquid is
introduced into an evacuated chamber (part (a) in Figure 4.3Applicationof I M F s. 2), the initial pressure above the liquid is
approximately zero because there are as yet no molecules in the vapor phase. Some molecules at the surface, however, will have

4.3 Application of IMFs.1 [Link]

sufficient kinetic energy to escape from the liquid and form a vapor, thus increasing the pressure inside the container. As long as the
temperature of the liquid is held constant, the fraction of molecules with KE > E will not change, and the rate at which
0

molecules escape from the liquid into the vapor phase will depend only on the surface area of the liquid phase.

Figure 4.3Applicationof I M F s. 2 : Vapor Pressure. (a) When a liquid is introduced into an evacuated chamber, molecules
with sufficient kinetic energy escape from the surface and enter the vapor phase, causing the pressure in the chamber to increase.
(b) When sufficient molecules are in the vapor phase for a given temperature, the rate of condensation equals the rate of
evaporation (a steady state is reached), and the pressure in the container becomes constant.
As soon as some vapor has formed, a fraction of the molecules in the vapor phase will collide with the surface of the liquid and
reenter the liquid phase in a process known as condensation (part (b) in Figure 4.3Applicationof I M F s. 2). As the number of
molecules in the vapor phase increases, the number of collisions between vapor-phase molecules and the surface will also increase.
Eventually, a steady state will be reached in which exactly as many molecules per unit time leave the surface of the liquid
(vaporize) as collide with it (condense). At this point, the pressure over the liquid stops increasing and remains constant at a
particular value that is characteristic of the liquid at a given temperature. The rates of evaporation and condensation over time for a
system such as this are shown graphically in Figure 4.3Applicationof I M F s. 3.

Figure 4.3Applicationof I M F s. 3 : The Relative Rates of Evaporation and Condensation as a Function of Time after a
Liquid Is Introduced into a Sealed Chamber. The rate of evaporation depends only on the surface area of the liquid and is
essentially constant. The rate of condensation depends on the number of molecules in the vapor phase and increases steadily until
it equals the rate of evaporation.

Equilibrium Vapor Pressure

Two opposing processes (such as evaporation and condensation) that occur at the same rate and thus produce no net change in a
system, constitute a dynamic equilibrium. In the case of a liquid enclosed in a chamber, the molecules continuously evaporate and
condense, but the amounts of liquid and vapor do not change with time. The pressure exerted by a vapor in dynamic equilibrium
with a liquid is the equilibrium vapor pressure of the liquid.

4.3 Application of IMFs.2 [Link]

If a liquid is in an open container, however, most of the molecules that escape into the vapor phase will not collide with the surface
of the liquid and return to the liquid phase. Instead, they will diffuse through the gas phase away from the container, and an
equilibrium will never be established. Under these conditions, the liquid will continue to evaporate until it has “disappeared.” The
speed with which this occurs depends on the vapor pressure of the liquid and the temperature. Volatile liquids have relatively high
vapor pressures and tend to evaporate readily; nonvolatile liquids have low vapor pressures and evaporate more slowly. Although
the dividing line between volatile and nonvolatile liquids is not clear-cut, as a general guideline, we can say that substances with
vapor pressures greater than that of water (Figure 4.3Applicationof I M F s. 4) are relatively volatile, whereas those with vapor
pressures less than that of water are relatively nonvolatile. Thus diethyl ether (ethyl ether), acetone, and gasoline are volatile, but
mercury, ethylene glycol, and motor oil are nonvolatile.

Figure 4.3Applicationof I M F s. 4 : The Vapor Pressures of Several Liquids as a Function of Temperature. The point at
which the vapor pressure curve crosses the P = 1 atm line (dashed) is the normal boiling point of the liquid.
The equilibrium vapor pressure of a substance at a particular temperature is a characteristic of the material, like its molecular mass,
melting point, and boiling point (Table 11.4). It does not depend on the amount of liquid as long as at least a tiny amount of liquid
is present in equilibrium with the vapor. The equilibrium vapor pressure does, however, depend very strongly on the temperature
and the intermolecular forces present, as shown for several substances in Figure 4.3Applicationof I M F s. 4. Molecules that can
hydrogen bond, such as ethylene glycol, have a much lower equilibrium vapor pressure than those that cannot, such as octane. The
nonlinear increase in vapor pressure with increasing temperature is much steeper than the increase in pressure expected for an ideal
gas over the corresponding temperature range. The temperature dependence is so strong because the vapor pressure depends on the
fraction of molecules that have a kinetic energy greater than that needed to escape from the liquid, and this fraction increases
exponentially with temperature. As a result, sealed containers of volatile liquids are potential bombs if subjected to large increases
in temperature. The gas tanks on automobiles are vented, for example, so that a car won’t explode when parked in the sun.
Similarly, the small cans (1–5 gallons) used to transport gasoline are required by law to have a pop-off pressure release.

Volatile substances have low boiling points and relatively weak intermolecular
interactions; nonvolatile substances have high boiling points and relatively strong
intermolecular interactions.

Boiling Points
As the temperature of a liquid increases, the vapor pressure of the liquid increases until it equals the external pressure, or the
atmospheric pressure in the case of an open container. Bubbles of vapor begin to form throughout the liquid, and the liquid begins
to boil. The temperature at which a liquid boils at exactly 1 atm pressure is the normal boiling point of the liquid. For water, the
normal boiling point is exactly 100°C. The normal boiling points of the other liquids in Figure 4.3Applicationof I M F s. 4 are
represented by the points at which the vapor pressure curves cross the line corresponding to a pressure of 1 atm. Although we
usually cite the normal boiling point of a liquid, the actual boiling point depends on the pressure. At a pressure greater than 1 atm,
water boils at a temperature greater than 100°C because the increased pressure forces vapor molecules above the surface to

4.3 Application of IMFs.3 [Link]

condense. Hence the molecules must have greater kinetic energy to escape from the surface. Conversely, at pressures less than 1
atm, water boils below 100°C.
Table 4.3Applicationof I M F s. 1 : The Boiling Points of Water at Various Locations on Earth
Place Altitude above Sea Level (ft) Atmospheric Pressure (mmHg) Boiling Point of Water (°C)

Mt. Everest, Nepal/Tibet 29,028 240 70

Bogota, Colombia 11,490 495 88

Denver, Colorado 5280 633 95

Washington, DC 25 759 100

Dead Sea, Israel/Jordan −1312 799 101.4

Typical variations in atmospheric pressure at sea level are relatively small, causing only minor changes in the boiling point of
water. For example, the highest recorded atmospheric pressure at sea level is 813 mmHg, recorded during a Siberian winter; the
lowest sea-level pressure ever measured was 658 mmHg in a Pacific typhoon. At these pressures, the boiling point of water
changes minimally, to 102°C and 96°C, respectively. At high altitudes, on the other hand, the dependence of the boiling point of
water on pressure becomes significant. Table 4.3Applicationof I M F s. 1 lists the boiling points of water at several locations with
different altitudes. At an elevation of only 5000 ft, for example, the boiling point of water is already lower than the lowest ever
recorded at sea level. The lower boiling point of water has major consequences for cooking everything from soft-boiled eggs (a
“three-minute egg” may well take four or more minutes in the Rockies and even longer in the Himalayas) to cakes (cake mixes are
often sold with separate high-altitude instructions). Conversely, pressure cookers, which have a seal that allows the pressure inside
them to exceed 1 atm, are used to cook food more rapidly by raising the boiling point of water and thus the temperature at which
the food is being cooked.

As pressure increases, the boiling point of a liquid increases and vice versa.
Example 4.3Applicationof I MF s. 2: Boiling Mercury
Use Figure 4.3Applicationof I M F s. 4 to estimate the following.
a. the boiling point of water in a pressure cooker operating at 1000 mmHg
b. the pressure required for mercury to boil at 250°C

Mercury boils at 356 °C at room pressure. To see video go to [Link]

Given: Data in Figure 4.3Applicationof I M F s. 4, pressure, and boiling point
Asked for: corresponding boiling point and pressure
Strategy:
A. To estimate the boiling point of water at 1000 mmHg, refer to Figure 4.3Applicationof I M F s. 4 and find the point where
the vapor pressure curve of water intersects the line corresponding to a pressure of 1000 mmHg.
B. To estimate the pressure required for mercury to boil at 250°C, find the point where the vapor pressure curve of mercury
intersects the line corresponding to a temperature of 250°C.
Solution:

4.3 Application of IMFs.4 [Link]

 a. A The vapor pressure curve of water intersects the P = 1000 mmHg line at about 110°C; this is therefore the boiling point of
water at 1000 mmHg.
b. B The vertical line corresponding to 250°C intersects the vapor pressure curve of mercury at P ≈ 75 mmHg. Hence this is the
pressure required for mercury to boil at 250°C.

Exercise 4.3Applicationof I MF s. 2: Boiling Ethlyene Glycol

Ethylene glycol is an organic compound primarily used as a raw material in the manufacture of polyester fibers and fabric
industry, and polyethylene terephthalate resins (PET) used in bottling. Use the data in Figure 4.3Applicationof I M F s. 4 to
estimate the following.
a. the normal boiling point of ethylene glycol
b. the pressure required for diethyl ether to boil at 20°C.

Answer a
200°C
Answer b
450 mmHg

Summary
Because the molecules of a liquid are in constant motion and possess a wide range of kinetic energies, at any moment some fraction
of them has enough energy to escape from the surface of the liquid to enter the gas or vapor phase. This process, called
vaporization or evaporation, generates a vapor pressure above the liquid. Molecules in the gas phase can collide with the liquid
surface and reenter the liquid via condensation. Eventually, a steady state is reached in which the number of molecules
evaporating and condensing per unit time is the same, and the system is in a state of dynamic equilibrium. Under these conditions,
a liquid exhibits a characteristic equilibrium vapor pressure that depends only on the temperature. We can express the nonlinear
relationship between vapor pressure and temperature as a linear relationship using the Clausius–Clapeyron equation. This
equation can be used to calculate the enthalpy of vaporization of a liquid from its measured vapor pressure at two or more
temperatures. Volatile liquids are liquids with high vapor pressures, which tend to evaporate readily from an open container;
nonvolatile liquids have low vapor pressures. When the vapor pressure equals the external pressure, bubbles of vapor form within
the liquid, and it boils. The temperature at which a substance boils at a pressure of 1 atm is its normal boiling point.

Contributors
Modified by Joshua Halpern (Howard University)
Modified by Tom Neils (Grand Rapids Community College)

4.3 Application of IMFs: Evaporation, Vapor Pressure, and Boiling Points is shared under a CC BY-NC-SA 4.0 license and was authored,
remixed, and/or curated by LibreTexts.

4.3 Application of IMFs.5 [Link]

4.4: Intermolecular Forces in Action: Surface Tension, Viscosity, and Capillary Action
Skills to Develop
To describe the unique properties of liquids.

Although you have been introduced to some of the interactions that hold molecules together in a liquid, we have not yet discussed
the consequences of those interactions for the bulk properties of liquids. We now turn our attention to three unique properties of
liquids that intimately depend on the nature of intermolecular interactions:
surface tension,
capillary action, and
viscosity.

Surface Tension
If liquids tend to adopt the shapes of their containers, then, do small amounts of water on a freshly waxed car form raised droplets
instead of a thin, continuous film? The answer lies in a property called surface tension, which depends on intermolecular forces.
Surface tension is the energy required to increase the surface area of a liquid by a unit amount and varies greatly from liquid to
liquid based on the nature of the intermolecular forces, e.g., water with hydrogen bonds has a surface tension of 7.29 x 10-2 J/m2 (at
20°C), while mercury with metallic (electrostatic) bonds has as surface tension that is 15-times higher: 4.86 x 10-1 J/m2 (at 20°C).
Figure 4.4.1 presents a microscopic view of a liquid droplet. A typical molecule in the interior of the droplet is surrounded by other
molecules that exert attractive forces from all directions. Consequently, there is no net force on the molecule that would cause it to
move in a particular direction. In contrast, a molecule on the surface experiences a net attraction toward the drop because there are
no molecules on the outside to balance the forces exerted by adjacent molecules in the interior. Because a sphere has the smallest
possible surface area for a given volume, intermolecular attractive interactions between water molecules cause the droplet to adopt
a spherical shape. This maximizes the number of attractive interactions and minimizes the number of water molecules at the
surface. Hence raindrops are almost spherical, and drops of water on a waxed (nonpolar) surface, which does not interact strongly
with water, form round beads (see the chapter opener photo). A dirty car is covered with a mixture of substances, some of which
are polar. Attractive interactions between the polar substances and water cause the water to spread out into a thin film instead of
forming beads.

Figure 4.4.1 : A Representation of Surface Tension in a Liquid. Molecules at the surface of water experience a net attraction to
other molecules in the liquid, which holds the surface of the bulk sample together. In contrast, those in the interior experience
uniform attractive forces.
The same phenomenon holds molecules together at the surface of a bulk sample of water, almost as if they formed a skin. When
filling a glass with water, the glass can be overfilled so that the level of the liquid actually extends above the rim. Similarly, a
sewing needle or a paper clip can be placed on the surface of a glass of water where it “floats,” even though steel is much denser
than water. Many insects take advantage of this property to walk on the surface of puddles or ponds without sinking. This is even
better describe in the zero gravity conditions of space as Figure 4.4.2 indicates (and more so in the video link).

4.4.1 [Link]
 Figure 4.4.2 : The Effects of the High Surface Tension of Liquid Water. The Full video can be found at
[Link]
Such phenomena are manifestations of surface tension, which is defined as the energy required to increase the surface area of a
liquid by a specific amount. Surface tension is therefore measured as energy per unit area, such as joules per square meter (J/m2) or
dyne per centimeter (dyn/cm), where 1 dyn = 1 × 10−5 N. The values of the surface tension of some representative liquids are listed
in Table 4.4.1. Note the correlation between the surface tension of a liquid and the strength of the intermolecular forces: the
stronger the intermolecular forces, the higher the surface tension. For example, water, with its strong intermolecular hydrogen
bonding, has one of the highest surface tension values of any liquid, whereas low-boiling-point organic molecules, which have
relatively weak intermolecular forces, have much lower surface tensions. Mercury is an apparent anomaly, but its very high surface
tension is due to the presence of strong metallic bonding.
Table 4.4.1: Surface Tension, Viscosity, Vapor Pressure (at 25°C Unless Otherwise Indicated), and Normal Boiling Points of Common
Liquids
Surface Tension (× 10−3
Substance Viscosity (mPa•s) Vapor Pressure (mmHg) Normal Boiling Point (°C)
J/m2)

Organic Compounds

diethyl ether 17 0.22 531 34.6

n-hexane 18 0.30 149 68.7

acetone 23 0.31 227 56.5

ethanol 22 1.07 59 78.3

ethylene glycol 48 16.1 ~0.08 198.9

Liquid Elements

bromine 41 0.94 218 58.8

mercury 486 1.53 0.0020 357

Water

0°C 75.6 1.79 4.6 —

20°C 72.8 1.00 17.5 —

60°C 66.2 0.47 149 —

100°C 58.9 0.28 760 —

Adding soaps and detergents that disrupt the intermolecular attractions between adjacent water molecules can reduce the surface
tension of water. Because they affect the surface properties of a liquid, soaps and detergents are called surface-active agents, or

4.4.2 [Link]
surfactants. In the 1960s, US Navy researchers developed a method of fighting fires aboard aircraft carriers using “foams,” which
are aqueous solutions of fluorinated surfactants. The surfactants reduce the surface tension of water below that of fuel, so the
fluorinated solution is able to spread across the burning surface and extinguish the fire. Such foams are now used universally to
fight large-scale fires of organic liquids.

Capillary Action
Intermolecular forces also cause a phenomenon called capillary action, which is the tendency of a polar liquid to rise against
gravity into a small-diameter tube (a capillary), as shown in Figure 4.4.3.

Figure 4.4.3 : The Phenomenon of Capillary Action. Capillary action seen as water climbs to different levels in glass tubes of
different diameters. Credit: Dr. Clay Robinson, PhD, West Texas A&M University.
When a glass capillary is is placed in liquid water, water rises up into the capillary. The height to which the water rises depends on
the diameter of the tube and the temperature of the water but not on the angle at which the tube enters the water. The smaller the
diameter, the higher the liquid rises.

Cohesive forces bind molecules of the same type together

Adhesive forces bind a substance to a surface

The same phenomenon holds molecules together at the surface of a bulk sample of water, almost as if they formed a skin. When
filling a glass with water, the glass can be overfilled so that the level of the liquid actually extends
Capillary action is the net result of two opposing sets of forces: cohesive forces, which are the intermolecular forces that hold a
liquid together, and adhesive forces, which are the attractive forces between a liquid and the substance that composes the capillary.
Water has both strong adhesion to glass, which contains polar SiOH groups, and strong intermolecular cohesion. When a glass
capillary is put into water, the surface tension due to cohesive forces constricts the surface area of water within the tube, while
adhesion between the water and the glass creates an upward force that maximizes the amount of glass surface in contact with the
water. If the adhesive forces are stronger than the cohesive forces, as is the case for water, then the liquid in the capillary rises to
the level where the downward force of gravity exactly balances this upward force. If, however, the cohesive forces are stronger
than the adhesive forces, as is the case for mercury and glass, the liquid pulls itself down into the capillary below the surface of the
bulk liquid to minimize contact with the glass (Figure 4.4.4). The upper surface of a liquid in a tube is called the meniscus, and the
shape of the meniscus depends on the relative strengths of the cohesive and adhesive forces. In liquids such as water, the meniscus
is concave; in liquids such as mercury, however, which have very strong cohesive forces and weak adhesion to glass, the meniscus
is convex (Figure 4.4.4).

Figure 4.4.4 : The Phenomenon of Capillary Action. Capillary action of water compared to mercury, in each case with respect to
a polar surface such as glass. Differences in the relative strengths of cohesive and adhesive forces result in different meniscus
shapes for mercury (left) and water (right) in glass tubes. (credit: Mark Ott)

4.4.3 [Link]
 Polar substances are drawn up a glass capillary and generally have a concave meniscus.

Fluids and nutrients are transported up the stems of plants or the trunks of trees by capillary action. Plants contain tiny rigid tubes
composed of cellulose, to which water has strong adhesion. Because of the strong adhesive forces, nutrients can be transported
from the roots to the tops of trees that are more than 50 m tall. Cotton towels are also made of cellulose; they absorb water because
the tiny tubes act like capillaries and “wick” the water away from your skin. The moisture is absorbed by the entire fabric, not just
the layer in contact with your body.

Viscosity
Viscosity (η) is the resistance of a liquid to flow. Some liquids, such as gasoline, ethanol, and water, flow very readily and hence
have a low viscosity. Others, such as motor oil, molasses, and maple syrup, flow very slowly and have a high viscosity. The two
most common methods for evaluating the viscosity of a liquid are (1) to measure the time it takes for a quantity of liquid to flow
through a narrow vertical tube and (2) to measure the time it takes steel balls to fall through a given volume of the liquid. The
higher the viscosity, the slower the liquid flows through the tube and the steel balls fall. Viscosity is expressed in units of the poise
(mPa•s); the higher the number, the higher the viscosity. The viscosities of some representative liquids are listed in Table 11.3.1 and
show a correlation between viscosity and intermolecular forces. Because a liquid can flow only if the molecules can move past one
another with minimal resistance, strong intermolecular attractive forces make it more difficult for molecules to move with respect
to one another. The addition of a second hydroxyl group to ethanol, for example, which produces ethylene glycol
(HOCH2CH2OH), increases the viscosity 15-fold. This effect is due to the increased number of hydrogen bonds that can form
between hydroxyl groups in adjacent molecules, resulting in dramatically stronger intermolecular attractive forces.

There is also a correlation between viscosity and molecular shape. Liquids consisting of long, flexible molecules tend to have
higher viscosities than those composed of more spherical or shorter-chain molecules. The longer the molecules, the easier it is for
them to become “tangled” with one another, making it more difficult for them to move past one another. London dispersion forces
also increase with chain length. Due to a combination of these two effects, long-chain hydrocarbons (such as motor oils) are highly
viscous.

Viscosity increases as intermolecular interactions or molecular size increases.

Application: Motor Oils
Motor oils and other lubricants demonstrate the practical importance of controlling viscosity. The oil in an automobile engine
must effectively lubricate under a wide range of conditions, from subzero starting temperatures to the 200°C that oil can reach in
an engine in the heat of the Mojave Desert in August. Viscosity decreases rapidly with increasing temperatures because the
kinetic energy of the molecules increases, and higher kinetic energy enables the molecules to overcome the attractive forces that
prevent the liquid from flowing. As a result, an oil that is thin enough to be a good lubricant in a cold engine will become too
“thin” (have too low a viscosity) to be effective at high temperatures.

4.4.4 [Link]
 Figure 4.4.5 : Oil being drained from a car
The viscosity of motor oils is described by an SAE (Society of Automotive Engineers) rating ranging from SAE 5 to SAE 50 for
engine oils: the lower the number, the lower the viscosity (Figure 4.4.5). So-called single-grade oils can cause major problems.
If they are viscous enough to work at high operating temperatures (SAE 50, for example), then at low temperatures, they can be
so viscous that a car is difficult to start or an engine is not properly lubricated. Consequently, most modern oils are multigrade,
with designations such as SAE 20W/50 (a grade used in high-performance sports cars), in which case the oil has the viscosity of
an SAE 20 oil at subzero temperatures (hence the W for winter) and the viscosity of an SAE 50 oil at high temperatures. These
properties are achieved by a careful blend of additives that modulate the intermolecular interactions in the oil, thereby
controlling the temperature dependence of the viscosity. Many of the commercially available oil additives “for improved engine
performance” are highly viscous materials that increase the viscosity and effective SAE rating of the oil, but overusing these
additives can cause the same problems experienced with highly viscous single-grade oils.

Example 4.4.1
Based on the nature and strength of the intermolecular cohesive forces and the probable nature of the liquid–glass adhesive
forces, predict what will happen when a glass capillary is put into a beaker of SAE 20 motor oil. Will the oil be pulled up into
the tube by capillary action or pushed down below the surface of the liquid in the beaker? What will be the shape of the
meniscus (convex or concave)? (Hint: the surface of glass is lined with Si–OH groups.)
Given: substance and composition of the glass surface
Asked for: behavior of oil and the shape of meniscus
Strategy:
A. Identify the cohesive forces in the motor oil.
B. Determine whether the forces interact with the surface of glass. From the strength of this interaction, predict the behavior of
the oil and the shape of the meniscus.
Solution
A Motor oil is a nonpolar liquid consisting largely of hydrocarbon chains. The cohesive forces responsible for its high boiling
point are almost solely London dispersion forces between the hydrocarbon chains.
B Such a liquid cannot form strong interactions with the polar Si–OH groups of glass, so the surface of the oil inside the
capillary will be lower than the level of the liquid in the beaker. The oil will have a convex meniscus similar to that of mercury.

Exercise 4.4.1
Predict what will happen when a glass capillary is put into a beaker of ethylene glycol. Will the ethylene glycol be pulled up into
the tube by capillary action or pushed down below the surface of the liquid in the beaker? What will be the shape of the
meniscus (convex or concave)?

Answer
Capillary action will pull the ethylene glycol up into the capillary. The meniscus will be concave.

Summary
Surface tension, capillary action, and viscosity are unique properties of liquids that depend on the nature of intermolecular
interactions. Surface tension is the energy required to increase the surface area of a liquid by a given amount. The stronger the
intermolecular interactions, the greater the surface tension. Surfactants are molecules, such as soaps and detergents, that reduce
the surface tension of polar liquids like water. Capillary action is the phenomenon in which liquids rise up into a narrow tube
called a capillary. It results when cohesive forces, the intermolecular forces in the liquid, are weaker than adhesive forces, the
attraction between a liquid and the surface of the capillary. The shape of the meniscus, the upper surface of a liquid in a tube, also
reflects the balance between adhesive and cohesive forces. The viscosity of a liquid is its resistance to flow. Liquids that have
strong intermolecular forces tend to have high viscosities.

4.4.5 [Link]
Modified by Tom Neils (Grand Rapids Community College)

4.4: Intermolecular Forces in Action: Surface Tension, Viscosity, and Capillary Action is shared under a CC BY-NC-SA 4.0 license and was
authored, remixed, and/or curated by LibreTexts.

4.4.6 [Link]
4.5: Solids, Liquids, and Gases: A Molecular Comparison
Skills to Develop
To be familiar with the kinetic molecular description of liquids.

The physical properties of a substance depends upon its physical state. Water vapor, liquid water and ice all have the same chemical
properties, but their physical properties are considerably different. In general Covalent bonds determine: molecular shape, bond
energies, chemical properties, while intermolecular forces (non-covalent bonds) influence the physical properties of liquids and
solids. The kinetic molecular theory of gases gives a reasonably accurate description of the behavior of gases. A similar model can
be applied to liquids, but it must take into account the nonzero volumes of particles and the presence of strong intermolecular
attractive forces.

Figure 4.5.1 : The four fundamental states of matter. Clockwise from top left, they are solid, liquid, plasma, and gas, represented
by an ice sculpture, a drop of water, electrical arcing from a tesla coil, and the air around clouds, respectively. Images used with
permission from Wikipedia.
The state of a substance depends on the balance between the kinetic energy of the individual particles (molecules or atoms) and the
intermolecular forces. The kinetic energy keeps the molecules apart and moving around, and is a function of the temperature of the
substance and the intermolecular forces try to draw the particles together (Table 4.5.2). A discussed previously, gasses are very
sensitive to temperatures and pressure. However, these also affect liquids and solids too. Heating and cooling can change the kinetic
energy of the particles in a substance, and so, we can change the physical state of a substance by heating or cooling it. Increasing
the pressure on a substance forces the molecules closer together, which increases the effectiveness of intermolecular forces
Table 4.5.2: Molecular level picture of gases, liquids and solids.

(a) in the gaseous state (b) as a liquid (c) in solid form

Below is an overview of the general properties of the three different phases of matter.

Properties of Gases
A collection of widely separated molecules
The kinetic energy of the molecules is greater than any attractive forces between the molecules
The lack of effective attractive force between molecules allows a gas to expand to fill its container
If attractive forces become large enough, then the gases exhibit non-ideal behavior

Properties of Liquids
The intermolecular attractive forces are strong enough to hold molecules close together
Liquids are more dense and less compressible than gases
Liquids have a definite volume, independent of the size and shape of their container
The attractive forces are not strong enough, however, to keep neighboring molecules in a fixed position and molecules are free
to move past or slide over one another

4.5.1 [Link]
 Thus, liquids can be poured and assume the shape of their containers

Properties of Solids
The intermolecular forces between neighboring molecules are strong enough to keep them locked in relatively stable positions
Solids (like liquids) are not very compressible due to the lack of space between molecules
If the molecules in a solid adopt a highly ordered packing arrangement, the structures are said to be crystalline

Due to the strong intermolecular forces between neighboring molecules, solids are rigid
Cooling a gas may change the state to a liquid
Cooling a liquid may change the state to a solid
Increasing the pressure on a gas may change the state to a liquid
Increasing the pressure on a liquid may change the state to a solid

Video 4.5.1 : Video highlighting the properties for the three states of matter. Source found at [Link]
KvoVzukHo.

Physical Properties of Liquids

In a gas, the distance between molecules, whether monatomic or polyatomic, is very large compared with the size of the molecules;
thus gases have a low density and are highly compressible. In contrast, the molecules in liquids are very close together, with
essentially no empty space between them. As in gases, however, the molecules in liquids are in constant motion, and their kinetic
energy (and hence their speed) depends on their temperature. We begin our discussion by examining some of the characteristic
properties of liquids to see how each is consistent with a modified kinetic molecular description.
The properties of liquids can be explained using a modified version of the kinetic molecular theory of gases described previously
This model explains the higher density, greater order, and lower compressibility of liquids versus gases; the thermal expansion of
liquids; why they diffuse; and why they adopt the shape (but not the volume) of their containers. A kinetic molecular description of
liquids must take into account both the nonzero volumes of particles and the presence of strong intermolecular attractive forces.
Solids and liquids have particles that are fairly close to one another, and are thus called "condensed phases" to distinguish them
from gases
Density: The molecules of a liquid are packed relatively close together. Consequently, liquids are much denser than gases. The
density of a liquid is typically about the same as the density of the solid state of the substance. Densities of liquids are therefore
more commonly measured in units of grams per cubic centimeter (g/cm3) or grams per milliliter (g/mL) than in grams per liter
(g/L), the unit commonly used for gases.
Molecular Order: Liquids exhibit short-range order because strong intermolecular attractive forces cause the molecules to
pack together rather tightly. Because of their higher kinetic energy compared to the molecules in a solid, however, the molecules
in a liquid move rapidly with respect to one another. Thus unlike the ions in the ionic solids, the molecules in liquids are not
arranged in a repeating three-dimensional array. Unlike the molecules in gases, however, the arrangement of the molecules in a
liquid is not completely random.

4.5.2 [Link]
 Compressibility: Liquids have so little empty space between their component molecules that they cannot be readily
compressed. Compression would force the atoms on adjacent molecules to occupy the same region of space.
Thermal Expansion: The intermolecular forces in liquids are strong enough to keep them from expanding significantly when
heated (typically only a few percent over a 100°C temperature range). Thus the volumes of liquids are somewhat fixed. Notice
from Table S1 (with a shorten version in Table 4.5.1) that the density of water, for example, changes by only about 3% over a
90-degree temperature range.
Table 4.5.1: The Density of Water at Various Temperatures
T (°C) Density (g/cm3)

0 0.99984

30 0.99565

60 0.98320

90 0.96535

Diffusion: Molecules in liquids diffuse because they are in constant motion. A molecule in a liquid cannot move far before
colliding with another molecule, however, so the mean free path in liquids is very short, and the rate of diffusion is much slower
than in gases.
Fluidity: Liquids can flow, adjusting to the shape of their containers, because their molecules are free to move. This freedom of
motion and their close spacing allow the molecules in a liquid to move rapidly into the openings left by other molecules, in turn
generating more openings, and so forth (Figure 11.1.3).

Figure 4.5.3 : Why Liquids Flow. Molecules in a liquid are in constant motion. Consequently, when the flask is tilted, molecules
move to the left and down due to the force of gravity, and the openings are occupied by other molecules. The result is a net flow of
liquid out of the container.

Contributors
Mike Blaber (Florida State University)
Modified by Tom Neils (Grand Rapids Community College)

4.5: Solids, Liquids, and Gases: A Molecular Comparison is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated
by LibreTexts.

4.5.3 [Link]
4.6 Phase Changes
We have previously described evaporation, the change of a liquid to a gas. This process is always endothermic, because energy is
required to completely disrupt the IMFs of attraction between the particles. The reverse process of evaporation is condensation,
which is always an exothermic process because IMFs of attraction form among the particles as they congregate into droplets. The
phase changes involving solids are described below.

Sublimation and Deposition

Some solids can transition directly into the gaseous state, bypassing the liquid state, via a process known as sublimation. At room
temperature and standard pressure, a piece of dry ice (solid CO2) sublimes, appearing to gradually disappear without ever forming
any liquid. Snow and ice sublime at temperatures below the melting point of water, a slow process that may be accelerated by
winds and the reduced atmospheric pressures at high altitudes. When solid iodine is warmed, the solid sublimes and a vivid purple
vapor forms (Figure 1). The reverse of sublimation is called deposition, a process in which gaseous substances directly change into
the solid state, bypassing the liquid state. The formation of frost is an example of deposition.

Figure 1 : Sublimation of solid iodine in the bottom of the tube produces a purple gas that subsequently deposits as solid iodine on
the colder part of the tube above. (credit: modification of work by Mark Ott)
Like vaporization, the process of sublimation requires an input of energy to overcome intermolecular attractions. The enthalpy of
sublimation, ΔHsub, is the energy required to convert one mole of a substance from the solid to the gaseous state. For example, the
sublimation of carbon dioxide is represented by:
CO (s) ⟶ CO (g) ΔHsub = 26.1 kJ/mol (1)
2 2

Likewise, the enthalpy change for the reverse process of deposition is equal in magnitude but opposite in sign to that for
sublimation:
CO (g) ⟶ CO (s) ΔHdep = −ΔHsub = −26.1 kJ/mol (2)
2 2

Fusion/Melting and Solidification/Freezing

When we heat a crystalline solid, we increase the average energy of its atoms, molecules, or ions and the solid gets hotter. At some
point, the added energy becomes large enough to partially overcome the forces holding the molecules or ions of the solid in their
melting. At this point, the
fixed positions, and the solid begins the process of transitioning to the liquid state, or
temperature of the solid stops rising, despite the continual input of heat, and it remains constant until all
of the solid is melted. Only after all of the solid has melted will continued heating increase the
temperature of the liquid (Figure \(\PageIndex{2}\).

1 [Link]
Figure 2 : (a) This beaker of ice has a temperature of −12.0 °C. (b) After 10 minutes the ice has absorbed enough heat from the air
to warm to 0 °C. A small amount has melted. (c) Thirty minutes later, the ice has absorbed more heat, but its temperature is still 0
°C. The ice melts without changing its temperature. (d) Only after all the ice has melted does the heat absorbed cause the
temperature to increase to 22.2 °C. (credit: modification of work by Mark Ott).
If we stop heating during melting and place the mixture of solid and liquid in a perfectly insulated container so no heat can enter or
escape, the solid and liquid phases remain in equilibrium. This is almost the situation with a mixture of ice and water in a very good
thermos bottle; almost no heat gets in or out, and the mixture of solid ice and liquid water remains for hours. In a mixture of solid
and liquid at equilibrium, the reciprocal process of melting and freezing occur at equal rates, and the quantities of solid and liquid
therefore remain constant. The temperature at which the solid and liquid phases of a given substance are in equilibrium is called the
melting point of the solid or the freezing point of the liquid. Use of one term or the other is normally dictated by the direction of the
phase transition being considered, for example, solid to liquid (melting) or liquid to solid (freezing).
The enthalpy of fusion and the melting point of a crystalline solid depend on the strength of the attractive forces between the units
present in the crystal. Molecules with weak attractive forces form crystals with low melting points. Crystals consisting of particles
with stronger attractive forces melt at higher temperatures.
The amount of heat required to change one mole of a substance from the solid state to the liquid state is the enthalpy of fusion,
ΔH of the substance. The enthalpy of fusion of ice is 6.0 kJ/mol at 0 °C. Fusion (melting) is an endothermic process:
f us

H O(s) → H O(l) ΔHfus = 6.01 kJ/mol (3)

2 2

The reciprocal process, freezing, is an exothermic process whose enthalpy change is −6.0 kJ/mol at 0 °C:
H O(l) → H O(s) ΔHfrz = −ΔHfus = −6.01 kJ/mol (4)
2 2

Selected molar enthalpies of fusion are tabulated in Table 1. Solids like ice which have strong intermolecular forces have much
higher values than those like CH4 with weak ones. Note that the enthalpies of fusion and vaporization change with temperature.
Table 1 : Molar Enthalpies of Fusion and Vaporization of Selected Substances.
ΔH(fusion) ΔH(vaporization) (ΔHv/Tb)
Substance Formula Melting Point / K Boiling Point / K
/ kJ mol1 / kJ mol-1 / JK-1 mol-1

Neon Ne 0.33 24 1.80 27 67

Oxygen O2 0.44 54 6.82 90.2 76

Methane CH4 0.94 90.7 8.18 112 73

Ethane C2H6 2.85 90.0 14.72 184 80

Chlorine Cl2 6.40 172.2 20.41 239 85

Carbon
CCl4 2.67 250.0 30.00 350 86
tetrachloride

6.00678 at 0°C,
40.657 at 100 °C,
101kPa
Water* H2O 273.1 45.051 at 0 °C, 373.1 109
6.354 at 81.6 °C,
46.567 at -33 °C
2.50 MPa

n-Nonane C9H20 19.3 353 40.5 491 82

Mercury Hg 2.30 234 58.6 630 91

2 [Link]
 ΔH(fusion) ΔH(vaporization) (ΔHv/Tb)
Substance Formula Melting Point / K Boiling Point / K
/ kJ mol1 / kJ mol-1 / JK-1 mol-1

Sodium Na 2.60 371 98 1158 85

Aluminum Al 10.9 933 284 2600 109

Lead Pb 4.77 601 178 2022 88

*[Link]

Energy Changes Associated with Phase Changes

Consider the extent to which intermolecular attractions must be overcome to achieve a given phase transition. Converting a solid
into a liquid requires that these attractions be only partially overcome; transition to the gaseous state requires that they be
completely overcome. As a result, the enthalpy of fusion for a substance is less than its enthalpy of vaporization. This same logic
can be used to derive an approximate relation between the enthalpies of all phase changes for a given substance. Though not an
entirely accurate description, sublimation may be conveniently modeled as a sequential two-step process of melting followed by
vaporization in order to apply Hess’s Law.
solid ⟶ liquid ΔHfus (5)

liquid ⟶ gas ΔHvap

–––––––––––––––––––––––
solid ⟶ gas ΔHsub = ΔHfus + ΔHvap

Viewed in this manner, the enthalpy of sublimation for a substance may be estimated as the sum of its enthalpies of fusion and
vaporization, as illustrated in Figure 3. For example:

Figure 3 : For a given substance, the sum of its enthalpy of fusion and enthalpy of vaporization is approximately equal to its
enthalpy of sublimation.

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).

4.6 Phase Changes is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

3 [Link]
4.7: Pressure: The Result of Particle Collisions
Skills to Develop
Define the property of pressure
Define and convert among the units of pressure measurements
Describe the operation of common tools for measuring gas pressure
Calculate pressure from manometer data

The earth’s atmosphere exerts a pressure, as does any other gas. Although we do not normally notice atmospheric pressure, we are
sensitive to pressure changes—for example, when your ears “pop” during take-off and landing while flying, or when you dive
underwater. Gas pressure is caused by the force exerted by gas molecules colliding with the surfaces of objects (Figure 4.7.1).
Although the force of each collision is very small, any surface of appreciable area experiences a large number of collisions in a
short time, which can result in a high pressure. In fact, normal air pressure is strong enough to crush a metal container when not
balanced by equal pressure from inside the container.

Figure 4.7.1 : The atmosphere above us exerts a large pressure on objects at the surface of the earth, roughly equal to the weight
of a bowling ball pressing on an area the size of a human thumbnail.
Atmospheric pressure is caused by the weight of the column of air molecules in the atmosphere above an object, such as the tanker
car. At sea level, this pressure is roughly the same as that exerted by a full-grown African elephant standing on a doormat, or a
typical bowling ball resting on your thumbnail. These may seem like huge amounts, and they are, but life on earth has evolved
under such atmospheric pressure. If you actually perch a bowling ball on your thumbnail, the pressure experienced is twice the
usual pressure, and the sensation is unpleasant.

A dramatic illustration of atmospheric pressure is provided in this brief video, which shows a railway tanker car imploding when
its internal pressure is decreased.
Pressure is defined as the force exerted on a given area:
F
P = (4.7.1)
A

Since pressure is directly proportional to force and inversely proportional to area (Equation 4.7.1), pressure can be increased
either by either increasing the amount of force or by decreasing the area over which it is applied. Correspondingly, pressure

4.7.1 [Link]
 can be decreased by either decreasing the force or increasing the area.

Let’s apply the definition of pressure (Equation 4.7.1) to determine which would be more likely to fall through thin ice in Figure
4.7.2.—the elephant or the figure skater?

Figure 4.7.2 : Although (a) an elephant’s weight is large, creating a very large force on the ground, (b) the figure skater exerts a
much higher pressure on the ice due to the small surface area of her skates. (credit a: modification of work by Guido da Rozze;
credit b: modification of work by Ryosuke Yagi).
A large African elephant can weigh 7 tons, supported on four feet, each with a diameter of about 1.5 ft (footprint area of 250 in2),
so the pressure exerted by each foot is about 14 lb/in2:
lb 1 elephant 1 f oot 2
pressure per elephant f oot = 14, 000 × × = 14 lb/i n (4.7.2)
2
elephant 4 f eet 250 in

The figure skater weighs about 120 lbs, supported on two skate blades, each with an area of about 2 in2, so the pressure exerted by
each blade is about 30 lb/in2:
lb 1 skater 1 blade 2
pressure per skate blade = 120 × × = 30 lb/i n (4.7.3)
skater 2 blades 2 in2

Even though the elephant is more than one hundred-times heavier than the skater, it exerts less than one-half of the pressure and
would therefore be less likely to fall though thin ice. On the other hand, if the skater removes her skates and stands with bare feet
(or regular footwear) on the ice, the larger area over which her weight is applied greatly reduces the pressure exerted:
lb 1 skater 1 f oot 2
pressure per human f oot = 120 × × = 2 lb/i n (4.7.4)
2
skater 2 f eet 30 in

The SI unit of pressure is the pascal (Pa), with 1 Pa = 1 N/m2, where N is the newton, a unit of force defined as 1 kg m/s2. One
pascal is a small pressure; in many cases, it is more convenient to use units of kilopascal (1 kPa = 1000 Pa) or bar (1 bar = 100,000
Pa). In the United States, pressure is often measured in pounds of force on an area of one square inch—pounds per square inch (psi)
—for example, in car tires. Pressure can also be measured using the unit atmosphere (atm), which originally represented the
average sea level air pressure at the approximate latitude of Paris (45°). Table 4.7.1 provides some information on these and a few
other common units for pressure measurements
Table 4.7.1: Pressure Units
Unit Name and Abbreviation Definition or Relation to Other Unit Comment

pascal (Pa) 1 Pa = 1 N/m2 recommended IUPAC unit

kilopascal (kPa) 1 kPa = 1000 Pa

pounds per square inch (psi) air pressure at sea level is ~14.7 psi

atmosphere (atm) 1 atm = 101,325 Pa air pressure at sea level is ~1 atm

bar (bar, or b) 1 bar = 100,000 Pa (exactly) commonly used in meteorology

millibar (mbar, or mb) 1000 mbar = 1 bar

used by aviation industry, also some weather

inches of mercury (in. Hg) 1 in. Hg = 3386 Pa
reports

4.7.2 [Link]
 Unit Name and Abbreviation Definition or Relation to Other Unit Comment

1 named after Evangelista Torricelli, inventor of

torr 1 torr = atm
760 the barometer

millimeters of mercury (mm Hg) 1 mm Hg ~1 torr

Example 4.7.1 : Conversion of Pressure Units

The United States National Weather Service reports pressure in both inches of Hg and millibars. Convert a pressure of 29.2 in.
Hg into:
a. torr
b. atm
c. kPa
d. mbar
Solution
This is a unit conversion problem. The relationships between the various pressure units are given in Table 9.2.1.
25.4 mm 1 torr
a. 29.2 in Hg × × = 742 torr
1 in 1 mm Hg

1 atm
b. 742 torr × = 0.976 atm
760 torr

101.325 kPa
c. 742 torr × = 98.9 kPa
760 torr

1000 Pa 1 bar 1000 mbar

d. 98.9 kPa × × × = 989 mbar
1 kPa 100, 000 Pa 1 bar

Exercise 4.7.1
A typical barometric pressure in Kansas City is 740 torr. What is this pressure in atmospheres, in millimeters of mercury, in
kilopascals, and in bar?

Answer
0.974 atm; 740 mm Hg; 98.7 kPa; 0.987 bar

We can measure atmospheric pressure, the force exerted by the atmosphere on the earth’s surface, with a barometer (Figure 4.7.3).
A barometer is a glass tube that is closed at one end, filled with a nonvolatile liquid such as mercury, and then inverted and
immersed in a container of that liquid. The atmosphere exerts pressure on the liquid outside the tube, the column of liquid exerts
pressure inside the tube, and the pressure at the liquid surface is the same inside and outside the tube. The height of the liquid in the
tube is therefore proportional to the pressure exerted by the atmosphere.

4.7.3 [Link]
Figure 4.7.3 : In a barometer, the height, h, of the column of liquid is used as a measurement of the air pressure. Using very dense
liquid mercury (left) permits the construction of reasonably sized barometers, whereas using water (right) would require a
barometer more than 30 feet tall.
If the liquid is water, normal atmospheric pressure will support a column of water over 10 meters high, which is rather inconvenient
for making (and reading) a barometer. Because mercury (Hg) is about 13.6-times denser than water, a mercury barometer only
1
needs to be as tall as a water barometer—a more suitable size. Standard atmospheric pressure of 1 atm at sea level (101,325
13.6
Pa) corresponds to a column of mercury that is about 760 mm (29.92 in.) high. The torr was originally intended to be a unit equal
to one millimeter of mercury, but it no longer corresponds exactly. The pressure exerted by a fluid due to gravity is known as
hydrostatic pressure, p:
p = hρg (4.7.5)

where
h is the height of the fluid,
ρ is the density of the fluid, and
g is acceleration due to gravity.

Example 4.7.2 : Calculation of Barometric Pressure

Show the calculation supporting the claim that atmospheric pressure near sea level corresponds to the pressure exerted by a
column of mercury that is about 760 mm high. The density of mercury = 13.6 g/cm . 3

Solution
The hydrostatic pressure is given by Equation 4.7.5, with h = 760 mm, ρ = 13.6 g/cm , and g = 9.81 m/s . Plugging these
3 2

values into the Equation 4.7.5 and doing the necessary unit conversions will give us the value we seek. (Note: We are expecting
to find a pressure of ~101,325 Pa:)
2
kg ⋅ m/s kg
2
101, 325 N/ m = 101, 325 = 101, 325 (4.7.6)
2 2
m m⋅s

3
1 m 13.6 g 1 kg (100 cm) 9.81 m
p = (760 mm × ) ×( × × ) ×( )
3 3 2
1000 mm 1 cm 1000 g (1 m) 1 s
3 2 5 2 5 2
= (0.760 m)(13, 600 kg/ m )(9.81 m/ s ) = 1.01 × 10 kg/ms = 1.01 × 10 N/ m
5
= 1.01 × 10 Pa

Exercise 4.7.2

4.7.4 [Link]
 Calculate the height of a column of water at 25 °C that corresponds to normal atmospheric pressure. The density of water at this
temperature is 1.0 g/cm3.

Answer
10.3 m

A manometer is a device similar to a barometer that can be used to measure the pressure of a gas trapped in a container. A closed-
end manometer is a U-shaped tube with one closed arm, one arm that connects to the gas to be measured, and a nonvolatile liquid
(usually mercury) in between. As with a barometer, the distance between the liquid levels in the two arms of the tube (h in the
diagram) is proportional to the pressure of the gas in the container. An open-end manometer (Figure 4.7.3) is the same as a closed-
end manometer, but one of its arms is open to the atmosphere. In this case, the distance between the liquid levels corresponds to the
difference in pressure between the gas in the container and the atmosphere.

Figure 4.7.4 : A manometer can be used to measure the pressure of a gas. The (difference in) height between the liquid levels (h)
is a measure of the pressure. Mercury is usually used because of its large density.

Example 4.7.3 : Calculation of Pressure Using an Open-End Manometer

The pressure of a sample of gas is measured at sea level with an open-end Hg (mercury) manometer, as shown below. Determine
the pressure of the gas in:
a. mm Hg
b. atm
c. kPa

Solution
The pressure of the gas equals the hydrostatic pressure due to a column of mercury of height 13.7 cm plus the pressure of the
atmosphere at sea level. (The pressure at the bottom horizontal line is equal on both sides of the tube. The pressure on the left is
due to the gas and the pressure on the right is due to 13.7 cm of Hg plus atmospheric pressure.)
a. In mm Hg, this is: 137 mm Hg + 760 mm Hg = 897 mm Hg

4.7.5 [Link]
 1 atm
b. 897 mmHg × = 1.18 atm
760 mmHg

101.325 kPa
c. 1.18 atm × = 1.20 × 10
2
kPa
1 atm

Exercise 4.7.3
The pressure of a sample of gas is measured at sea level with an open-end Hg manometer, as shown below Determine the
pressure of the gas in:
a. mm Hg
b. atm
c. kPa

Answer a

642 mm Hg
Answer b
0.845 atm
Answer c
85.6 kPa

Application: Measuring Blood Pressure

Blood pressure is measured using a device called a sphygmomanometer (Greek sphygmos = “pulse”). It consists of an inflatable
cuff to restrict blood flow, a manometer to measure the pressure, and a method of determining when blood flow begins and
when it becomes impeded (Figure 4.7.5). Since its invention in 1881, it has been an essential medical device. There are many
types of sphygmomanometers: manual ones that require a stethoscope and are used by medical professionals; mercury ones,
used when the most accuracy is required; less accurate mechanical ones; and digital ones that can be used with little training but
that have limitations. When using a sphygmomanometer, the cuff is placed around the upper arm and inflated until blood flow is
completely blocked, then slowly released. As the heart beats, blood forced through the arteries causes a rise in pressure. This
rise in pressure at which blood flow begins is the systolic pressure—the peak pressure in the cardiac cycle. When the cuff’s
pressure equals the arterial systolic pressure, blood flows past the cuff, creating audible sounds that can be heard using a
stethoscope. This is followed by a decrease in pressure as the heart’s ventricles prepare for another beat. As cuff pressure
continues to decrease, eventually sound is no longer heard; this is the diastolic pressure—the lowest pressure (resting phase) in
the cardiac cycle. Blood pressure units from a sphygmomanometer are in terms of millimeters of mercury (mm Hg).

4.7.6 [Link]
 Figure 4.7.5 : (a) A medical technician prepares to measure a patient’s blood pressure with a sphygmomanometer. (b) A typical
sphygmomanometer uses a valved rubber bulb to inflate the cuff and a diaphragm gauge to measure pressure. (credit a:
modification of work by Master Sgt. Jeffrey Allen)

Meteorology, Climatology, and Atmospheric Science

Throughout the ages, people have observed clouds, winds, and precipitation, trying to discern patterns and make predictions: when
it is best to plant and harvest; whether it is safe to set out on a sea voyage; and much more. We now face complex weather and
atmosphere-related challenges that will have a major impact on our civilization and the ecosystem. Several different scientific
disciplines use chemical principles to help us better understand weather, the atmosphere, and climate. These are meteorology,
climatology, and atmospheric science. Meteorology is the study of the atmosphere, atmospheric phenomena, and atmospheric
effects on earth’s weather. Meteorologists seek to understand and predict the weather in the short term, which can save lives and
benefit the economy. Weather forecasts (Figure 4.7.5) are the result of thousands of measurements of air pressure, temperature, and
the like, which are compiled, modeled, and analyzed in weather centers worldwide.

Figure 4.7.6 : Meteorologists use weather maps to describe and predict weather. Regions of high (H) and low (L) pressure have
large effects on weather conditions. The gray lines represent locations of constant pressure known as isobars. (credit: modification
of work by National Oceanic and Atmospheric Administration)
In terms of weather, low-pressure systems occur when the earth’s surface atmospheric pressure is lower than the surrounding
environment: Moist air rises and condenses, producing clouds. Movement of moisture and air within various weather fronts
instigates most weather events.
The atmosphere is the gaseous layer that surrounds a planet. Earth’s atmosphere, which is roughly 100–125 km thick, consists of
roughly 78.1% nitrogen and 21.0% oxygen, and can be subdivided further into the regions shown in Figure 4.7.7: the exosphere
(furthest from earth, > 700 km above sea level), the thermosphere (80–700 km), the mesosphere (50–80 km), the stratosphere
(second lowest level of our atmosphere, 12–50 km above sea level), and the troposphere (up to 12 km above sea level, roughly 80%
of the earth’s atmosphere by mass and the layer where most weather events originate). As you go higher in the troposphere, air
density and temperature both decrease.

4.7.7 [Link]
 Figure 4.7.7 : Earth’s atmosphere has five layers: the troposphere, the stratosphere, the mesosphere, the thermosphere, and the
exosphere.
Climatology is the study of the climate, averaged weather conditions over long time periods, using atmospheric data. However,
climatologists study patterns and effects that occur over decades, centuries, and millennia, rather than shorter time frames of hours,
days, and weeks like meteorologists. Atmospheric science is an even broader field, combining meteorology, climatology, and other
scientific disciplines that study the atmosphere.

Summary
Gases exert pressure, which is force per unit area. The pressure of a gas may be expressed in the SI unit of pascal or kilopascal, as
well as in many other units including torr, atmosphere, and bar. Atmospheric pressure is measured using a barometer; other gas
pressures can be measured using one of several types of manometers.

Key Equations
F
P =
A
p = hρg

Glossary
atmosphere (atm)
unit of pressure; 1 atm = 101,325 Pa

bar
(bar or b) unit of pressure; 1 bar = 100,000 Pa

barometer
device used to measure atmospheric pressure

hydrostatic pressure
pressure exerted by a fluid due to gravity

manometer
device used to measure the pressure of a gas trapped in a container

pascal (Pa)
SI unit of pressure; 1 Pa = 1 N/m2

pounds per square inch (psi)

unit of pressure common in the US

pressure
force exerted per unit area

torr

4.7.8 [Link]
 1
unit of pressure; 1 torr = atm
760

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).
Modified by Tom Neils (Grand Rapids Community College)

4.7: Pressure: The Result of Particle Collisions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

4.7.9 [Link]
4.8: Gases
The Ideal Gas Law
An ideal gas is a mythical substance in which the gas particles have neither volume nor attractive intermolecular forces. Such a
substance does not exist, but using the approximation creates a very simple mathematical description of a gas sample, the ideal gas
law. The ideal gas law, PV = nRT, relates the four variables that describe any sample of a gas:
P is pressure, the force per unit area exerted by gas molecules as they bounce off of the surfaces that they hit. There are
many units for measuring gas pressure. A unit you may have seen in a weather report is inches of mercury (in Hg), which are
convenient units to use when measuring pressure with a mercury manometer. Another common unit is pounds per square
inch (psi). However, we will use the unit of atmospheres (atm), an older pressure unit that was once defined as the pressure
required to hold up a 760 mm column of Hg at 0oC. Colloquially, 1.00 atm is the pressure exerted by the atmosphere at sea
level on an average day.
V is for volume, the amount of space that the gas sample is confined in. We will use the unit of Liters for our volume
measurements.
n is for moles, the number of moles of gas particles in the sample.
T is for temperature, the property that allows us to determine the direction of heat flow and also gives us an idea of the
kinetic energy of the gas molecules. We will use the Kelvin temperature scale for temperature, because we can not have any
negative temperatures when describing gases. (Remember, the temperature in Kelvin = the temperature in Celsius plus
273.15o. K = 273.15 + oC.)
L ⋅ atm (22.4 L)(1.00 atm)
R is the gas constant, 0.08206 . This value can be obtained from the ratio of ,
mole ⋅ K (1.00 mole)(273.15 K)

employing the volume that 1.00 mole of an ideal gas occupies when held at 1.00 atm pressure and a temperature of 273.15 K,
but it is true for any ideal gas under any set of conditions.
The ideal gas law is useful because if we know the values of any three of the four variables (P, V, T, and n) for a sample of gas, we
can calculate the value of the fourth variable for that gaseous sample. The equation also allows us to predict the final state of a
sample of a gas (i.e., its final temperature, pressure, volume, and amount) following any changes in conditions if the parameters (P,
V, T, and n) are specified for an initial state. Some applications are illustrated in the following examples. The approach used
throughout is always to start with the same equation—the ideal gas law—and then determine which quantities are given and which
need to be calculated. Let’s begin with simple cases in which we are given three of the four parameters needed for a complete
physical description of a gaseous sample.

Example 4.8.1
A balloon with a volume of 31,150 L is to be filled with an ideal gas. If the temperature at ground level is 303 K, and the
atmospheric pressure is 0.980 atm, how many moles of hydrogen gas will be needed to fill the balloon?
Given: volume, temperature, and pressure
Asked for: moles of gas
Strategy:
1. Solve the ideal gas law for the unknown quantity, in this case n.
2. Make sure that all quantities are given in units that are compatible with the units of the gas constant. If necessary, convert
them to the appropriate units, insert them into the equation you have derived, and then calculate the number of moles of
hydrogen gas needed.
Solution
PV (0.980 atm)(31150 L)
3
n = = = 1.23 × 10 moles
RT L atm
(0.08206 )(303 K)
mole K

Exercise 4.8.1

4.8.1 [Link]
 Suppose that an “empty” aerosol spray-paint can has a volume of 0.406 L and contains 0.0250 mol of a propellant gas such as
CO2. What is the pressure of the gas at 25.0°C?

Answer
1.51 L

A Practical Use of Air Pressure

A water well is an excavation or structure created in the ground by digging, driving, boring, or drilling to access groundwater in
underground aquifers. The well water is often drawn by a pump (Figure 4.8.1). Unfortunately, it impossible to pump water from
very deep in the ground with just a surface pump. The key to understanding why is realizing that suction generated by the pump is
not a force, but simply removing an opposing force to the force of air pressure which is already there. When you stick a pipe down
a deep hole into a pool of water at the bottom of a well, air inside the pipe is pushing down on the water in the pipe, and air outside
the pipe is pushing down on the water outside the pipe, which in turn pushes up on water inside the pipe - all is in a balance.

Figure 4.8.1 : The manual water pump draws water up from a well by creating a vacuum that water rushes in to fill. Hand pump
to pump water from a well in a village near Chennai in India. Image used with permission (CC BY 2.0; Sustainable Sanitation
Alliance).
Let's say you remove the air inside the pipe. The water is pushed up the the same as it was before, but there is no counter acting
force pushing the water down, so the water begins to rise inside the pipe (Figure 4.8.2). So far so good, but the water stops rising at
some height because the water is pulled down by gravity (i.e., the more water in the pipe, the more it weighs). Because the force of
the air outside the pipe is not changing, eventually the weight of the water is equal to the air pressure outside the pipe. When this
happens, the system is in balance again and water stops flowing.

Suction is not a force. Atmospheric pressure is the force that pushes the water up the pipe
Water is pumped from a well by creating a partial vacuum above the water by the pump. The amount of vacuum is equal to the
weight of the column of water from the water table to the surface. Atmospheric pressure at sea level is 760 mm of mercury (
1.01 × 10 P ascals ), which is equivalent to a 10.3-meter column of water. This is how deep water can be pumped from (with a
5

surface pump; other pressurized pumps can go deeper).

4.8.2 [Link]
 Figure 4.8.2 : Cross section and details of a surface pump used in a well. Image used with permission (CC BY-SA 3.0; Manco
Capac).
Modified by Tom Neils (Grand Rapids Community College)

4.8: Gases is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

4.8.3 [Link]
4.9 Solutions - What Mixes Together and Why
Solutions with Liquid Solvents
A solution is a homogeneous mixture in which the solute particles are so small that they cannot be filtered out and they do not
scatter light. For a solution to form, there needs to be the correct combination of enthalpic (intermolecular forces) and entropic
effects to enable the solvent and solute particles to interact strongly with each other without decreasing the entropy of the system.
In this section we will closely examine the effects of enthalpy, but we will not spend too much time discussing the effects of
entropy. To understand the effects of intermolecular forces, we need to go all the way back to bonds.

How Does Bond Polarity Affect/Determine Bond Type?

A bond is defined as the sharing of electrons by two atoms. Bond polarity occurs when two atoms share electrons unequally
because of a difference in the strength of attraction for the shared electrons by the nuclei of the two different atoms. The strength of
attraction scale that is most commonly used is electronegativity (EN). There are three common categories of bonds, based on the
difference in electronegativity (∆EN) values of the two bonding atoms:
a. If two atoms have identical, or similar EN values, their nuclei both pull on the shared electrons nearly equally. This equal
sharing is called a nonpolar covalent bond – neither nucleus has a greater electron density after forming the bond than it did
before forming the bond. Examples: H-H, F-F
b. If two atoms have a modest difference in EN values, the nucleus of the atom with the higher EN value has a greater pull on the
shared electrons, so that these electrons are more likely to be found closer to that nucleus than the nucleus with the lower EN
value. This unequal sharing is called a polar covalent bond – there is a partial negative charge around the nucleus of the atom
with the higher EN value because it is “using/borrowing” the electron(s) of the atom with the lower EN value. This leaves a
partial positive charge around the nucleus of the atom with the lower EN value because its electron(s) are less likely to be found
near it. Examples: H-Cl, C-F
c. If two atoms have a large difference in EN values, the shared electrons are much more likely to be found closer to the nucleus of
the atom with the higher EN value. There is always some small likelihood of finding the shared electron(s) near the nucleus of
the atom with the smaller EN value, so there are never really separate, fully-charged ions in a sample of a pure substance.
Nevertheless, it is common practice to designate these bonds as ionic bonds. This practice is reasonable because of the
formation of separate, fully-charged ions when compounds involving these extremely polar bonds are placed in water. (See ion-
dipole IMFs below.) Examples: Na-Cl, K-F
There are many approaches to the task of determining into which category a given bond should be placed. Some methods are more
rigorous than others, but often the rigorous methods are too complicated to be used quickly and simply. You should find a method
that you like and that serves your needs sufficiently and stick with it until you are asked to use a more rigorous method. The
simplest method is that a bond between a metal and a nonmetal is ionic, whereas a bond between two nonmetals is covalent.
There are two common conventions used to show the polarity of a bond:
a. lower case deltas (δ+ and δ-): These two symbols must always be used together, because they show the partial positive pole and
the partial negative pole of the polar bond. Example:
δ+ δ-

B – Cl

a. a dipole arrow : This symbol is used to show the positive end of the dipole and the negative end at which the electron
density is greatest. Example:

B – Cl

1 [Link]
What is Molecular Polarity?
The concept of molecular polarity is most easily applied to small molecules, but it can be applied to larger molecules with the
understanding that larger molecules may have multiple “identities.” The first task in determining molecular polarity is to identify
whether a substance is comprised of ions or of molecules. Individual small ions are not polar, because they do not have a charge
separation that leads to the existence of a positive pole and a negative pole. Thus, if you identify a compound as consisting of ions
(either monatomic or small polyatomic), you are no longer concerned about molecular polarity of that substance. To determine the
molecular polarity of a compound that contains only covalent bonds, you need to consider three aspects of the molecule:
a. the shape of the molecule
b. the polarity of all of the bonds in the molecule
c. the presence of atoms with lone pairs.
Taking these three aspects into account, you should be able to determine if a small molecule is polar or nonpolar. Some helpful
shortcuts that are almost always true:
a) If the central atom(s) in a molecule has at least one lone electron pair, the molecule will be polar.
NH3 is polar, and so is O3
b) If the molecule contains only nonpolar bonds and there are no lone pairs on the central atom(s), the molecule will be nonpolar.
All CxHy molecules are nonpolar
c) If all of the atoms attached to the central atom are of the same element and there are no lone pairs on the central atom, the
molecule is nonpolar.
CCl4 and CO2 are nonpolar
d) If the atoms attached to the central atom are of different elements, the molecule is polar.
CH2Cl2 and OCS are polar
e) If a molecule of a compound contains at least one N, O, F, or Cl atom, the molecule is usually polar, unless c) is true.
CH3CH2OH, HF, CH3NH2, and CH3Cl are all polar
f) When molecules get large enough, they might have polar sections and nonpolar sections. A general rule of thumb for carbon-
containing compounds is that molecules with 4/5 or fewer C atoms per polar bond can be considered to act as if they are polar.
Thus, molecules with 4/5 or more C atoms per polar bond can be considered to act as if they were nonpolar.
CH3CH2OH is considered polar; CH3CH2CH2CH2CH2CH2CH2OH is considered nonpolar; CH3CH2CH2CH2OH is right
on the polar/nonpolar divide
g) All single atoms are nonpolar. Most, but not all, molecules of elements are nonpolar.
Polar molecules have a dipole moment greater than zero, and thus are considered dipoles.

What is an Intermolecular Force?

If you have a collection of independent atoms, molecules, or ions, these particles will always exert forces of attraction and
repulsion among themselves as they more closely approach each other. The repulsive forces tend to be ignored, but they do exist
and come about mainly because of the repulsion of the negatively-charged electron clouds surrounding each particle (even for
cations, although the positive charges do lead to repulsion with other cations and the nucleus of other atoms.)
A great deal of time is spent studying the attractive forces among independent particles. These forces are what enable molecules
and atoms to gather together and remain in a condensed phase as liquids and solids. Collectively, these attractive forces are
commonly known as intermolecular forces (IMFs). They are the forces of electrostatic attraction that exist between separate
particles.

How is an IMF different from a bond?

Along with the common definition that bonds occur within molecules and IMFs occur between molecules, there are two closely
related factors that distinguish bonds and IMFs:
a. The atomic nuclei are closer together in a bond between two atoms than in an IMF between two particles.

2 [Link]
 b. The potential energy released when a bond forms is greater than the potential energy released when an IMF forms.
These statements are generalizations, and there are certainly exceptions, but they hold true for most common substances.

What are the Types of IMFs?

The simplest way to categorize IMFs is to classify the particles that are interacting as one of the following:
a. ions
b. polar molecules
c. nonpolar molecules
From these three particle types, you can describe five different types of interparticle interactions:
1. dipole/dipole forces
2. ion/dipole forces
3. dipole/induced dipole forces.
4. ion/induced dipole forces
5. dispersion or London forces
(All particles exert and experience London forces, but the only forces among nonpolar particles are London forces)
The only remaining interaction would be ions interacting with ions, but that is an ionic bond. There is, however, a sixth IMF. It is a
case of extreme dipole/dipole interactions:
6. molecules with very polar bonds interacting with molecules with very polar bonds – known as hydrogen bonding (but it is
NOT a bond!)
The only bonds that are polar enough to result in a large enough partial positive charge on a small atom are:
δ- δ+ δ- δ+ δ- δ+
F—H, O—H, and N—H bonds.
The only atoms that have a large enough EN value to result in a large enough partial negative charge on a small atom are:
δ- δ- δ-
F, O, and N

What Substances Will Mix with Each Other to Create a Solution?

This discussion ignores entropy and focuses on enthalpy, but entropy definitely plays a role. That discussion is for later.

A solution is a homogeneous mixture in which the solute particles are so small that they cannot be filtered out and so dispersed
throughout the mixture that they do not scatter a beam of light that travels through the mixture. The probability of one substance
dissolving/mixing in/with another substance to form a solution depends on whether or not the newly formed IMFs are as
energetically favorable as the currently existing IMFs. Thus, the mutual solubility of two substances depends mainly on the
substance with the IMFs that involve the largest charge separation. In other words, there is a hierarchy of what will mix:
a) Ionically-bonded solids will form a solution (dissolve) in a solvent only if the solvent can provide very strong ion/dipole
interactions.

- Usually water is the only material that can dissolve inorganic salts to any great extent, although some inorganic salts
dissolve slightly in methanol and DMSO. You can find tables of solubility rules for common inorganic salts in water.
One of these rules is that almost all compounds containing Group IA cations are soluble.

- Organic salts have a reasonable solubility in many polar organic solvents, but are generally much more soluble in water
than in these organic solvents. The non-organic counter cations are usually Na+, K+, or NH4+, all of which generally
form soluble salts. The non-organic counter anions are usually Cl-, NO3-, and SO42-, all of which generally form
soluble salts.
b) Water will form a solution (mix or dissolve) with another covalently-bonded substance only if:

3 [Link]
 i) the molecules of that substance can form hydrogen bonds with the water molecules.
-The molecules of the other substance do not need to be able to form hydrogen bonds among themselves when in the pure form, but
they must be polar molecules and contain an N, O, or F atom that has a partial negative charge. Acetone is an example of such a
substance.
The ability of a molecule to form hydrogen bonds with water molecules does not guarantee that the molecule will dissolve in water.
If there is a portion of the molecule that is nonpolar, this nonpolar section interferes with the water molecules’ ability to form
hydrogen bonds among themselves. Thus, the larger the nonpolar section, the less soluble the substance is in water. A general rule
of thumb is the 4-5 carbon atom rule: Molecules with fewer than 4-5 C atoms per hydrogen bonding group will likely be soluble
in water. Molecules with more than 4-5 C atoms per hydrogen bonding group will likely be insoluble in water. The water solubility
of molecules with 4-5 C atoms per hydrogen bonding group is best determined by experiment or by a search of the literature. For
instance, the following compounds, all of which are polar and can form hydrogen bonds with water, contain four C atoms per
molecule: butanoic acid is soluble with water in all ratios; 1-butanol is reasonably soluble in water; and diethyl ether is so slightly
soluble in water that it is considered insoluble.
or
ii) the molecules of that substance react with water molecules to form ions, which then dissolve in the water because of
ion/dipole interactions.
- The six strong acids (HCl, HBr, HI, HNO3, HClO4, and H2SO4) are the most common examples. All of these acids have Ka values
greater than 10. (Remember, the Ka value tells you how likely it is for the acid to react with water, and a Ka greater than 1 means
that the reaction is product-favored at equilibrium)
All molecular weak acids and molecular weak bases react with water to some extent to create ions, but these weak acids all have Ka
values that are less than 1 and these weak bases all have Kb values that are less than 1. Thus, all these reactions are considered
reactant-favored, and for purposes of predicting water solubility, we ignore the fact that some ions are formed. Remember that the
intact weak acid or weak base molecules may themselves dissolve in water through hydrogen bonding. (See section b) (i) above.
c) The common adage “Like dissolves like” works well for most organic compounds. Polar compounds tend to mix well with other
polar compounds. The IMFs involved can be hydrogen boding, dipole/dipole, and London forces. Nonpolar compounds tend to mix
well with other nonpolar compounds, with London forces being the only IMF involved.
- With a few notable exceptions (CCl4, for instance), organic compounds containing chlorine and bromine and iodine do
have a dipole moment, and are therefore polar molecules. These molecules cannot, however, form hydrogen bonds
with water, nor are the halogen atoms present as ions. Thus, halogenated organic compounds do not dissolve well in
water.
- Because most organic compounds have at least one small nonpolar section on their molecules, some polar organic
compounds mix well with nonpolar organic compounds.
d) Solubility in aqueous acid solutions and/or aqueous base solutions is a confusing concept, mainly because of the way that
chemists talk about the process. The statement, “Check the solubility of benzoic acid in 3 M NaOH” may be clear to a practicing
chemist, but it is misleading to most beginning students. The statement would be much clearer if it were written, “Check the water
solubility of the organic anion formed when benzoic acid reacts with the OH- ion in an aqueous 3M NaOH solution.” The same
clarity, or lack thereof, is true for statements about solubility in aqueous acid solutions.
The order of events when an aqueous solution of a base is added to an organic compound that can act as an acid is:
i) The organic compound reacts with the OH- ion, donating an H+ ion to the OH- ion.
ii) The products of this reaction are water and the conjugate base of the organic compound. If the original organic compound
was a neutral molecule, the conjugate base will be a water-soluble anion.
The order of events when an aqueous solution of an acid is added to an organic compound that can act as a base is:
i) The organic compound reacts with the acid, accepting an H+ ion.
ii) The products of this reaction are the conjugate base of the acid, and the conjugate acid of the organic compound. If the
original organic compound was a neutral molecule, the conjugate acid will be a water-soluble cation.

4 [Link]
If no acid/base reaction occurs between the aqueous acid/base and the organic compound, then the organic compound remains as a
neutral substance, and maintains its original solubility (or lack thereof ) in water.

If knowing the solubility of two compounds is an essential piece of information for your work, it is always best to not
only look up the solubility data, but also perform careful solubility tests yourself in the lab.

4.9 Solutions - What Mixes Together and Why is shared under a CC BY-SA 4.0 license and was authored, remixed, and/or curated by Tom Neils.

5 [Link]
4.10 Factors Affecting Solubility
Skills to Develop
To understand the relationship among temperature, pressure, and solubility.
The understand that the solubility of a solid may increase or decrease with increasing temperature,
To understand that the solubility of a gas decreases with an increase in temperature and a decrease in pressure.

Experimentally it is found that the solubility of most compounds depends strongly on temperature and, if a gas, on pressure as well.
As we shall see, the ability to manipulate the solubility by changing the temperature and pressure has several important
consequences.

Effect of Temperature on the Solubility of Solids

Figure 1 shows plots of the solubilities of several organic and inorganic compounds in water as a function of temperature. Although
the solubility of a solid generally increases with increasing temperature, there is no simple relationship between the structure of a
substance and the temperature dependence of its solubility. Many compounds (such as glucose and C H C O N a) exhibit a 3 2

dramatic increase in solubility with increasing temperature. Others (such as N aC l and K SO ) exhibit little variation, and still
2 4

others (such as Li SO ) become less soluble with increasing temperature.

2 4

Figure 1 : Solubilities of Several Inorganic and Organic Solids in Water as a Function of Temperature. Solubility may increase or
decrease with temperature; the magnitude of this temperature dependence varies widely among compounds.
Notice in particular the curves for N H N O and C aC l . The dissolution of ammonium nitrate in water is endothermic (
4 3 2

ΔH soln= +25.7 kJ/mol), whereas the dissolution of calcium chloride is exothermic (ΔH = −68.2 kJ/mol), yet Figure 1
soln

shows that the solubility of both compounds increases sharply with increasing temperature. In fact, the magnitudes of the changes
in both enthalpy and entropy for dissolution are temperature dependent. Because the solubility of a compound is ultimately
determined by relatively small differences between large numbers, there is generally no good way to predict how the solubility will
vary with temperature.
The variation of solubility with temperature has been measured for a wide range of compounds, and the results are published in
many standard reference books. Chemists are often able to use this information to separate the components of a mixture by
fractional crystallization, the separation of compounds on the basis of their solubilities in a given solvent. For example, if we have a
mixture of 150 g of sodium acetate (C H C O N a) and 50 g of KBr , we can separate the two compounds by dissolving the
3 2

mixture in 100 g of water at 80°C and then cooling the solution slowly to 0°C. According to the temperature curves in Figure 1,
both compounds dissolve in water at 80°C, and all 50 g of KBr remains in solution at 0°C. Only about 36 g of C H C O N a are 3 2

soluble in 100 g of water at 0°C, however, so approximately 114 g (150 g − 36 g) of C H C O N a crystallizes out on cooling. The
3 2

1 [Link]
crystals can then be separated by filtration. Thus fractional crystallization allows us to recover about 75% of the original
C H C O N a in essentially pure form in only one step.
3 2

Fractional crystallization is a common technique for purifying compounds as diverse as those shown in Figure 1 and from
antibiotics to enzymes. For the technique to work properly, the compound of interest must be more soluble at high temperature than
at low temperature, so that lowering the temperature causes it to crystallize out of solution. In addition, the impurities must be more
soluble than the compound of interest (as was KBr in this example) and preferably present in relatively small amounts.

Effect of Temperature on the Solubility of Gases

The solubility of gases in liquids decreases with increasing temperature, as shown in Figure 2. Attractive intermolecular
interactions in the gas phase are essentially zero for most substances. When a gas dissolves, it does so because its molecules
interact with solvent molecules. Because heat is released when these new attractive interactions form, dissolving most gases in
liquids is an exothermic process (ΔH < 0 ). Conversely, adding heat to the solution provides thermal energy that overcomes the
soln

attractive forces between the gas and the solvent molecules, thereby decreasing the solubility of the gas. The phenomenon is similar
to that involved in the increase in vapor pressure of a pure liquid with increasing temperature. In the case of vapor pressure,
however, it is attractive forces between solvent molecules that are being overcome by the added thermal energy when the
temperature is increased.

Figure 2 : Solubilities of Several Common Gases in Water as a Function of Temperature at Partial Pressure of 1 atm. The
solubilities of all gases decrease with increasing temperature.
The decrease in the solubilities of gases at higher temperatures has both practical and environmental implications. Anyone who
routinely boils water in a teapot or electric kettle knows that a white or gray deposit builds up on the inside and must eventually be
removed. The same phenomenon occurs on a much larger scale in the giant boilers used to supply hot water or steam for industrial
applications, where it is called “boiler scale,” a deposit that can seriously decrease the capacity of hot water pipes (Figure 3). The
problem is not a uniquely modern one: aqueducts that were built by the Romans 2000 years ago to carry cold water from alpine
regions to warmer, drier regions in southern France were clogged by similar deposits. The chemistry behind the formation of these
deposits is moderately complex and will be described elsewhere, but the driving force is the loss of dissolved C O from solution.
2

Hard water contains dissolved C a and H C O (bicarbonate) ions. Calcium bicarbonate (C a(H C O ) is rather soluble in water,
2+ −

3 3 2

but calcium carbonate (C aC O ) is quite insoluble. A solution of bicarbonate ions can react to form carbon dioxide, carbonate ion,
3

and water:
− 2−
2H C O → CO + H2 O(l) + C O2(aq) (13.9)
3(aq) 3(aq)

Heating the solution decreases the solubility of C O , which escapes into the gas phase above the solution. In the presence of
2

calcium ions, the carbonate ions precipitate as insoluble calcium carbonate, the major component of boiler scale.

2 [Link]
Figure 3 : Calcium carbonate deposits (left) Calcium carbonate (C aC O ) deposits in hot water pipes can significantly reduce pipe
3

capacity. These deposits, called boiler scale, form when dissolved C O is driven into the gas phase at high temperatures. (right)
2

Highly calcified remains of Eiffel aqueduct near Euskirchen-Kreuzweingarten, Germany. Figure used with permission from
Wikipedia
In thermal pollution, lake or river water that is used to cool an industrial reactor or a power plant is returned to the environment at a
higher temperature than normal. Because of the reduced solubility of O at higher temperatures (Figure 2), the warmer water
2

contains less dissolved oxygen than the water did when it entered the plant. Fish and other aquatic organisms that need dissolved
oxygen to live can literally suffocate if the oxygen concentration of their habitat is too low. Because the warm, oxygen-depleted
water is less dense, it tends to float on top of the cooler, denser, more oxygen-rich water in the lake or river, forming a barrier that
prevents atmospheric oxygen from dissolving. Eventually even deep lakes can be suffocated if the problem is not corrected.
Additionally, most fish and other nonmammalian aquatic organisms are cold-blooded, which means that their body temperature is
the same as the temperature of their environment. Temperatures substantially greater than the normal range can lead to severe stress
or even death. Cooling systems for power plants and other facilities must be designed to minimize any adverse effects on the
temperatures of surrounding bodies of water.
A similar effect is seen in the rising temperatures of bodies of water such as the Chesapeake Bay, the largest estuary in North
America, where global warming has been implicated as the cause. For each 1.5°C that the bay’s water warms, the capacity of water
to dissolve oxygen decreases by about 1.1%. Many marine species that are at the southern limit of their distributions have shifted
their populations farther north. In 2005, the eelgrass, which forms an important nursery habitat for fish and shellfish, disappeared
from much of the bay following record high water temperatures. Presumably, decreased oxygen levels decreased populations of
clams and other filter feeders, which then decreased light transmission to allow the eelsgrass to grow. The complex relationships in
ecosystems such as the Chesapeake Bay are especially sensitive to temperature fluctuations that cause a deterioration of habitat
quality.

Effect of Pressure on the Solubility of Gases: Henry’s Law

External pressure has very little effect on the solubility of liquids and solids. In contrast, the solubility of gases increases as the
partial pressure of the gas above a solution increases. This point is illustrated in Figure 4, which shows the effect of increased
pressure on the dynamic equilibrium that is established between the dissolved gas molecules in solution and the molecules in the
gas phase above the solution. Because the concentration of molecules in the gas phase increases with increasing pressure, the
concentration of dissolved gas molecules in the solution at equilibrium is also higher at higher pressures.

Figure 4 : A Model Depicting Why the Solubility of a Gas Increases as the Partial Pressure Increases at Constant Temperature. (a)
When a gas comes in contact with a pure liquid, some of the gas molecules (purple spheres) collide with the surface of the liquid
and dissolve. When the concentration of dissolved gas molecules has increased so that the rate at which gas molecules escape into
the gas phase is the same as the rate at which they dissolve, a dynamic equilibrium has been established, as depicted here. This
equilibrium is entirely analogous to the one that maintains the vapor pressure of a liquid. (b) Increasing the pressure of the gas
increases the number of molecules of gas per unit volume, which increases the rate at which gas molecules collide with the surface

3 [Link]
 of the liquid and dissolve. (c) As additional gas molecules dissolve at the higher pressure, the concentration of dissolved gas
increases until a new dynamic equilibrium is established.
The relationship between pressure and the solubility of a gas is described quantitatively by Henry’s law, which is named for its
discoverer, the English physician and chemist, William Henry (1775–1836):

C = kP (13.3.1)

where
C is the concentration of dissolved gas at equilibrium,
P is the partial pressure of the gas, and
k is the Henry’s law constant, which must be determined experimentally for each combination of gas, solvent, and temperature.
Although the gas concentration may be expressed in any convenient units, we will use molarity exclusively. The units of the
Henry’s law constant are therefore mol/(L·atm) = M/atm. Values of the Henry’s law constants for solutions of several gases in
water at 20°C are listed in Table 1.
As the data in Table 1 demonstrate, the concentration of a dissolved gas in water at a given pressure depends strongly on its
physical properties. For a series of related substances, London dispersion forces increase as molecular mass increases. Thus among
the elements of group 18, the Henry’s law constants increase smoothly from He to Ne to Ar. The table also shows that O is almost 2

twice as soluble as N . Although London dispersion forces are too weak to explain such a large difference, O is paramagnetic and
2 2

hence more polarizable than N , which explains its high solubility.

2

Table 1 : Henry’s Law Constants for Selected Gases in Water at 20°C

Gas Henry’s Law Constant [mol/(L·atm)] × 10−4

He 3.9

Ne 4.7

Ar 15

H2 8.1

N2 7.1

O2 14

CO2 392

Gases that react chemically with water, such as H C l and the other hydrogen halides, H S , and N H , do not obey Henry’s law; all
2 3

of these gases are much more soluble than predicted by Henry’s law. For example, H C l reacts with water to give H and C l , +

(aq)
−

(aq)

not dissolved H C l molecules, and its dissociation into ions results in a much higher solubility than expected for a neutral molecule.

Gases that react with water do not obey Henry’s law.

Henry’s law has important applications. For example, bubbles of C O form as soon as a carbonated beverage is opened because
2

the drink was bottled under C O at a pressure greater than 1 atm. When the bottle is opened, the pressure of C O above the
2 2

solution drops rapidly, and some of the dissolved gas escapes from the solution as bubbles. Henry’s law also explains why scuba
divers have to be careful to ascend to the surface slowly after a dive if they are breathing compressed air. At the higher pressures
under water, more N2 from the air dissolves in the diver’s internal fluids. If the diver ascends too quickly, the rapid pressure change
causes small bubbles of N2 to form throughout the body, a condition known as “the bends.” These bubbles can block the flow of
blood through the small blood vessels, causing great pain and even proving fatal in some cases.
Due to the low Henry’s law constant for O in water, the levels of dissolved oxygen in water are too low to support the energy
2

needs of multicellular organisms, including humans. To increase the O concentration in internal fluids, organisms synthesize
2

highly soluble carrier molecules that bind O reversibly. For example, human red blood cells contain a protein called hemoglobin
2

that specifically binds O and facilitates its transport from the lungs to the tissues, where it is used to oxidize food molecules to
2

provide energy. The concentration of hemoglobin in normal blood is about 2.2 mM, and each hemoglobin molecule can bind four
O molecules. Although the concentration of dissolved O in blood serum at 37°C (normal body temperature) is only 0.010 mM,
2 2

the total dissolved O concentration is 8.8 mM, almost a thousand times greater than would be possible without hemoglobin.
2

4 [Link]
Synthetic oxygen carriers based on fluorinated alkanes have been developed for use as an emergency replacement for whole blood.
Unlike donated blood, these “blood substitutes” do not require refrigeration and have a long shelf life. Their very high Henry’s law
constants for O result in dissolved oxygen concentrations comparable to those in normal blood.
2

Summary
The solubility of most substances depends strongly on the temperature and, in the case of gases, on the pressure. The solubility of
most solid or liquid solutes increases with increasing temperature. The components of a mixture can often be separated using
fractional crystallization, which separates compounds according to their solubilities. The solubility of a gas decreases with
increasing temperature. Henry’s law describes the relationship between the pressure and the solubility of a gas.
Modified by Tom Neils (Grand Rapids Community College)

4.10 Factors Affecting Solubility is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

5 [Link]
4.11 Suspensions and Colloids
Skills to Develop
To distinguish between true solutions and solutions with aggregate particles.

Suspensions and colloids are two common types of mixtures whose properties are in many ways intermediate between those of
homogeneous and heterogeneous mixtures. A suspension is a mixture of particles with diameters of about 1 µm (1000 nm) that are
distributed throughout a second phase. Common suspensions include paint, blood, and hot chocolate, which are solid particles in a
liquid, and aerosol sprays, which are liquid particles in a gas. If the suspension is allowed to stand, the two phases will separate,
which is why paints must be thoroughly stirred or shaken before use. A colloid is also a mixture, but the particles of a colloid are
typically smaller than those of a suspension, generally in the range of 2 to about 500 nm in diameter. Colloids include fog and
clouds (liquid particles in a gas), milk (solid particles in a liquid), and butter (solid particles in a solid). Other colloids are used
industrially as catalysts. Unlike in a suspension, the particles in a colloid do not separate into two phases on standing. The only
combination of substances that cannot produce a suspension or a colloid is a mixture of two gases because their particles are so
small that they always form true solutions.
Deciding whether to categorize the colloid or suspension as a homogeneous or heterogeneous mixture is a challenge. If
"homogeneous" is defined to mean that the mixture is uniform in concentration and appearance throughout the entire mixture, then
most colloids and well-mixed suspensions are homogeneous. Examples would be fog and milk (colloids); and freshly stirred paint
and hot chocolate (suspensions). If you let a suspension sit for long enough, however, the particles will settle out, leaving you with
a heterogeneous mixture.
Table 1 : Properties of Liquid Solutions, Colloids, and Suspensions
Approximate Size of Particles
Type of Mixture Characteristic Properties Examples
(nm)

not filterable; does not separate on

air, white wine, gasoline, salt
solution <2 standing; does not scatter visible
water
light

scatters visible light; translucent

smoke, fog, ink, milk, butter,
colloid 2–500 or opaque; not filterable; does not
cheese
separate on standing

cloudy or opaque; filterable; muddy water, hot cocoa, blood,

suspension 500–1000
separates on standing paint

Colloids and Suspensions

Colloids were first characterized in about 1860 by Thomas Graham, who also gave us Graham’s law of diffusion and effusion.
Although some substances, such as starch, gelatin, and glue, appear to dissolve in water to produce solutions, Graham found that
they diffuse very slowly or not at all compared with solutions of substances such as salt and sugar. Graham coined the word colloid
(from the Greek kólla, meaning “glue”) to describe these substances, as well as the words sol and gel to describe certain types of
colloids in which all of the solvent has been absorbed by the solid particles, thus preventing the mixture from flowing readily, as we
see in Jell-O. Two other important types of colloids are aerosols, which are dispersions of solid or liquid particles in a gas, and
emulsions, which are dispersions of one liquid in another liquid with which it is immiscible.
Colloids share many properties with solutions. For example, the particles in both are invisible without a powerful microscope, do
not settle on standing, and pass through most filters. However, the particles in a colloid scatter a beam of visible light, a
phenomenon known as the Tyndall effect,The effect is named after its discoverer, John Tyndall, an English physicist (1820–1893).
whereas the particles of a solution do not. The Tyndall effect is responsible for the way the beams from automobile headlights are
clearly visible from the side on a foggy night but cannot be seen from the side on a clear night. It is also responsible for the colored
rays of light seen in many sunsets, where the sun’s light is scattered by water droplets and dust particles high in the atmosphere. An
example of the Tyndall effect is shown in Figure 1.

1 [Link]
 Figure 1 : Tyndall Effect, the Scattering of Light by Colloids
Although colloids and suspensions can have particles similar in size, the two differ in stability: the particles of a colloid remain
dispersed indefinitely unless the temperature or chemical composition of the dispersing medium is changed. The chemical
explanation for the stability of colloids depends on whether the colloidal particles are hydrophilic or hydrophobic.
Most proteins, including those responsible for the properties of gelatin and glue, are hydrophilic because their exterior surface is
largely covered with polar or charged groups. Starch, a long-branched polymer of glucose molecules, is also hydrophilic. A
hydrophilic colloid particle interacts strongly with water, resulting in a shell of tightly bound water molecules that prevents the
particles from aggregating when they collide. Heating such a colloid can cause aggregation because the particles collide with
greater energy and disrupt the protective shell of solvent. Moreover, heat causes protein structures to unfold, exposing previously
buried hydrophobic groups that can now interact with other hydrophobic groups and cause the particles to aggregate and precipitate
from solution. When an egg is boiled, for example, the egg white, which is primarily a colloidal suspension of a protein called
albumin, unfolds and exposes its hydrophobic groups, which aggregate and cause the albumin to precipitate as a white solid.

Figure 2 : Sickle-Cell Anemia The characteristic shape of sickled red blood cells is the result of fibrous aggregation of hemoglobin
molecules inside the cell.
In some cases, a stable colloid can be transformed to an aggregated suspension by a minor chemical modification. Consider, for
example, the behavior of hemoglobin, a major component of red blood cells. Hemoglobin molecules normally form a colloidal
suspension inside red blood cells, which typically have a “donut” shape and are easily deformed, allowing them to squeeze through
the capillaries to deliver oxygen to tissues. In a common inherited disease called sickle-cell anemia, one of the amino acids in
hemoglobin that has a hydrophilic carboxylic acid side chain (glutamate) is replaced by another amino acid that has a hydrophobic
side chain (valine). Under some conditions, the abnormal hemoglobin molecules can aggregate to form long, rigid fibers that cause
the red blood cells to deform, adopting a characteristic sickle shape that prevents them from passing through the capillaries (Figure
2 ). The reduction in blood flow results in severe cramps, swollen joints, and liver damage. Until recently, many patients with

sickle-cell anemia died before the age of 30 from infection, blood clots, or heart or kidney failure, although individuals with the
sickle-cell genetic trait are more resistant to malaria than are those with “normal” hemoglobin.

2 [Link]
Figure 3 : Formation of New Land by the Destabilization of a Colloid Suspension. This satellite photograph shows the Mississippi
River delta from New Orleans (top) to the Gulf of Mexico (bottom). Where seawater mixes with freshwater from the Mississippi
River, colloidal clay particles in the river water precipitate (tan area).
Aggregation and precipitation can also result when the outer, charged layer of a particle is neutralized by ions with the opposite
charge. In inland waterways, clay particles, which have a charged surface, form a colloidal suspension. High salt concentrations in
seawater neutralize the charge on the particles, causing them to precipitate and form land at the mouths of large rivers, as seen in
the satellite view in Figure 3. Charge neutralization is also an important strategy for precipitating solid particles from gaseous
colloids such as smoke, and it is widely used to reduce particulate emissions from power plants that burn fossil fuels.

Emulsions
Emulsions are colloids formed by the dispersion of a hydrophobic liquid in water, thereby bringing two mutually insoluble liquids,
such as oil and water, in close contact. Various agents have been developed to stabilize emulsions, the most successful being
molecules that combine a relatively long hydrophobic “tail” with a hydrophilic “head”:

Examples of such emulsifying agents include soaps, which are salts of long-chain carboxylic acids, such as sodium stearate
CO − Na ] , and detergents, such as sodium dodecyl sulfate [ CH (CH ) OSO − Na ] , whose structures are as
+ +
[ CH (CH )
3 2 16 2 3 2 11 3

follows:

When you wash your laundry, the hydrophobic tails of soaps and detergents interact with hydrophobic particles of dirt or grease
through dispersion forces, dissolving in the interior of the hydrophobic particle. The hydrophilic group is then exposed at the
surface of the particle, which enables it to interact with water through ion–dipole forces and hydrogen bonding. This causes the

3 [Link]
particles of dirt or grease to disperse in the wash water and allows them to be removed by rinsing. Similar agents are used in the
food industry to stabilize emulsions such as mayonnaise.
A related mechanism allows us to absorb and digest the fats in buttered popcorn and French fries. To solubilize the fats so that they
can be absorbed, the gall bladder secretes a fluid called bile into the small intestine. Bile contains a variety of bile salts, detergent-
like molecules that emulsify the fats.

Micelles
Detergents and soaps are surprisingly soluble in water in spite of their hydrophobic tails. The reason for their solubility is that they
do not, in fact, form simple solutions. Instead, above a certain concentration they spontaneously form micelles, which are spherical
or cylindrical aggregates that minimize contact between the hydrophobic tails and water. In a micelle, only the hydrophilic heads
are in direct contact with water, and the hydrophobic tails are in the interior of the aggregate (Figure 4a).

Figure 4 : Micelles and a Phospholipid Bilayer. (a) Soaps and detergents, which contain a single hydrophobic tail on each
molecule, form spherical micelles with the intertwined tails in the interior and the hydrophilic head groups on the exterior. (b)
Phospholipids, which have two hydrophobic tails, tend to form extended double layers in which the hydrophobic tails are
sandwiched between the hydrophilic head groups.
A large class of biological molecules called phospholipids consists of detergent-like molecules with a hydrophilic head and two
hydrophobic tails, as can be seen in the molecule of phosphatidylcholine. The additional tail results in a cylindrical shape that
prevents phospholipids from forming a spherical micelle. Consequently, phospholipids form bilayers, extended sheets consisting of
a double layer of molecules. As shown in Figure 4b, the hydrophobic tails are in the center of the bilayer, where they are not in
contact with water, and the hydrophilic heads are on the two surfaces, in contact with the surrounding aqueous solution.

A cell membrane is essentially a mixture of phospholipids that form a phospholipid bilayer. One definition of a cell is a collection
of molecules surrounded by a phospholipid bilayer that is capable of reproducing itself. The simplest cells are bacteria, which
consist of only a single compartment surrounded by a single membrane. Animal and plant cells are much more complex, however,
and contain many different kinds of compartments, each surrounded by a membrane and able to carry out specialized tasks.

4 [Link]
Summary
A suspension is a heterogeneous mixture of particles of one substance distributed throughout a second phase; the dispersed
particles separate from the dispersing phase on standing. In contrast, the particles in a colloid are smaller and do not separate on
standing. A colloid can be classified as a sol, a dispersion of solid particles in a liquid or solid; a gel, a semisolid sol in which all of
the liquid phase has been absorbed by the solid particles; an aerosol, a dispersion of solid or liquid particles in a gas; or an
emulsion, a dispersion of one liquid phase in another. A colloid can be distinguished from a true solution by its ability to scatter a
beam of light, known as the Tyndall effect. Hydrophilic colloids contain an outer shell of groups that interact favorably with water,
whereas hydrophobic colloids have an outer surface with little affinity for water. Emulsions are prepared by dispersing a
hydrophobic liquid in water. In the absence of a dispersed hydrophobic liquid phase, solutions of detergents in water form
organized spherical aggregates called micelles. Phospholipids are a class of detergent-like molecules that have two hydrophobic
tails attached to a hydrophilic head. A bilayer is a two-dimensional sheet consisting of a double layer of phospholipid molecules
arranged tail to tail with a hydrophobic interior and a hydrophilic exterior. Cells are collections of molecules that are surrounded by
a phospholipid bilayer called a cell membrane and are able to reproduce themselves.

4.11 Suspensions and Colloids is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

5 [Link]
4.12 Practice Problems
4.12 Practice Problems is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1 [Link]
Intermolecular Forces

Intermolecular Forces is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1 [Link]
 CHAPTER OVERVIEW

5: The Numbers Game - Solutions and Stoichiometry

5.1 Expressing Solution Concentration
5.2 Types of Aqueous Solutions and Solubility
5.3 Colligative Properties and Freezing Point Depression and Boiling Point Elevation and Osmosis
5.4 Writing and Balancing Chemical Equations
5.4a Example How Much Carbon Dioxide
5.5 Limiting Reactant and Theoretical Yield and Percent Yield
5.6 Representing Aqueous Reactions Molecular and Ionic and Complete Ionic Equations
5.7 Chemical Reactions and Aqueous Reactions (Exercises)

5: The Numbers Game - Solutions and Stoichiometry is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

1
5.1 Expressing Solution Concentration
Skills to Develop
To describe the concentrations of solutions quantitatively
To describe the concentration of a solution in the way that is most appropriate for a particular problem or application.
To be familiar with the different units used to express the concentrations of a solution.

Many people have a qualitative idea of what is meant by concentration. Anyone who has made instant coffee or lemonade knows
that too much powder gives a strongly flavored, highly concentrated drink, whereas too little results in a dilute solution that may be
hard to distinguish from water. In chemistry, the concentration of a solution is the quantity of a solute that is contained in a
particular quantity of solvent or solution. Knowing the concentration of solutes is important in controlling the stoichiometry of
reactants for solution reactions. Chemists use many different methods to define concentrations, some of which are described in this
section.

Molarity
The most common unit of concentration is molarity, which is also the most useful for calculations involving the stoichiometry of
reactions in solution. The molarity (M) is defined as the number of moles of solute present in exactly 1 L of solution. It is,
equivalently, the number of millimoles of solute present in exactly 1 mL of solution:
moles of solute mmoles of solute
molarity = = (1)
liters of solution milliliters of solution

The units of molarity are therefore moles per liter of solution (mol/L), abbreviated as M . An aqueous solution that contains 1 mol
(342 g) of sucrose in enough water to give a final volume of 1.00 L has a sucrose concentration of 1.00 mol/L or 1.00 M. In
chemical notation, square brackets around the name or formula of the solute represent the molar concentration of a solute.
Therefore,
[sucrose] = 1.00 M (2)

is read as “the concentration of sucrose is 1.00 molar.” The relationships between volume, molarity, and moles may be expressed as
either

mol
VL x Mmol/L = L ( ) = moles (3)
L

or

mmol
VmL x Mmmol/mL = mL ( ) = mmoles (4)
mL

Figure 1 illustrates the use of Equations 3 and 4.

Figure 1 : Preparation of a Solution of Known Concentration Using a Solid Solute

1 [Link]
 Example 1 : Calculating Moles from Concentration of NaOH
Calculate the number of moles of sodium hydroxide (NaOH) in 2.50 L of 0.100 M NaOH.
Given: identity of solute and volume and molarity of solution
Asked for: amount of solute in moles
Strategy:
Use either Equation 3 or Equation 4, depending on the units given in the problem.
Solution:
Because we are given the volume of the solution in liters and are asked for the number of moles of substance, Equation 3 is
more useful:

0.100 mol
moles N aOH = VL x Mmol/L = (2.50 L )( ) = 0.250 mol N aOH
L

Exercise 1 : Calculating Moles from Concentration of Alanine

Calculate the number of millimoles of alanine, a biologically important molecule, in 27.2 mL of 1.53 M alanine.

Answer
41.6 mmol

The Preparation of Solutions

To prepare a solution that contains a specified concentration of a substance, it is necessary to dissolve the desired number of moles
of solute in enough solvent to give the desired final volume of solution. Figure 1 illustrates this procedure for a solution of
cobalt(II) chloride dihydrate in ethanol. Note that the volume of the solvent is not specified. Because the solute occupies space in
the solution, the volume of the solvent needed is almost always less than the desired volume of solution. For example, if the desired
volume were 1.00 L, it would be incorrect to add 1.00 L of water to 342 g of sucrose because that would produce more than 1.00 L
of solution. As shown in Figure 2, for some substances this effect can be significant, especially for concentrated solutions.

Figure 2 : Preparation of 250 mL of a Solution of (NH4)2Cr2O7 in Water. The solute occupies space in the solution, so less than
250 mL of water are needed to make 250 mL of solution.

Example 2
The solution contains 10.0 g of cobalt(II) chloride dihydrate, CoCl2•2H2O, in enough ethanol to make exactly 500 mL of
solution. What is the molar concentration of CoCl ∙ 2 H O ?
2 2

Given: mass of solute and volume of solution

Asked for: concentration (M)

2 [Link]
 Strategy:
To find the number of moles of CoCl ∙ 2 H O , divide the mass of the compound by its molar mass. Calculate the molarity of
2 2

the solution by dividing the number of moles of solute by the volume of the solution in liters.
Solution:
The molar mass of CoCl2•2H2O is 165.87 g/mol. Therefore,
10.0 g
moles C oC l2 ⋅ 2 H2 O = ( ) = 0.0603 mol
165.87 g /mol

The volume of the solution in liters is

1 L
volume = 500 mL ( ) = 0.500 L
1000 mL

Molarity is the number of moles of solute per liter of solution, so the molarity of the solution is
0.0603 mol
molarity = = 0.121 M = C oC l2 ⋅ H2 O
0.500 L

Exercise 2
The solution shown in Figure 2 contains 90.0 g of (NH4)2Cr2O7 in enough water to give a final volume of exactly 250 mL.
What is the molar concentration of ammonium dichromate?

Answer
(N H4 )2 C r2 O7 = 1.43 M

To prepare a particular volume of a solution that contains a specified concentration of a solute, we first need to calculate the
number of moles of solute in the desired volume of solution using the relationship shown in Equation 3. We then convert the
number of moles of solute to the corresponding mass of solute needed. This procedure is illustrated in Example 3.

Example 3 : D5W Solution

The so-called D5W solution used for the intravenous replacement of body fluids contains 0.310 M glucose. (D5W is an
approximately 5% solution of dextrose [the medical name for glucose] in water.) Calculate the mass of glucose necessary to
prepare a 500 mL pouch of D5W. Glucose has a molar mass of 180.16 g/mol.
Given: molarity, volume, and molar mass of solute
Asked for: mass of solute
Strategy:
A. Calculate the number of moles of glucose contained in the specified volume of solution by multiplying the volume of the
solution by its molarity.
B. Obtain the mass of glucose needed by multiplying the number of moles of the compound by its molar mass.
Solution:
A We must first calculate the number of moles of glucose contained in 500 mL of a 0.310 M solution:
VL Mmol/L = moles

1 L 0.310 mol glucose

500 mL ( )( ) = 0.155 mol glucose
1000 mL 1 L

B We then convert the number of moles of glucose to the required mass of glucose:

3 [Link]
 ⎛ 180.16 g glucose ⎞
mass of glucose = 0.155 mol glucose = 27.9 g glucose
⎝ 1 mol glucose ⎠

Exercise 3
Another solution commonly used for intravenous injections is normal saline, a 0.16 M solution of sodium chloride in water.
Calculate the mass of sodium chloride needed to prepare 250 mL of normal saline solution.

Answer
2.3 g NaCl

Dilution
A solution of a desired concentration can also be prepared by diluting a small volume of a more concentrated solution with
additional solvent. A stock solution is a commercially prepared solution of known concentration and is often used for this purpose.
Diluting a stock solution is preferred because the alternative method, weighing out tiny amounts of solute, is difficult to carry out
with a high degree of accuracy. Dilution is also used to prepare solutions from substances that are sold as concentrated aqueous
solutions, such as strong acids.
The procedure for preparing a solution of known concentration from a stock solution is shown in Figure 3. It requires calculating
the number of moles of solute desired in the final volume of the more dilute solution and then calculating the volume of the stock
solution that contains this amount of solute. Remember that diluting a given quantity of stock solution with solvent does not change
the number of moles of solute present. The relationship between the volume and concentration of the stock solution and the volume
and concentration of the desired diluted solution is therefore
(Vs )(Ms ) = moles of solute = (Vd )(Md ) (5)

where the subscripts s and d indicate the concentrated stock solution and the desired dilute solution, respectively. Example 4

demonstrates the calculations involved in diluting a concentrated stock solution.

Figure 3 : Preparation of a Solution of Known Concentration by Diluting a Stock Solution. (a) A volume (Vs) containing the
desired moles of solute (Ms) is measured from a stock solution of known concentration. (b) The measured volume of stock solution
is transferred to a second volumetric flask. (c) The measured volume in the second flask is then diluted with solvent up to the
volumetric mark [(Vs)(Ms) = (Vd)(Md)].

Example 4
What volume of a 3.00 M glucose stock solution is necessary to prepare 2500 mL of the D5W solution in Example 3?

4 [Link]
 Given: volume and molarity of dilute solution
Asked for: volume of stock solution
Strategy:
A. Calculate the number of moles of glucose contained in the indicated volume of dilute solution by multiplying the volume of
the solution by its molarity.
B. To determine the volume of stock solution needed, divide the number of moles of glucose by the molarity of the stock
solution.
Solution:
A The D5W solution in Example 4.5.3 was 0.310 M glucose. We begin by using Equation 4.5.4 to calculate the number of
moles of glucose contained in 2500 mL of the solution:

1 L 0.310 mol glucose

moles glucose = 2500 mL ( )( ) = 0.775 mol glucose (6)
1000 mL 1 L

B We must now determine the volume of the 3.00 M stock solution that contains this amount of glucose:

⎛ 1 L ⎞
volume of stock soln = 0.775 mol glucose = 0.258 L or 258 mL (7)
⎝ 3.00 mol glucose ⎠

In determining the volume of stock solution that was needed, we had to divide the desired number of moles of glucose by the
concentration of the stock solution to obtain the appropriate units. Also, the number of moles of solute in 258 mL of the stock
solution is the same as the number of moles in 2500 mL of the more dilute solution; only the amount of solvent has changed.
The answer we obtained makes sense: diluting the stock solution about tenfold increases its volume by about a factor of 10 (258
mL → 2500 mL). Consequently, the concentration of the solute must decrease by about a factor of 10, as it does (3.00 M →
0.310 M).
We could also have solved this problem in a single step by solving Equation 4.5.4 for Vs and substituting the appropriate values:

(Vd )(Md ) (2.500 L)(0.310 M )

Vs = = = 0.258 L (8)
Ms 3.00 M

As we have noted, there is often more than one correct way to solve a problem.

Exercise 4
What volume of a 5.0 M NaCl stock solution is necessary to prepare 500 mL of normal saline solution (0.16 M NaCl)?

Answer
16 mL

Ion Concentrations in Solution

In Example 2, the concentration of a solution containing 90.00 g of ammonium dichromate in a final volume of 250 mL were
calculated to be 1.43 M. Let’s consider in more detail exactly what that means. Ammonium dichromate is an ionic compound that
contains two NH4+ ions and one Cr2O72− ion per formula unit. Like other many ionic compounds, it is a strong electrolyte that
dissociates in aqueous solution to give hydrated NH4+ and Cr2O72− ions:
H2 O(l)
+ 2−
(N H4 )2 C r2 O7 (s) −−−−→ 2N H (aq) + C r2 O (aq) (9)
4 7

Thus 1 mol of ammonium dichromate formula units dissolves in water to produce 1 mol of Cr2O72− anions and 2 mol of NH4+
cations (see Figure 4).

5 [Link]
 Figure 4 : Dissolution of 1 mol of an Ionic Compound. In this case, dissolving 1 mol of (NH4)2Cr2O7 produces a solution that
contains 1 mol of Cr2O72− ions and 2 mol of NH4+ ions. (Water molecules are omitted from a molecular view of the solution for
clarity.)
When carrying out a chemical reaction using a solution of a salt such as ammonium dichromate, it is important to know the
concentration of each ion present in the solution. If a solution contains 1.43 M (NH4)2Cr2O7, then the concentration of Cr2O72−
must also be 1.43 M because there is one Cr2O72− ion per formula unit. However, there are two NH4+ ions per formula unit, so the
concentration of NH4+ ions is 2 × 1.43 M = 2.86 M. Because each formula unit of (NH4)2Cr2O7 produces three ions when
dissolved in water (2NH4+ + 1Cr2O72−), the total concentration of ions in the solution is 3 × 1.43 M = 4.29 M.

Example 5
What are the concentrations of all species derived from the solutes in these aqueous solutions?
a. 0.21 M NaOH
b. 3.7 M (CH3)2CHOH
c. 0.032 M In(NO3)3
Given: molarity
Asked for: concentrations
Strategy:
A Classify each compound as either a strong electrolyte or a nonelectrolyte.
B If the compound is a nonelectrolyte, its concentration is the same as the molarity of the solution. If the compound is a strong
electrolyte, determine the number of each ion contained in one formula unit. Find the concentration of each species by
multiplying the number of each ion by the molarity of the solution.
Solution:
1. Sodium hydroxide is an ionic compound that is a strong electrolyte (and a strong base) in aqueous solution:
H2 O(l)
+ −
N aOH (s) −−−−→ Na (aq) + OH (aq)

B Because each formula unit of NaOH produces one Na+ ion and one OH− ion, the concentration of each ion is the same as
the concentration of NaOH: [Na+] = 0.21 M and [OH−] = 0.21 M.
2. A The formula (CH3)2CHOH represents 2-propanol (isopropyl alcohol) and contains the –OH group, so it is an alcohol.
Recall from Section 4.1 that alcohols are covalent compounds that dissolve in water to give solutions of neutral molecules.
Thus alcohols are nonelectrolytes.
B The only solute species in solution is therefore (CH3)2CHOH molecules, so [(CH3)2CHOH] = 3.7 M.
3. A Indium nitrate is an ionic compound that contains In3+ ions and NO3− ions, so we expect it to behave like a strong
electrolyte in aqueous solution:
H2 O(l)
3+ −
I n(N O3 )3 (s) −−−−→ In (aq) + 3N O (aq)
3

6 [Link]
 B One formula unit of In(NO3)3 produces one In3+ ion and three NO3− ions, so a 0.032 M In(NO3)3 solution contains 0.032
M In3+ and 3 × 0.032 M = 0.096 M NO3–—that is, [In3+] = 0.032 M and [NO3−] = 0.096 M.

Exercise 5
What are the concentrations of all species derived from the solutes in these aqueous solutions?
a. 0.0012 M Ba(OH)2
b. 0.17 M Na2SO4
c. 0.50 M (CH3)2CO, commonly known as acetone

Answer a
2+ −
[Ba ] = 0.0012 M ; [OH ] = 0.0024 M

Answer b
+ 2−
[N a ] = 0.34 M ; [S O ] = 0.17 M
4

Answer c
[(C H3 )2 C O] = 0.50 M

Other Concentration Units

There are several different ways to quantitatively describe the concentration of a solution. For example, mole fraction,
moles solute
, is used not only to describe gas concentrations but also to determine the vapor pressures of
total moles of all components

mixtures of similar liquids. Example 6 shows the methods for calculating the molarity and mole fraction of a solution when the
masses of its components are known.

Example 6 : Molarity and Mole Fraction

Commercial vinegar is essentially a solution of acetic acid in water. A bottle of vinegar has 3.78 g of acetic acid per 100.0 g of
solution. Assume that the density of the solution is 1.00 g/mL.
a. What is its molarity?
b. What is its mole fraction?
Given: mass of substance and mass and density of solution
Asked for: molarity and mole fraction
Strategy:
A. Calculate the number of moles of acetic acid in the sample. Then calculate the number of liters of solution from its mass and
density. Use these results to determine the molarity of the solution.
B. Determine the mass of the water in the sample and calculate the number of moles of water. Then determine the mole fraction
of acetic acid by dividing the number of moles of acetic acid by the total number of moles of substances in the sample.
Solution:
A The molarity is the number of moles of acetic acid per liter of solution. We can calculate the number of moles of acetic acid as
its mass divided by its molar mass. The volume of the solution equals its mass divided by its density. The calculations follow:
3.78 g C H3 C O2 H
moles CH CO H = = 0.0629 mol
3 2
60.05 g /mol

7 [Link]
 100.0 g solution
mass
volume = = = 100 mL
density 1.00 g /mL

moles CH CO H
3 2
molarity of CH CO H =
3 2
liter solution

0.0629 mol CH CO H
3 2
= = 0.629 M CH CO H
3 2
(100 mL )(1 L/1000 mL )

This result makes intuitive sense. If 100.0 g of aqueous solution (equal to 100 mL) contains 3.78 g of acetic acid, then 1 L of
solution will contain 37.8 g of acetic acid, which is a little more than mole. Keep in mind, though, that the mass and volume
1

of a solution are related by its density; concentrated aqueous solutions often have densities greater than 1.00 g/mL.
B To calculate the mole fraction of acetic acid in the solution, we need to know the number of moles of both acetic acid and
water. The number of moles of acetic acid is 0.0629 mol, as calculated in part (a). We know that 100.0 g of vinegar contains
3.78 g of acetic acid; hence the solution also contains (100.0 g − 3.78 g) = 96.2 g of water. We have
96.2 g H O
2
moles H O = = 5.34 mol H O
2 2
18.02 g /mol

The mole fraction χ of acetic acid is the ratio of the number of moles of acetic acid to the total number of moles of substances
present:
moles CH CO H
3 2
χCH CO H =
3 2
moles CH CO H + moles H O
3 2 2

0.0629 mol
=
0.0629 mol + 5.34 mol

−2
= 0.0116 = 1.16 × 10

This answer makes sense, too. There are approximately 100 times as many moles of water as moles of acetic acid, so the ratio
should be approximately 0.01.

Exercise 6 : Molarity and Mole Fraction

A solution of HCl gas dissolved in water (sold commercially as “muriatic acid,” a solution used to clean masonry surfaces) has
20.22 g of HCl per 100.0 g of solution, and its density is 1.10 g/mL.
a. What is its molarity?
b. What is its mole fraction?

Answer a
6.10 M HCl
Answer b
χH C l = 0.111

The concentration of a solution can also be described by its molality (m), the number of moles of solute per kilogram of solvent:
moles solute
molality (m) = (10)
kilogram solvent

Molality, therefore, has the same numerator as molarity (the number of moles of solute) but a different denominator (kilogram of
solvent rather than liter of solution). For dilute aqueous solutions, the molality and molarity are nearly the same because dilute
solutions are mostly solvent. Thus because the density of water under standard conditions is very close to 1.0 g/mL, the volume of
1.0 kg of H O under these conditions is very close to 1.0 L, and a 0.50 M solution of KBr in water, for example, has
2

approximately the same concentration as a 0.50 m solution.

8 [Link]
Another common way of describing concentration is as the ratio of the mass of the solute to the total mass of the solution. The
result can be expressed as percent by mass, parts per million (ppm), or parts per billion (ppb):
mass of solute
percent by mass = × 100 (11)
mass of solution

mass of solute
6
parts per million (ppm) = × 10 (12)
mass of solution

mass of solute 9
parts per billion (ppb) = × 10 (13)
mass of solution

In the health sciences, the concentration of a solution is often expressed as parts per thousand (ppt), indicated as a proportion. For
example, adrenalin, the hormone produced in high-stress situations, is available in a 1:1000 solution, or one gram of adrenalin per
1000 g of solution.
The labels on bottles of commercial reagents often describe the contents in terms of mass percentage. Sulfuric acid, for example, is
sold as a 95% aqueous solution, or 95 g of H SO per 100 g of solution. Parts per million and parts per billion are used to describe
2 4

concentrations of highly dilute solutions. These measurements correspond to milligrams and micrograms of solute per kilogram of
solution, respectively. For dilute aqueous solutions, this is equal to milligrams and micrograms of solute per liter of solution
(assuming a density of 1.0 g/mL).

Example 7 : Molarity and Mass

Several years ago, millions of bottles of mineral water were contaminated with benzene at ppm levels. This incident received a
great deal of attention because the lethal concentration of benzene in rats is 3.8 ppm. A 250 mL sample of mineral water has
12.7 ppm of benzene. Because the contaminated mineral water is a very dilute aqueous solution, we can assume that its density
is approximately 1.00 g/mL.
a. What is the molarity of the solution?
b. What is the mass of benzene in the sample?
Given: volume of sample, solute concentration, and density of solution
Asked for: molarity of solute and mass of solute in 250 mL
Strategy:
A. Use the concentration of the solute in parts per million to calculate the molarity.
B. Use the concentration of the solute in parts per million to calculate the mass of the solute in the specified volume of solution.
Solution:
a. A To calculate the molarity of benzene, we need to determine the number of moles of benzene in 1 L of solution. We know
that the solution contains 12.7 ppm of benzene. Because 12.7 ppm is equivalent to 12.7 mg/1000 g of solution and the density of
the solution is 1.00 g/mL, the solution contains 12.7 mg of benzene per liter (1000 mL). The molarity is therefore
moles
molarity =
liter solution

1 g
1 mol
(12.7 mg ) ( )( )
1000 mg 78.114 g

=
1.00 L

−4
= 1.63 × 10 M

b. B We are given that there are 12.7 mg of benzene per 1000 g of solution, which is equal to 12.7 mg/L of solution. Hence the
mass of benzene in 250 mL (250 g) of solution is

(12.7 mg benzene)(250 mL )
mass of benzene =
1000 mL

= 3.18 mg

−3
= 3.18 × 10 g benzene

9 [Link]
 Exercise 7 : Molarity of Lead Solution
The maximum allowable concentration of lead in drinking water is 9.0 ppb.
a. What is the molarity of Pb in a 9.0 ppb aqueous solution?
2 +

b. Use your calculated concentration to determine how many grams of Pb 2 +

are in an 8 oz glass of water.

Answer a
4.3 × 10−8 M
Answer b
2 × 10−6 g

Concentrations are also often reported on a mass-to-volume (m/v) basis, particularly in clinical laboratories and engineering
applications. A concentration expressed on an m/v basis is the number of grams of solute per milliliter of solution. Each
measurement can be expressed as a percentage by multiplying the ratio by 100; the result is reported as percent m/v. Even though
reported on a mass-to-volume basis, the concentrations of very dilute solutions are often expressed in parts per million (ppm) or in
parts per billion (ppb). For aqueous solutions at 20°C, 1 ppm corresponds to 1 μg per milliliter, and 1 ppb corresponds to 1 ng per
milliliter.
How do chemists decide which units of concentration to use for a particular application? Although molarity is commonly used to
express concentrations for reactions in solution or for titrations, it does have one drawback—molarity is the number of moles of
solute divided by the volume of the solution, and the volume of a solution depends on its density, which is a function of
temperature. Because volumetric glassware is calibrated at a particular temperature, typically 20°C, the molarity may differ from
the original value by several percent if a solution is prepared or used at a significantly different temperature, such as 40°C or 0°C.
For many applications this may not be a problem, but for precise work these errors can become important. In contrast, mole
fraction, molality, and mass percentage depend on only the masses of the solute and solvent, which are independent of temperature.
Mole fraction is not very useful for experiments that involve quantitative reactions, but it is convenient for calculating the partial
pressure of gases in mixtures, as discussed previously. Mole fractions are also useful for calculating the vapor pressures of certain
types of solutions. Molality is particularly useful for determining how properties such as the freezing or boiling point of a solution
vary with solute concentration. Because mass percentage and parts per million or billion are simply different ways of expressing
the ratio of the mass of a solute to the mass of the solution, they enable us to express the concentration of a substance even when
the molecular mass of the substance is unknown. Units of ppb or ppm are also used to express very low concentrations, such as
those of residual impurities in foods or of pollutants in environmental studies.
Table 1 summarizes the different units of concentration and typical applications for each. When the molar mass of the solute and
the density of the solution are known, it becomes relatively easy with practice to convert among the units of concentration we have
discussed, as illustrated in Example 8.
Table 1 : Different Units for Expressing the Concentrations of Solutions*
Unit Definition Application

Used for quantitative reactions in solution and

molarity (M) moles of solute/liter of solution (mol/L) titrations; mass and molecular mass of solute
and volume of solution are known.
Used for partial pressures of gases and vapor
mole fraction (χ) moles of solute/total moles present (mol/mol) pressures of some solutions; mass and
molecular mass of each component are known.
Used in determining how colligative properties
molality (m) moles of solute/kg of solvent (mol/kg) vary with solute concentration; masses and
molecular mass of solute are known.
Useful when masses are known but molecular
percent by mass (%) [mass of solute (g)/mass of solution (g)] × 100
masses are unknown.

*The molarity of a solution is temperature dependent, but the other units shown in this table are independent of temperature.

10 [Link]
 Unit Definition Application

Used in the health sciences, ratio solutions are

[mass of solute/mass of solution] × 103 (g
parts per thousand (ppt) typically expressed as a proportion, such as
solute/kg solution)
1:1000.

[mass of solute/mass of solution] × 106 (mg Used for trace quantities; masses are known
parts per million (ppm)
solute/kg solution) but molecular masses may be unknown.

[mass of solute/mass of solution] × 109 (µg Used for trace quantities; masses are known
parts per billion (ppb)
solute/kg solution) but molecular masses may be unknown.

*The molarity of a solution is temperature dependent, but the other units shown in this table are independent of temperature.

Example 8 : Vodka
Vodka is essentially a solution of ethanol in water. Typical vodka is sold as “80 proof,” which means that it contains 40.0%
ethanol by volume. The density of pure ethanol is 0.789 g/mL at 20°C. If we assume that the volume of the solution is the sum
of the volumes of the components (which is not strictly correct), calculate the following for the ethanol in 80-proof vodka.
a. the percent by mass
b. the mole fraction
c. the molarity
d. the molality
Given: volume percent and density
Asked for: percent by mass, mole fraction, molarity, and molality
Strategy:
A. Use the density of the solute to calculate the mass of the solute in 100.0 mL of solution. Calculate the mass of water in 100.0
mL of solution.
B. Determine the percent by mass of solute by dividing the mass of ethanol by the mass of the solution and multiplying by 100.
C. Convert grams of solute and solvent to moles of solute and solvent. Calculate the mole fraction of solute by dividing the
moles of solute by the total number of moles of substances present in solution.
D. Calculate the molarity of the solution: moles of solute per liter of solution. Determine the molality of the solution by
dividing the number of moles of solute by the kilograms of solvent.
Solution:
The key to this problem is to use the density of pure ethanol to determine the mass of ethanol (C H C H OH), abbreviated as
3 2

EtOH, in a given volume of solution. We can then calculate the number of moles of ethanol and the concentration of ethanol in
any of the required units. A Because we are given a percentage by volume, we assume that we have 100.0 mL of solution. The
volume of ethanol will thus be 40.0% of 100.0 mL, or 40.0 mL of ethanol, and the volume of water will be 60.0% of 100.0 mL,
or 60.0 mL of water. The mass of ethanol is obtained from its density:

0.789 g
mass of EtOH = (40.0 mL ) ( ) = 31.6 g EtOH
mL

If we assume the density of water is 1.00 g/mL, the mass of water is 60.0 g. We now have all the information we need to
calculate the concentration of ethanol in the solution.
B The percent by mass of ethanol is the ratio of the mass of ethanol to the total mass of the solution, expressed as a percentage:
mass of EtOH
%EtOH = ( ) (100)
mass of solution

31.6 g EtOH
=( ) (100)
31.6 g EtOH + 60.0 g H2 O

= 34.5%

11 [Link]
C The mole fraction of ethanol is the ratio of the number of moles of ethanol to the total number of moles of substances in the
solution. Because 40.0 mL of ethanol has a mass of 31.6 g, we can use the molar mass of ethanol (46.07 g/mol) to determine the
number of moles of ethanol in 40.0 mL:

⎛ 1 mol ⎞
moles CH CH OH = (31.6 g CH CH OH )
3 2 3 2
⎝ 46.07 g CH CH OH ⎠
3 2

= 0.686 mol CH CH OH
3 2

Similarly, the number of moles of water is

⎛ 1 mol H O ⎞
2
moles H O = (60.0 g H O )⎜ ⎟ = 3.33 mol H2 O
2 2
⎝ 18.02 g H O ⎠
2

The mole fraction of ethanol is thus

0.686 mol
χCH CH OH = = 0.171
3 2

0.686 mol + 3.33 mol

D The molarity of the solution is the number of moles of ethanol per liter of solution. We already know the number of moles of
ethanol per 100.0 mL of solution, so the molarity is

0.686 mol 1000 mL

MCH CH OH =( )( ) = 6.86 M
3 2
L
100 mL

The molality of the solution is the number of moles of ethanol per kilogram of solvent. Because we know the number of moles
of ethanol in 60.0 g of water, the calculation is again straightforward:

0.686 mol EtOH 1000 g 11.4 mol EtOH

mCH CH2 OH
=( )( ) = = 11.4 m
3
60.0 g H2 O kg kg H2 O

Exercise 8 : Toluene/Benzene Solution

A solution is prepared by mixing 100.0 mL of toluene with 300.0 mL of benzene. The densities of toluene and benzene are
0.867 g/mL and 0.874 g/mL, respectively. Assume that the volume of the solution is the sum of the volumes of the components.
Calculate the following for toluene.
a. percent by mass
b. mole fraction
c. molarity
d. molality

Answer a
percent by mass toluene = 24.8%
Answer b
χtoluene = 0.219

Answer c
2.35 M toluene
Answer d
3.59 m toluene

12 [Link]
Summary
The concentration of a substance is the quantity of solute present in a given quantity of solution.
Different units are used to express the concentrations of a solution depending on the application. The concentration of a solution is
the quantity of solute in a given quantity of solution. It can be expressed in several ways: molarity, moles of solute per liter of
solution; mole fraction, the ratio of the number of moles of solute to the total number of moles of substances present; percent by
mass, the ratio of the mass of the solute to the mass of the solution times 100; parts per thousand (ppt), grams of solute per
kilogram of solution; parts per million (ppm), milligrams of solute per kilogram of solution; parts per billion (ppb), micrograms
of solute per kilogram of solution; and molality (m), the number of moles of solute per kilogram of solvent.
Solution concentrations are typically expressed in terms of molarity and can be prepared by dissolving a known mass of solute in a
solvent or diluting a stock solution.
definition of molarity:
moles of solute mmoles of solute
molarity = = (14)
liters of solution milliliters of solution

relationship among volume, molarity, and moles:

mol
VL x Mmol/L = L ( ) = moles (15)
L

relationship between volume and concentration of stock and dilute solutions:

(Vs )(Ms ) = moles of solute = (Vd )(Md ) (16)

Contributors
Modified by Joshua Halpern (Howard University)
Modified by Tom Neils (Grand Rapids Community College)

5.1 Expressing Solution Concentration is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

13 [Link]
5.2 Types of Aqueous Solutions and Solubility
When an ionic compound dissolves in water, the positive and negative ions originally present in the crystal lattice persist in
solution. Their ability to move nearly independently through the solution permits them to carry positive or negative electrical
charges from one place to another. Hence the solution conducts an electrical current.

Electrolytes
Substances whose solutions conduct electricity are called electrolytes. All soluble ionic compounds are strong electrolytes. They
conduct very well because they provide a plentiful supply of ions in solution. An example of an ionically-bonded compound that is
a strong electrolyte is NaCl:
+ −
N aC l(s) → N a Cl (1)
(aq) (aq)

Some ionically-bonded substances behave as weak electrolytes—their solutions allow only a small current flow, but it is greater
than that of the pure solvent. An example is mercury(II) chloride (seen in the Figure above). For a 100-M HgCl2 solution the meter
reading shows only about 0.2 percent as much current as for 0.10 M NaCl. When the solid dissolves only a few ions dissociate
according to the equation
+ −
H gC l2 ⇌ H gC l + Cl (2)
 
99.8% 0.2%

(The double arrows indicate that the ionization proceeds only to a limited extent and an equilibrium state is attained.)

Figure 1 : The conductivity of electrolyte solutions: (a) 0.1 M NaCl (b) 0.05 M NaCl (c) 0.1 M HgCl2. An electrolyte solution
conducts electricity because of the movement of ions in the solution (see above). The larger the concentration of ions, the better the
solutions conducts. Weak electrolytes, such as HgCl2, conduct badly because they produce few ions when dissolved (low
concentration of ions).
The effect of the concentration of ions on the electrical current flowing through a solution is illustrated in Fig. 1. Part a of the
figure shows what happens when a battery is connected through an electrical meter to two inert metal strips (electrodes) dipping in
ethanol. Each cubic decimeter of such a solution contains 0.10 mol NaCl (that is, 0.10 mol Na+ and 0.10 mol Cl–). An electrical
current is carried through the solution both by the Na+ ions moving toward the negative electrode and by the Cl- ions which are
attracted toward the positive electrode. The dial on the meter indicates the quantity of current.
Figure 1b shows that if we replace the 0.10-M NaCl solution with a 0.05-M NaCl solution, the meter reading falls to about one-half
its former value. Halving the concentration of NaCl halves the number of ions between the electrodes, and half as many ions can
only carry half as much electrical charge. Therefore the current is half as great. Because it responds in such a direct way to the
concentration of ions, conductivity of electrical current is a useful tool in the study of solutions.
Figure 1c shows that if we replace the 0.10-M NaCl solution with a 0.10-M HgCl2 solution, the meter reading falls to a small
fraction of its former value. Very few ions are formed in solution by the HgCl2. Since only 0.2 percent of the HgCl2 forms ions, the
0.10 M solution can conduct only about 0.2 percent as much current as 0.10 M NaCl.
Conductivity measurements reveal that most covalent compounds, if they dissolve in water at all, retain their original molecular
structures. Neutral molecules cannot carry electrical charges through the solution, and so no current flows. A substance whose

1 [Link]
aqueous solution conducts no better than water itself is called a nonelectrolyte. Some examples are oxygen, O2, ethanol, C2H5OH,
and sugar, C12H22O11. The process of the molecules dissolving intact is shown by an equation such as:
O2(g) ⇌ O2(aq) (3)

However, some polar covalent compounds are also strong electrolytes because they react with water to form ions. Common
examples are HCl, HBr, HI and H2SO4, all of which react with H2O to form large concentrations of ions. For HCl, the reaction is:
+ −
H C l(g) + H2 O(l) → H3 O + Cl (4)
(aq) (aq)

There are also some covalently-bonded compounds that behave as weak electrolytes. Ammonia is a common example. Only a
small fraction of ammonia molecules react with water to form ions:
− +
N H3(g) + H2 O(l) → OH +NH (5)
(aq) (4aq)

Conductivity measurements can tell us more than whether a substance is a strong, a weak, or a nonelectrolyte. Consider, for
instance, the data in Table 1 which shows the electrical current conducted through various aqueous solutions under identical
conditions. At the rather low concentration of 0.001 M, the strong electrolyte solutions conduct between 2500 and 10 000 times as
much current as pure H2O and about 10 times as much as the weak electrolytes HC2H3O2 (acetic acid) and NH3 (ammonia).
Closer examination of the data for strong electrolytes reveals that some compounds which contain H or OH groups [such as HCl or
Ba(OH)2] conduct unusually well. If these compounds are excluded, we find that 1:1 electrolytes (compounds which consist of
equal numbers of +1 ions and –1 ions) usually conduct about half as much current as 2:2 electrolytes (+2 and -2 ions), 1:2
electrolytes (+1 and -2 ions), or 2:1 electrolytes (+2 and -1 ions).
TABLE 1 : Electrical Current Conducted Through Various 0.001 M Aqueous Solutions at 18°C.*
Substance Current /mA Substance Current /mA

Pure Water 1:2 Electrolytes

-4
H2O 3.69 x 10 Na2SO4 2.134

Weak Electrolytes Na2CO3 2.24

HC2H3O2 0.41 K2CO3 2.660

NH3 0.28 2:1 Electrolytes

1:1 Electrolytes MgCl2 2.128

NaCl 1.065 CaCl2 2.239

NaI 1.069 SrCl2 2.290

KCl 1.273 BaCl2 2.312

KI 1,282 Ba(OH)2 4.14

AgNO3 1.131 2:2 Electrolytes

HCl 3.77 MgSO4 2.00

HNO3 3.75 CaSO4 2.086

NaOH 2.08 CuSO4 1.97

KOH 2.34 ZnSO4 1.97

* All measurements refer to a cel1 in which the distance between the electrodes is 1.0 mm and the area of each electrode is 1.0 cm².
A potential difference of 1.0 V is applied to produce the tabulated currents.
There is a simple reason for this behavior. Under similar conditions, most ions move through water at comparable speeds. This
means that ions like Mg2+ or SO42–, which are doubly charged, will carry twice as much current through the solution as will singly
charged ions like Na+ or Cl–. Consequently, a 0.001 M solution of a 2:2 electrolyte like MgSO4 will conduct about twice as well as
a 0.001 M solution of a 1:1 electrolyte like NaCl.

2 [Link]
A similar argument applies to solutions of 1:2 and 2:1 electrolytes. A solution like 0.001 M Na2SO4 conducts about twice as well as
0.001 M NaCl partly because there are twice as many Na– ions available to move when a battery is connected, but also because
SO42– ions carry twice as much charge as Cl– ions when moving at the same speed. These differences in conductivity between
different types of strong electrolytes can sometimes be very useful in deciding what ions are actually present in a given electrolyte
solution as the following example makes clear.
A second, slightly more subtle, conclusion can be drawn from the data in Table 1 . When an electrolyte dissolves, each type of ion
makes an independent contribution to the current the solution conducts. This can be seen by comparing NaCl with KCl, and NaI
with KI. In each case the compound containing K+ conducts about 0.2 mA more than the one containing Na+. If we apply this
observation to Na2CO3 and K2CO3, each of which produces twice as many Na+ or K+ ions in solution, we find that the difference
in current is also twice as great—about 0.4 mA.
Thus conductivity measurements confirm our statement that each ion exhibits its own characteristic properties in aqueous solutions,
independent of the presence of other ions. One such characteristic property is the quantity of electrical current that a given
concentration of a certain type of ion can carry.

Example 1 : Ions
At 18°C a 0.001-M aqueous solution of potassium hydrogen carbonate, KHCO3, conducts a current of 1.10 mA in a cell of the
same design as that used to obtain the data in Table 11.1. What ions are present in solution?
Solution
Referring to Table 6.2 which lists possible polyatomic ions, we can arrive at three possibilities for the ions from which KHCO3
is made:
a. K+ and H+ and C4+ and three O2–
b. K+ and H+ and CO32–
c. K+ and HCO3–
Since the current conducted by the solution falls in the range of 1.0 to 1.3 mA characteristic of 1:1 electrolytes, possibility c is
the only reasonable choice.

Contributors
Ed Vitz (Kutztown University), John W. Moore (UW-Madison), Justin Shorb (Hope College), Xavier Prat-Resina (University of
Minnesota Rochester), Tim Wendorff, and Adam Hahn.
Modified by Tom Neils (Grand Rapids Community College)

5.2 Types of Aqueous Solutions and Solubility is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

3 [Link]
5.3 Colligative Properties and Freezing Point Depression and Boiling Point Elevation
and Osmosis
Skills to Develop
To describe the relationship between solute concentration and the physical properties of a solution.
To understand that the total number of nonvolatile solute particles determines the decrease in vapor pressure, increase in
boiling point, and decrease in freezing point of a solution versus the pure solvent.

Many of the physical properties of solutions differ significantly from those of the pure substances discussed in earlier chapters, and
these differences have important consequences. For example, the limited temperature range of liquid water (0°C–100°C) severely
limits its use. Aqueous solutions have both a lower freezing point and a higher boiling point than pure water. Probably one of the
most familiar applications of this phenomenon is the addition of ethylene glycol (“antifreeze”) to the water in an automobile
radiator. This solute lowers the freezing point of the water, preventing the engine from cracking in very cold weather from the
expansion of pure water on freezing. Antifreeze also enables the cooling system to operate at temperatures greater than 100°C
without generating enough pressure to explode.
Changes in the freezing point and boiling point of a solution depend primarily on the number of solute particles present rather than
the kind of particles. Such properties of solutions are called colligative properties (from the Latin colligatus, meaning “bound
together” as in a quantity). As we will see, the vapor pressure and osmotic pressure of solutions are also colligative properties.
Counting concentrations
When we determine the number of particles in a solution, it is important to remember that not all solutions with the same
molarity contain the same concentration of solute particles. Consider, for example, 0.01 M aqueous solutions of sucrose, NaCl,
and CaCl . Because sucrose dissolves to give a solution of neutral molecules, the concentration of solute particles in a 0.01 M
2

sucrose solution is 0.01 M. In contrast, both NaCl and CaCl are ionic compounds that dissociate in water to yield solvated
2

ions. As a result, a 0.01 M aqueous solution of NaCl contains 0.01 M Na ions and 0.01 M Cl ions, for a total particle
+ −

concentration of 0.02 M. Similarly, the CaCl solution contains 0.01 M Ca ions and 0.02 M Cl ions, for a total particle
2
2 + −

concentration of 0.03 M. These values are correct for dilute solutions, where the dissociation of the compounds to form
separately solvated ions is complete.
At higher concentrations (typically >1 M), especially with salts of small, highly charged ions (such as Mg 2 +
or Al ), or in
3 +

solutions with less polar solvents, dissociation to give separate ions is often incomplete. The sum of the concentrations of the
dissolved solute particles dictates the physical properties of a solution. In the following discussion, we must therefore keep the
chemical nature of the solute firmly in mind.

Vapor Pressure of Solutions and Raoult’s Law

Adding a nonvolatile solute, one whose vapor pressure is too low to measure readily, to a volatile solvent decreases the vapor
pressure of the solvent. We can understand this phenomenon qualitatively by examining Figure 1, which is a schematic diagram of
the surface of a solution of glucose in water. In an aqueous solution of glucose, a portion of the surface area is occupied by
nonvolatile glucose molecules rather than by volatile water molecules. As a result, fewer water molecules can enter the vapor phase
per unit time, even though the surface water molecules have the same kinetic energy distribution as they would in pure water. At
the same time, the rate at which water molecules in the vapor phase collide with the surface and reenter the solution is unaffected.
The net effect is to shift the dynamic equilibrium between water in the vapor and the liquid phases, decreasing the vapor pressure
of the solution compared with the vapor pressure of the pure solvent.

1 [Link]
Figure 1 : A Model Depicting Why the Vapor Pressure of a Solution of Glucose Is Less Than the Vapor Pressure of Pure Water. (a)
When water or any volatile solvent is in a closed container, water molecules move into and out of the liquid phase at the same rate
in a dynamic equilibrium. (b) If a nonvolatile solute such as glucose is added, some fraction of the surface area is occupied by
solvated solute molecules. As a result, the rate at which water molecules evaporate is decreased, although initially their rate of
condensation is unchanged. (c) When the glucose solution reaches equilibrium, the concentration of water molecules in the vapor
phase, and hence the vapor pressure, is less than that of pure water.
Figure 2 shows two beakers, one containing pure water and one containing an aqueous glucose solution, in a sealed chamber. We
can view the system as having two competing equilibria: water vapor will condense in both beakers at the same rate, but water
molecules will evaporate more slowly from the glucose solution because fewer water molecules are at the surface. Eventually all of
the water will evaporate from the beaker containing the liquid with the higher vapor pressure (pure water) and condense in the
beaker containing the liquid with the lower vapor pressure (the glucose solution). If the system consisted of only a beaker of water
inside a sealed container, equilibrium between the liquid and vapor would be achieved rather rapidly, and the amount of liquid
water in the beaker would remain constant.

Figure 2 : Transfer of Water to a Beaker Containing a Glucose Solution. (top) One beaker contains an aqueous solution of glucose,
and the other contains pure water. If they are placed in a sealed chamber, the lower vapor pressure of water in the glucose solution
results in a net transfer of water from the beaker containing pure water to the beaker containing the glucose solution. (bottom)
Eventually, all of the water is transferred to the beaker that has the glucose solution.

Boiling Point Elevation

Recall that the normal boiling point of a substance is the temperature at which the vapor pressure equals 1 atm. If a nonvolatile
solute lowers the vapor pressure of a solvent, it must also affect the boiling point. Because the vapor pressure of the solution at a
given temperature is less than the vapor pressure of the pure solvent, achieving a vapor pressure of 1 atm for the solution requires a
higher temperature than the normal boiling point of the solvent. Thus the boiling point of a solution is always greater than that of
the pure solvent. We can see why this must be true by comparing the phase diagram for an aqueous solution with the phase diagram
for pure water (Figure 4). The vapor pressure of the solution is less than that of pure water at all temperatures. Consequently, the
liquid–vapor curve for the solution crosses the horizontal line corresponding to P = 1 atm at a higher temperature than does the
curve for pure water.

2 [Link]
Figure 4 : Phase Diagrams of Pure Water and an Aqueous Solution of a Nonvolatile Solute. The vaporization curve for the solution
lies below the curve for pure water at all temperatures, which results in an increase in the boiling point and a decrease in the
freezing point of the solution.

The boiling point of a solution with a nonvolatile solute is always greater than the boiling
point of the pure solvent.
The magnitude of the increase in the boiling point is related to the magnitude of the decrease in the vapor pressure. As we have just
discussed, the decrease in the vapor pressure is proportional to the concentration of the solute in the solution. Hence the magnitude
of the increase in the boiling point must also be proportional to the concentration of the solute (Figure 5).

Figure 5 : Vapor Pressure Decrease and Boiling Point Increase as Functions of the Mole Fraction of a Nonvolatile Solute
We can define the boiling point elevation (ΔT ) as the difference between the boiling points of the solution and the pure solvent:
b

0
ΔTb = Tb − T (1)
b

where T is the boiling point of the solution and

b T
b
0
is the boiling point of the pure solvent. We can express the relationship
between ΔT and concentration as follows
b

3 [Link]
 ΔTb = m Kb (2)

where m is the concentration of the solute expressed in molality, and K is the molal boiling point elevation constant of the
b

solvent, which has units of °C/m. Table 1 lists characteristic K values for several commonly used solvents. For relatively dilute
b

solutions, the magnitude of both properties is proportional to the solute concentration.

Table 1 : Boiling Point Elevation Constants (Kb) and Freezing Point Depression Constants (Kf) for Some Solvents
Solvent Boiling Point (°C) Kb (°C/m) Freezing Point (°C) Kf (°C/m)

acetic acid 117.90 3.22 16.64 3.63

benzene 80.09 2.64 5.49 5.07

d-(+)-camphor 207.4 4.91 178.8 37.8

carbon disulfide 46.2 2.42 −112.1 3.74

carbon tetrachloride 76.8 5.26 −22.62 31.4

chloroform 61.17 3.80 −63.41 4.60

nitrobenzene 210.8 5.24 5.70 6.87

water 100.00 0.51 0.00 1.86

The concentration of the solute is typically expressed as molality rather than mole fraction or molarity for two reasons. First,
because the density of a solution changes with temperature, the value of molarity also varies with temperature. If the boiling point
depends on the solute concentration, then by definition the system is not maintained at a constant temperature. Second, molality
and mole fraction are proportional for relatively dilute solutions, but molality has a larger numerical value (a mole fraction can be
only between zero and one). Using molality allows us to eliminate nonsignificant zeros.
According to Table 1, the molal boiling point elevation constant for water is 0.51°C/m. Thus a 1.00 m aqueous solution of a
nonvolatile molecular solute such as glucose or sucrose will have an increase in boiling point of 0.51°C, to give a boiling point of
100.51°C at 1.00 atm. The increase in the boiling point of a 1.00 m aqueous NaCl solution will be approximately twice as large as
that of the glucose or sucrose solution because 1 mol of NaCl produces 2 mol of dissolved ions. Hence a 1.00 m NaCl solution
will have a boiling point of about 101.02°C.

Example 3
In Example 1, we calculated that the vapor pressure of a 30.2% aqueous solution of ethylene glycol at 100°C is 85.1 mmHg less
than the vapor pressure of pure water. We stated (without offering proof) that this should result in a higher boiling point for the
solution compared with pure water. Now that we have seen why this assertion is correct, calculate the boiling point of the
aqueous ethylene glycol solution.
Given: composition of solution
Asked for: boiling point
Strategy:
Calculate the molality of ethylene glycol in the 30.2% solution. Then use Equation 2 to calculate the increase in boiling point.
Solution:
From Example 1, we know that a 30.2% solution of ethylene glycol in water contains 302 g of ethylene glycol (4.87 mol) per
698 g of water. The molality of the solution is thus
1000 g
4.87 mol
molality of ethylene glycol = ( )( ) = 6.98 m
698 g H2 O 1 kg

From Equation 2, the increase in boiling point is therefore

4 [Link]
 ΔTb = m Kb = (6.98 m )(0.51°C / m ) = 3.6°C

The boiling point of the solution is thus predicted to be 104°C. With a solute concentration of almost 7 m, however, the
assumption of a dilute solution used to obtain Equation 2 may not be valid.

Exercise 3
Assume that a tablespoon (5.00 g) of NaCl is added to 2.00 L of water at 20.0°C, which is then brought to a boil to cook
spaghetti. At what temperature will the water boil?

Answer
100.04°C, or 100°C to three significant figures. (Recall that 1 mol of NaCl produces 2 mol of dissolved particles. The small
increase in temperature means that adding salt to the water used to cook pasta has essentially no effect on the cooking time.)

Freezing Point Depression

The phase diagram in Figure 4 shows that dissolving a nonvolatile solute in water not only raises the boiling point of the water but
also lowers its freezing point. The solid–liquid curve for the solution crosses the line corresponding to P = 1 atm at a lower
temperature than the curve for pure water.
We can understand this result by imagining that we have a sample of water at the normal freezing point temperature, where there is
a dynamic equilibrium between solid and liquid. Water molecules are continuously colliding with the ice surface and entering the
solid phase at the same rate that water molecules are leaving the surface of the ice and entering the liquid phase. If we dissolve a
nonvolatile solute such as glucose in the liquid, the dissolved glucose molecules will reduce the number of collisions per unit time
between water molecules and the ice surface because some of the molecules colliding with the ice will be glucose. Glucose,
though, has a very different structure than water, and it cannot fit into the ice lattice. Consequently, the presence of glucose
molecules in the solution can only decrease the rate at which water molecules in the liquid collide with the ice surface and solidify.
Meanwhile, the rate at which the water molecules leave the surface of the ice and enter the liquid phase is unchanged. The net
effect is to cause the ice to melt. The only way to reestablish a dynamic equilibrium between solid and liquid water is to lower the
temperature of the system, which decreases the rate at which water molecules leave the surface of the ice crystals until it equals the
rate at which water molecules in the solution collide with the ice.
By analogy to our treatment of boiling point elevation,the freezing point depression (ΔT ) is defined as the difference between the
f

freezing point of the pure solvent and the freezing point of the solution:
0
ΔTf = T − Tf (3)
f

where T is the freezing point of the pure solvent and T is the freezing point of the solution.
f
0
f

The order of the terms is reversed compared with Equation 1 to express the freezing point depression as a positive number. The
relationship between ΔT and the solute concentration is given by an equation analogous to Equation 2:
f

ΔTf = m Kf (4)

where m is the molality of the solution and K is the molal freezing point depression constant for the solvent (in units of °C/m).
f

Like K , each solvent has a characteristic value of K (see Table 1). Freezing point depression depends on the total number of
b f

dissolved nonvolatile solute particles, just as with boiling point elevation. Thus an aqueous NaCl solution has twice as large a
freezing point depression as a glucose solution of the same molality.
People who live in cold climates use freezing point depression to their advantage in many ways. For example, salt is used to melt
ice and snow on roads and sidewalks, ethylene glycol is added to engine coolant water to prevent an automobile engine from being
destroyed, and methanol is added to windshield washer fluid to prevent the fluid from freezing.

The decrease in vapor pressure, increase in boiling point, and decrease in freezing point of a solution versus a pure liquid all
depend on the total number of dissolved nonvolatile solute particles.

Example 4 : Salting the Roads

5 [Link]
In colder regions of the United States, NaCl or CaCl is often sprinkled on icy roads in winter to melt the ice and make driving
2

safer. Use the data in the Figure below to estimate the concentrations of two saturated solutions at 0°C, one of NaCl and one of
CaCl , and calculate the freezing points of both solutions to see which salt is likely to be more effective at melting ice.
2

Solubilities of Several Inorganic and Organic Solids in Water as a Function of Temperature. Solubility may increase or decrease
with temperature; the magnitude of this temperature dependence varies widely among compounds.
Given: solubilities of two compounds
Asked for: concentrations and freezing points
Strategy:
A. Estimate the solubility of each salt in 100 g of water from the figure. Determine the number of moles of each in 100 g and
calculate the molalities.
B. Determine the concentrations of the dissolved salts in the solutions. Substitute these values into Equation 4 to calculate the
freezing point depressions of the solutions.
Solution:
A From Figure above, we can estimate the solubilities of NaCl and CaCl to be about 36 g and 60 g, respectively, per 100 g of
2

water at 0°C. The corresponding concentrations in molality are

⎛ 36 g N aC l ⎞ ⎛ 1 mol N aC l ⎞ 1000 g
mN aC l = ( ) = 6.2 m
⎝ 100 g H2 O ⎠ ⎝ 58.44 g N aC l ⎠ 1 kg

⎛ 60 g C aC l2 ⎞ ⎛
1 mol C aC l2 ⎞ 1000 g
mC aC l2 = ( ) = 5.4 m
⎝ 100 g H2 O ⎠ ⎝ 110.98 g C aC l2 ⎠ 1kg

The lower formula mass of NaCl more than compensates for its lower solubility, resulting in a saturated solution that has a
slightly higher concentration than C aC l .2

B Because these salts are ionic compounds that dissociate in water to yield two and three ions per formula unit of NaCl and
C aC l , respectively, the actual concentrations of the dissolved species in the two saturated solutions are 2 × 6.2 m = 12 m for
2

NaCl and 3 × 5.4 m = 16 m for C aC l . The resulting freezing point depressions can be calculated using Equation 4 :
2

N aC l : ΔTf = m Kf = (12 m )(1.86°C / m ) = 22°C

C aC l2 : ΔTf = m Kf = (16 m )(1.86°C / m ) = 30°C

Because the freezing point of pure water is 0°C, the actual freezing points of the solutions are −22°C and −30°C, respectively.
Note that C aC l is substantially more effective at lowering the freezing point of water because its solutions contain three ions
2

6 [Link]
 per formula unit. In fact, C aC l is the salt usually sold for home use, and it is also often used on highways.
2

Because the solubilities of both salts decrease with decreasing temperature, the freezing point can be depressed by only a certain
amount, regardless of how much salt is spread on an icy road. If the temperature is significantly below the minimum
temperature at which one of these salts will cause ice to melt (say −35°C), there is no point in using salt until it gets warmer

Exercise 4
Calculate the freezing point of the 30.2% solution of ethylene glycol in water whose vapor pressure and boiling point we
calculated in Examples 5 and 5.

Answer
−13.0°C

Example 5
Arrange these aqueous solutions in order of decreasing freezing points: 0.1 m KC l , 0.1 m glucose, 0.1 m SrCl2, 0.1 m ethylene
glycol, 0.1 m benzoic acid, and 0.1 m HCl.
Given: molalities of six solutions
Asked for: relative freezing points
Strategy:
A. Identify each solute as a strong, weak, or nonelectrolyte, and use this information to determine the number of solute particles
produced.
B. Multiply this number by the concentration of the solution to obtain the effective concentration of solute particles. The
solution with the highest effective concentration of solute particles has the largest freezing point depression.
Solution:
A Because the molal concentrations of all six solutions are the same, we must focus on which of the substances are strong
electrolytes, which are weak electrolytes, and which are nonelectrolytes to determine the actual numbers of particles in solution.
KCl, SrCl , and HCl are strong electrolytes, producing two, three, and two ions per formula unit, respectively. Benzoic acid is
2

a weak electrolyte (approximately one particle per molecule), and glucose and ethylene glycol are both nonelectrolytes (one
particle per molecule).
B The molalities of the solutions in terms of the total particles of solute are: KCl and HCl, 0.2 m; SrC l , 0.3 m; glucose and
2

ethylene glycol, 0.1 m; and benzoic acid, 0.1–0.2 m. Because the magnitude of the decrease in freezing point is proportional to
the concentration of dissolved particles, the order of freezing points of the solutions is: glucose and ethylene glycol (highest
freezing point, smallest freezing point depression) > benzoic acid > HCl = KCl > SrCl . 2

Exercise 5
Arrange these aqueous solutions in order of increasing freezing points: 0.2 m NaCl, 0.3 m acetic acid, 0.1 m CaCl , and 0.2 m
2

sucrose.

Answer
0.2 m NaCl (lowest freezing point) < 0.3 m acetic acid ≈ 0.1 m CaCl < 0.2 m sucrose (highest freezing point)
2

Colligative properties can also be used to determine the molar mass of an unknown compound. One method that can be carried out
in the laboratory with minimal equipment is to measure the freezing point of a solution with a known mass of solute. This method
is accurate for dilute solutions (≤1% by mass) because changes in the freezing point are usually large enough to measure accurately
and precisely. By comparing K and K values in Table 1, we see that changes in the boiling point are smaller than changes in the
b f

freezing point for a given solvent. Boiling point elevations are thus more difficult to measure precisely. For this reason, freezing
point depression is more commonly used to determine molar mass than is boiling point elevation. Because of its very large value of
K (37.8°C/m), d-(+)-camphor (Table 1 ) is often used to determine the molar mass of organic compounds by this method.
f

7 [Link]
Example 6 : Sulfur
A 7.08 g sample of elemental sulfur is dissolved in 75.0 g of C S to create a solution whose freezing point is −113.5°C. Use
2

these data to calculate the molar mass of elemental sulfur and thus the formula of the dissolved Sn molecules (i.e., what is the
value of n ?).
Given: masses of solute and solvent and freezing point
Asked for: molar mass and number of S atoms per molecule
Strategy:
A. Use Equation 3, the measured freezing point of the solution, and the freezing point of C S from Table 1 to calculate the
2

freezing point depression. Then use Equation 4 and the value of K from Table 1 to calculate the molality of the solution.
f

B. From the calculated molality, determine the number of moles of solute present.
C. Use the mass and number of moles of the solute to calculate the molar mass of sulfur in solution. Divide the result by the
molar mass of atomic sulfur to obtain n , the number of sulfur atoms per mole of dissolved sulfur.
Solution:
A The first step is to calculate the freezing point depression using Equation 3:
0
ΔTf = T − Tf = −112.1°C − (−113.5°C ) = 1.4°C
f

Then Equation 4 gives

ΔTf 1.4° C
m = = = 0.37 m
Kf 3.74° C /m

B The total number of moles of solute present in the solution is

⎛ 0.37mol ⎞ 1kg
moles solute = (75.0 g) ( ) = 0.028 mol
⎝ kg ⎠ 1000 g

C We now know that 0.708 g of elemental sulfur corresponds to 0.028 mol of solute. The molar mass of dissolved sulfur is thus
7.08 g
molar mass = = 260 g/mol
0.028 mol

The molar mass of atomic sulfur is 32 g/mol, so there must be 260/32 = 8.1 sulfur atoms per mole, corresponding to a formula
of S .
8

Exercise 6
One of the byproducts formed during the synthesis of C is a deep red solid containing only carbon. A solution of 205 mg of
60

this compound in 10.0 g of C C l has a freezing point of −23.38°C. What are the molar mass and most probable formula of the
4

substance?

Answer
847 g/mol; C 70

8 [Link]
Osmotic Pressure
Osmotic pressure is a colligative property of solutions that is observed using a semipermeable membrane, a barrier with pores small
enough to allow solvent molecules to pass through but not solute molecules or ions. The net flow of solvent through a
semipermeable membrane is called osmosis (from the Greek osmós, meaning “push”). The direction of net solvent flow is always
from the side with the lower concentration of solute to the side with the higher concentration.
Osmosis can be demonstrated using a U-tube like the one shown in Figure 6, which contains pure water in the left arm and a dilute
aqueous solution of glucose in the right arm. A net flow of water through the membrane occurs until the levels in the arms
eventually stop changing, which indicates that equilibrium has been reached. The osmotic pressure (Π ) of the glucose solution is
the difference in the pressure between the two sides, in this case the heights of the two columns. Although the semipermeable
membrane allows water molecules to flow through in either direction, the rate of flow is not the same in both directions because the
concentration of water is not the same in the two arms. The net flow of water through the membrane can be prevented by applying
a pressure to the right arm that is equal to the osmotic pressure of the glucose solution.

Figure 6 : Osmotic Pressure. (a) A dilute solution of glucose in water is placed in the right arm of a U-tube, and the left arm is
filled to the same height with pure water; a semipermeable membrane separates the two arms. Because the flow of pure solvent
through the membrane from left to right (from pure water to the solution) is greater than the flow of solvent in the reverse direction,
the level of liquid in the right tube rises. (b) At equilibrium, the pressure differential, equal to the osmotic pressure of the solution (
Πsoln ), equalizes the flow rate of solvent in both directions. (c) Applying an external pressure equal to the osmotic pressure of the
original glucose solution to the liquid in the right arm reverses the flow of solvent and restores the original situation.
Just as with any other colligative property, the osmotic pressure of a solution depends on the concentration of dissolved solute
particles. Osmotic pressure obeys a law that resembles the ideal gas equation:
nRT
Π = = M RT (5)
V

where M is the number of moles of solute per unit volume of solution (i.e., the molarity of the solution), R is the ideal gas
constant, and T is the absolute temperature.
As shown in Example 7, osmotic pressures tend to be quite high, even for rather dilute solutions.

Example 7
When placed in a concentrated salt solution, certain yeasts are able to produce high internal concentrations of glycerol to
counteract the osmotic pressure of the surrounding medium. Suppose that the yeast cells are placed in an aqueous solution
containing 4.0% NaCl by mass; the solution density is 1.02 g/mL at 25°C.
a. Calculate the osmotic pressure of a 4.0% aqueous NaCl solution at 25°C.
b. If the normal osmotic pressure inside a yeast cell is 7.3 atm, corresponding to a total concentration of dissolved particles of
0.30 M, what concentration of glycerol must the cells synthesize to exactly balance the external osmotic pressure at 25°C?
Given: concentration, density, and temperature of NaCl solution; internal osmotic pressure of cell
Asked for: osmotic pressure of NaCl solution and concentration of glycerol needed
Strategy:

9 [Link]
 A. Calculate the molarity of the NaCl solution using the formula mass of the solute and the density of the solution. Then
calculate the total concentration of dissolved particles.
B. Use Equation 5 to calculate the osmotic pressure of the solution.
C. Subtract the normal osmotic pressure of the cells from the osmotic pressure of the salt solution to obtain the additional
pressure needed to balance the two. Use Equation 5 to calculate the molarity of glycerol needed to create this osmotic
pressure.
Solution:
A The solution contains 4.0 g of NaCl per 100 g of solution. Using the formula mass of NaCl (58.44 g/mol) and the density of
the solution (1.02 g/mL), we can calculate the molarity:
moles N aC l
MN aC l =
liter solution

4.0 g N aC l ⎛ 1 ⎞⎛ 1.02 g solution ⎞ 1000 mL

=( ) ( )
58.44 g /mol N aC l ⎝ 100 g solution ⎠ ⎝ 1.00 mL solution ⎠ 1 L

= 0.70 M NaCl

Because 1 mol of NaCl produces 2 mol of particles in solution, the total concentration of dissolved particles in the solution is
(2)(0.70 M) = 1.4 M.
B Now we can use Equation 5 to calculate the osmotic pressure of the solution:

Π = M RT

= (1.4 mol/L) [0.0821 (L ⋅ atm)/(K ⋅ mol)] (298 K)

= 34 atm

C If the yeast cells are to exactly balance the external osmotic pressure, they must produce enough glycerol to give an additional
internal pressure of (34 atm − 7.3 atm) = 27 atm. Glycerol is a nonelectrolyte, so we can solve Equation 5 for the molarity
corresponding to this osmotic pressure:
Π
M =
RT

27 atm
=
[0.0821(L ⋅ atm )/( K ⋅ mol)](298 K )

= 1.1 M glycerol

In solving this problem, we could also have recognized that the only way the osmotic pressures can be the same inside the cells
and in the solution is if the concentrations of dissolved particles are the same. We are given that the normal concentration of
dissolved particles in the cells is 0.3 M, and we have calculated that the NaCl solution is effectively 1.4 M in dissolved
particles. The yeast cells must therefore synthesize enough glycerol to increase the internal concentration of dissolved particles
from 0.3 M to 1.4 M—that is, an additional 1.1 M concentration of glycerol.

Exercise 7
Assume that the fluids inside a sausage are approximately 0.80 M in dissolved particles due to the salt and sodium nitrite used to
prepare them. Calculate the osmotic pressure inside the sausage at 100°C to learn why experienced cooks pierce the
semipermeable skin of sausages before boiling them.

Answer
24 atm

Because of the large magnitude of osmotic pressures, osmosis is extraordinarily important in biochemistry, biology, and medicine.
Virtually every barrier that separates an organism or cell from its environment acts like a semipermeable membrane, permitting the

10 [Link]
flow of water but not solutes. The same is true of the compartments inside an organism or cell. Some specialized barriers, such as
those in your kidneys, are slightly more permeable and use a related process called dialysis, which permits both water and small
molecules to pass through but not large molecules such as proteins.
The same principle has long been used to preserve fruits and their essential vitamins over the long winter. High concentrations of
sugar are used in jams and jellies not for sweetness alone but because they greatly increase the osmotic pressure. Thus any bacteria
not killed in the cooking process are dehydrated, which keeps them from multiplying in an otherwise rich medium for bacterial
growth. A similar process using salt prevents bacteria from growing in ham, bacon, salt pork, salt cod, and other preserved meats.
The effect of osmotic pressure is dramatically illustrated in Figure 7, which shows what happens when red blood cells are placed in
a solution whose osmotic pressure is much lower or much higher than the internal pressure of the cells.

Figure 7 : Effect on Red Blood Cells of the Surrounding Solution’s Osmotic Pressure. (a) When red blood cells are placed in a
dilute salt solution having the same osmotic pressure as the intracellular fluid, the rate of flow of water into and out of the cells is
the same and their shape does not change. (b) When cells are placed in distilled water whose osmotic pressure is less than that of
the intracellular fluid, the rate of flow of water into the cells is greater than the rate of flow out of the cells. The cells swell and
eventually burst. (c) When cells are placed in a concentrated salt solution with an osmotic pressure greater than that of the
intracellular fluid, the rate of flow of water out of the cells is greater than the rate of flow into the cells. The cells shrivel and
become so deformed that they cannot function.
In addition to capillary action, trees use osmotic pressure to transport water and other nutrients from the roots to the upper
branches. Evaporation of water from the leaves results in a local increase in the salt concentration, which generates an osmotic
pressure that pulls water up the trunk of the tree to the leaves.
Finally, a process called reverse osmosis can be used to produce pure water from seawater. As shown schematically in Figure 8,
applying high pressure to seawater forces water molecules to flow through a semipermeable membrane that separates pure water
from the solution, leaving the dissolved salt behind. Large-scale desalinization plants that can produce hundreds of thousands of
gallons of freshwater per day are common in the desert lands of the Middle East, where they supply a large proportion of the
freshwater needed by the population. Similar facilities are now being used to supply freshwater in southern California. Small, hand-
operated reverse osmosis units can produce approximately 5 L of freshwater per hour, enough to keep 25 people alive, and are now
standard equipment on US Navy lifeboats.

Figure 8 : Desalinization of Seawater by Reverse Osmosis. (top) When the pressure applied to seawater equals its osmotic pressure
(Π ), there is no net flow of water across the semipermeable membrane. (bottom) The application of pressure greater than the
soln

osmotic pressure of seawater forces water molecules to flow through the membrane, leaving behind a concentrated salt solution. In

11 [Link]
 desalinization plants, seawater is continuously introduced under pressure and pure water is collected, so the process continues
indefinitely.

Summary
The colligative properties of a solution depend on only the total number of dissolved particles in solution, not on their chemical
identity. Colligative properties include vapor pressure, boiling point, freezing point, and osmotic pressure. The addition of a
nonvolatile solute (one without a measurable vapor pressure) decreases the vapor pressure of the solvent. The vapor pressure of the
solution is proportional to the mole fraction of solvent in the solution, a relationship known as Raoult’s law. Solutions that obey
Raoult’s law are called ideal solutions. Most real solutions exhibit positive or negative deviations from Raoult’s law. The boiling
point elevation (ΔT ) and freezing point depression (ΔT ) of a solution are defined as the differences between the boiling and
b f

freezing points, respectively, of the solution and the pure solvent. Both are proportional to the molality of the solute. When a
solution and a pure solvent are separated by a semipermeable membrane, a barrier that allows solvent molecules but not solute
molecules to pass through, the flow of solvent in opposing directions is unequal and produces an osmotic pressure, which is the
difference in pressure between the two sides of the membrane. Osmosis is the net flow of solvent through such a membrane due to
different solute concentrations. Dialysis uses a semipermeable membrane with pores that allow only small solute molecules and
solvent molecules to pass through.
Henry’s law:

C = kP

Raoult’s law:
0
PA = χA P
A

vapor pressure lowering:

0 0
P − PA = ΔPA = χB P
A A

vapor pressure of a system containing two volatile components:

0 0
Ptot = χA P + (1 − χA )P
A B

boiling point elevation:

ΔTb = m Kb i

freezing point depression:

ΔTf = m Kf i

osmotic pressure:

Π = nRT V = M RT i

Modified by Tom Neils (Grand Rapids Community College)

5.3 Colligative Properties and Freezing Point Depression and Boiling Point Elevation and Osmosis is shared under a CC BY-NC-SA 4.0 license
and was authored, remixed, and/or curated by LibreTexts.

12 [Link]
5.4 Writing and Balancing Chemical Equations
Skills to Develop
To describe a chemical reaction.
To calculate the quantities of compounds produced or consumed in a chemical reaction

What happens to matter when it undergoes chemical changes? The Law of conservation of mass says that "Atoms are neither
created, nor distroyed, during any chemical reaction." Thus, the same collection of atoms is present after a reaction as before the
reaction. The changes that occur during a reaction just involve the rearrangement of atoms. In this section we will discuss
stoichiometry (the "measurement of elements").

Chemical Equations
As shown in Figure 1, applying a small amount of heat to a pile of orange ammonium dichromate powder results in a vigorous
reaction known as the ammonium dichromate volcano. Heat, light, and gas are produced as a large pile of fluffy green
chromium(III) oxide forms. This reaction is described with a chemical equation, an expression that gives the identities and
quantities of the substances in a chemical reaction.

Figure 1 : An Ammonium Dichromate Volcano: Change during a Chemical Reaction. The starting material is solid ammonium
dichromate. A chemical reaction transforms it to solid chromium(III) oxide, depicted showing a portion of its chained structure,
nitrogen gas, and water vapor (in addition, energy in the form of heat and light is released). During the reaction, the distribution of
atoms changes, but the number of atoms of each element does not change. Because the numbers of each type of atom are the same
in the reactants and the products, the chemical equation is balanced. Figure used with permission from Wikipedia. See video here:
[Link]
Chemical reactions are represented on paper by chemical equations. For example, hydrogen gas (H2) can react (burn) with oxygen
gas (O2) to form water (H2O). The chemical equation for this reaction is written as:

2H +O → 2H O (1)
2 2 2

Chemical formulas and other symbols are used to indicate the starting materials, or reactants, which by convention are written on
the left side of the equation, and the final compounds, or products, which are written on the right. An arrow points from the reactant
to the products. The chemical reaction for the ammonium dichromate volcano in Figure 1 is
(NH ) Cr O → Cr O +N +4 H O (2)
4 2 2 7 2 3 2 2
 
reactant products

The arrow is read as “yields” or “reacts to form.” Equation 2 indicates that ammonium dichromate (the reactant) yields
chromium(III) oxide, nitrogen, and water (the products). The equation for this reaction is even more informative when written as
follows:
(NH ) Cr O (s) → Cr O (s) + N (g) + 4 H O(g) (3)
4 2 2 7 2 3 2 2

Equation 3 is identical to Equation 2 except for the addition of abbreviations in parentheses to indicate the physical state of each
species. The abbreviations are (s) for solid, (l) for liquid, (g) for gas, and (aq) for an aqueous solution, a solution of the substance in
water.

1 [Link]
Consistent with the law of conservation of mass, the numbers of each type of atom are the same on both sides of Equations 2 and 3.
Each side of the reaction has two chromium atoms, seven oxygen atoms, two nitrogen atoms, and eight hydrogen atoms.
In a balanced chemical equation, both the numbers of each type of atom and the total charge are the same on both sides. Equations
2 and 3 are balanced chemical equations. What is different on each side of the equation is how the atoms are arranged to make

molecules or ions. A chemical reaction represents a change in the distribution of atoms, but not in the number of atoms. In this
reaction, and in most chemical reactions, bonds are broken in the reactants (here, Cr–O and N–H bonds), and new bonds are
formed to create the products (here, O–H and N≡N bonds). If the numbers of each type of atom are different on the two sides of a
chemical equation, then the equation is unbalanced, and it cannot correctly describe what happens during the reaction. To proceed,
the equation must first be balanced.
A chemical reaction changes only the distribution of atoms, not the number of atoms.

Balancing Simple Chemical Equations

When a chemist encounters a new reaction, it does not usually come with a label that shows the balanced chemical equation.
Instead, the chemist must identify the reactants and products and then write them in the form of a chemical equation that may or
may not be balanced as first written. Consider, for example, the combustion of n-heptane (C H ), an important component of
7 16

gasoline:

C H (l) + O (g) → CO (g) + H O(g) (4)

7 16 2 2 2

The complete combustion of any hydrocarbon with sufficient oxygen always yields carbon dioxide and water.

Figure 2 : An Example of a Combustion Reaction. The wax in a candle is a high-molecular-mass hydrocarbon, which produces
gaseous carbon dioxide and water vapor in a combustion reaction (Equation 4).
Equation 4 is not balanced: the numbers of each type of atom on the reactant side of the equation (7 carbon atoms, 16 hydrogen
atoms, and 2 oxygen atoms) is not the same as the numbers of each type of atom on the product side (1 carbon atom, 2 hydrogen
atoms, and 3 oxygen atoms). Consequently, the coefficients of the reactants and products must be adjusted to give the same
numbers of atoms of each type on both sides of the equation. Because the identities of the reactants and products are fixed, the
equation cannot be balanced by changing the subscripts of the reactants or the products. To do so would change the chemical
identity of the species being described, as illustrated in Figure 3.

Figure 3 : Balancing Equations. You cannot change subscripts in a chemical formula to balance a chemical equation; you can
change only the coefficients. Changing subscripts changes the ratios of atoms in the molecule and the resulting chemical
properties. For example, water (H2O) and hydrogen peroxide (H2O2) are chemically distinct substances. H2O2 decomposes to H2O
and O2 gas when it comes in contact with the metal platinum, whereas no such reaction occurs between water and platinum.

2 [Link]
The simplest and most generally useful method for balancing chemical equations is “inspection,” better known as trial and error.
The following is an efficient approach to balancing a chemical equation using this method.
Steps in Balancing a Chemical Equation
1. Identify the most complex substance.
2. Beginning with that substance, choose an element that appears in only one reactant and one product, if possible. Adjust the
coefficients to obtain the same number of atoms of this element on both sides.
3. Balance polyatomic ions (if present) as a unit.
4. Balance the remaining atoms, usually ending with the least complex substance and using fractional coefficients if necessary.
If a fractional coefficient has been used, multiply both sides of the equation by the denominator to obtain whole numbers for
the coefficients.
5. Check your work by counting the numbers of atoms of each kind on both sides of the equation to be sure that the chemical
equation is balanced.

Example 1A: Combustion of Heptane

To demonstrate this approach, let’s use the combustion of n-heptane (Equation 4) as an example.
1. Identify the most complex substance. The most complex substance is the one with the largest number of different atoms,
which is C H . We will assume initially that the final balanced chemical equation contains 1 molecule or formula unit of
7 16

this substance.
2. Adjust the coefficients. Try to adjust the coefficients of the molecules on the other side of the equation to obtain the same
numbers of atoms on both sides. Because one molecule of n-heptane contains 7 carbon atoms, we need 7 CO2 molecules,
each of which contains 1 carbon atom, on the right side:

C H +O → 7 CO +H O (5)
7 16 2 2 2

3. Balance polyatomic ions as a unit. There are no polyatomic ions to be considered in this reaction.
4. Balance the remaining atoms. Because one molecule of n-heptane contains 16 hydrogen atoms, we need 8 H2O molecules,
each of which contains 2 hydrogen atoms, on the right side:

C H +O → 7 CO +8 H O (6)
7 16 2 2 2

The carbon and hydrogen atoms are now balanced, but we have 22 oxygen atoms on the right side and only 2 oxygen atoms
on the left. We can balance the oxygen atoms by adjusting the coefficient in front of the least complex substance, O2, on the
reactant side:

C H (l) + 11 O (g) → 7 CO (g) + 8 H O(g) (7)

7 16 2 2 2

5. Check your work. The equation is now balanced, and there are no fractional coefficients: there are 7 carbon atoms, 16
hydrogen atoms, and 22 oxygen atoms on each side. Always check to be sure that a chemical equation is [Link]
assumption that the final balanced chemical equation contains only one molecule or formula unit of the most complex
substance is not always valid, but it is a good place to start.

Example 1B: Combustion of Isooctane

Consider, for example, a similar reaction, the combustion of isooctane (C H ). Because the combustion of any hydrocarbon
8 18

with oxygen produces carbon dioxide and water, the unbalanced chemical equation is as follows:
C H (l) + O (g) → CO (g) + H O(g) (8)
8 18 2 2 2

1. Identify the most complex substance. Begin the balancing process by assuming that the final balanced chemical equation
contains a single molecule of isooctane.
2. Adjust the coefficients. The first element that appears only once in the reactants is carbon: 8 carbon atoms in isooctane
means that there must be 8 CO2 molecules in the products:
C H +O → 8 CO +H O (9)
8 18 2 2 2

3. Balance polyatomic ions as a unit. This step does not apply to this equation.

3 [Link]
 4. Balance the remaining atoms. Eighteen hydrogen atoms in isooctane means that there must be 9 H2O molecules in the
products:
C H +O → 8 CO +9 H O (10)
8 18 2 2 2

The carbon and hydrogen atoms are now balanced, but we have 25 oxygen atoms on the right side and only 2 oxygen atoms
on the left. We can balance the least complex substance, O2, but because there are 2 oxygen atoms per O2 molecule, we must
use a fractional coefficient (25/2) to balance the oxygen atoms:
25
C H + O → 8 CO +9 H O (11)
8 18 2 2 2 2

Equation 11 is now balanced, but we usually write equations with whole-number coefficients. We can eliminate the
fractional coefficient by multiplying all coefficients on both sides of the chemical equation by 2:
2C H (l) + 25 O (g) → 16 CO (g) + 18 H O(g) (12)
8 18 2 2 2

5. Check your work. The balanced chemical equation has 16 carbon atoms, 36 hydrogen atoms, and 50 oxygen atoms on each
side.
Balancing equations requires some practice on your part as well as some common sense. If you find yourself using very large
coefficients or if you have spent several minutes without success, go back and make sure that you have written the formulas of
the reactants and products correctly.

Example 1C : Hydroxyapatite
The reaction of the mineral hydroxyapatite (Ca (PO ) (OH) ) with phosphoric acid and water gives
5 4 3
Ca (H PO )
2 4 2
∙H O
2

(calcium dihydrogen phosphate monohydrate). Write and balance the equation for this reaction.

Hydroxyapatite ((C a5(P O4)3(OH )) crystal

Given: reactants and product
Asked for: balanced chemical equation
Strategy:
A. Identify the product and the reactants and then write the unbalanced chemical equation.
B. Follow the steps for balancing a chemical equation.
Solution:
A We must first identify the product and reactants and write an equation for the reaction. The formulas for hydroxyapatite and
calcium dihydrogen phosphate monohydrate are given in the problem (recall that phosphoric acid is H3PO4). The initial
(unbalanced) equation is as follows:
Ca (PO ) (OH)(s) + H PO (aq) + H O → Ca (H PO ) ⋅H O (13)
5 4 3 3 4 2 (l) 2 4 2 2 (s)

1. B Identify the most complex substance. We start by assuming that only one molecule or formula unit of the most complex
substance, Ca (PO ) (OH) , appears in the balanced chemical equation.
5 4 3

2. Adjust the coefficients. Because calcium is present in only one reactant and one product, we begin with it. One formula unit
of Ca (PO ) (OH) contains 5 calcium atoms, so we need 5 Ca(H2PO4)2•H2O on the right side:
5 4 3

Ca (PO ) (OH) + H PO + H O → 5 Ca (H PO ) ⋅H O (14)

5 4 3 3 4 2 2 4 2 2

4 [Link]
 3. Balance polyatomic ions as a unit. It is usually easier to balance an equation if we recognize that certain combinations of
atoms occur on both sides. In this equation, the polyatomic phosphate ion (PO43−), shows up in three places. In H3PO4, the
phosphate ion is combined with three H+ ions to make phosphoric acid (H3PO4), whereas in Ca(H2PO4)2 • H2O it is combined
with two H+ ions to give the dihydrogen phosphate ion. Thus it is easier to balance PO4 as a unit rather than counting individual
phosphorus and oxygen atoms. There are 10 PO4 units on the right side but only 4 on the left. The simplest way to balance the
PO4 units is to place a coefficient of 7 in front of H3PO4:
Ca (PO ) (OH) + 7 H PO + H O → 5 Ca (H PO ) ⋅H O (15)
5 4 3 3 4 2 2 4 2 2

Although OH− is also a polyatomic ion, it does not appear on both sides of the equation. So oxygen and hydrogen must be
balanced separately.
4. Balance the remaining atoms. We now have 30 hydrogen atoms on the right side but only 24 on the left. We can balance the
hydrogen atoms using the least complex substance, H2O, by placing a coefficient of 4 in front of H2O on the left side, giving a
total of 4 H2O molecules:

Ca (PO ) (OH)(s) + 7 H PO (aq) + 4 H O(l) → 5 Ca (H PO ) ⋅ H O(s) (16)

5 4 3 3 4 2 2 4 2 2

The equation is now balanced. Even though we have not explicitly balanced the oxygen atoms, there are 41 oxygen atoms on
each side.
5. Check your work. Both sides of the equation contain 5 calcium atoms, 10 phosphorus atoms, 30 hydrogen atoms, and 41
oxygen atoms.

Exercise 1 : Fermentation
Fermentation is a biochemical process that enables yeast cells to live in the absence of oxygen. Humans have exploited it for
centuries to produce wine and beer and make bread rise. In fermentation, sugars such as glucose are converted to ethanol (
C H C H OH and carbon dioxide C O . Write a balanced chemical reaction for the fermentation of glucose.
3 2 2

Commercial use of fermentation. (a) Microbrewery vats are used to prepare beer. (b) The fermentation of glucose by yeast cells
is the reaction that makes beer production possible.

Answer
C6 H12 O6 (s) → 2 C2 H5 OH (l) + 2C O2 (g)

Interpreting Chemical Equations

In addition to providing qualitative information about the identities and physical states of the reactants and products, a balanced
chemical equation provides quantitative information. Specifically, it gives the relative amounts of reactants and products consumed
or produced in a reaction. The number of atoms, molecules, or formula units of a reactant or a product in a balanced chemical
equation is the coefficient of that species (e.g., the 4 preceding H2O in Equation 2). When no coefficient is written in front of a

5 [Link]
species, the coefficient is assumed to be 1. As illustrated in Figure 4, the coefficients allow Equation 2 to be interpreted in any of
the following ways:
Two NH4+ ions and one Cr2O72− ion yield 1 formula unit of Cr2O3, 1 N2 molecule, and 4 H2O molecules.
One mole of (NH4)2Cr2O7 yields 1 mol of Cr2O3, 1 mol of N2, and 4 mol of H2O.
A mass of 252 g of (NH4)2Cr2O7 yields 152 g of Cr2O3, 28 g of N2, and 72 g of H2O.
A total of 6.022 × 1023 formula units of (NH4)2Cr2O7 yields 6.022 × 1023 formula units of Cr2O3, 6.022 × 1023 molecules of N2,
and 24.09 × 1023 molecules of H2O.

Figure 4 : The Relationships among Moles, Masses, and Formula Units of Compounds in the Balanced Chemical Reaction for the
Ammonium Dichromate Volcano
These are all chemically equivalent ways of stating the information given in the balanced chemical equation, using the concepts of
the mole, molar or formula mass, and Avogadro’s number. The ratio of the number of moles of one substance to the number of
moles of another is called the mole ratio. For example, the mole ratio of H O to N in Equation 2 is 4:1. The total mass of
2 2

reactants equals the total mass of products, as predicted by Dalton’s law of conservation of mass:

252 g of (NH ) Cr O (17)

4 2 2 7

yield

152 + 28 + 72 = 252 g of products. (18)

The chemical equation does not, however, show the rate of the reaction (rapidly, slowly, or not at all) or whether energy in the form
of heat or light is given off. These issues are considered in more detail in later chapters.
An important chemical reaction was analyzed by Antoine Lavoisier, an 18th-century French chemist, who was interested in the
chemistry of living organisms as well as simple chemical systems. In a classic series of experiments, he measured the carbon
dioxide and heat produced by a guinea pig during respiration, in which organic compounds are used as fuel to produce energy,
carbon dioxide, and water. Lavoisier found that the ratio of heat produced to carbon dioxide exhaled was similar to the ratio
observed for the reaction of charcoal with oxygen in the air to produce carbon dioxide—a process chemists call combustion. Based
on these experiments, he proposed that “Respiration is a combustion, slow it is true, but otherwise perfectly similar to that of
charcoal.” Lavoisier was correct, although the organic compounds consumed in respiration are substantially different from those
found in charcoal. One of the most important fuels in the human body is glucose (C H O ), which is virtually the only fuel used
6 12 6

in the brain. Thus combustion and respiration are examples of chemical reactions.

Example 2 : Combustion of Glucose

The balanced chemical equation for the combustion of glucose in the laboratory (or in the brain) is as follows:

C H O (s) + 6 O (g) → 6 CO (g) + 6 H O(l) (19)

6 12 6 2 2 2

Construct a table showing how to interpret the information in this equation in terms of
a. a single molecule of glucose.
b. moles of reactants and products.
c. grams of reactants and products represented by 1 mol of glucose.

6 [Link]
 d. numbers of molecules of reactants and products represented by 1 mol of glucose.

The combustion of a sugar cube consisting of sucrose with a similar reaction to the combustion of glucose. Image used with
permission from Wikipedia.
Given: balanced chemical equation
Asked for: molecule, mole, and mass relationships
Strategy:
A. Use the coefficients from the balanced chemical equation to determine both the molecular and mole ratios.
B. Use the molar masses of the reactants and products to convert from moles to grams.
C. Use Avogadro’s number to convert from moles to the number of molecules.
Solution:
This equation is balanced as written: each side has 6 carbon atoms, 18 oxygen atoms, and 12 hydrogen atoms. We can therefore
use the coefficients directly to obtain the desired information.
a. One molecule of glucose reacts with 6 molecules of O2 to yield 6 molecules of CO2 and 6 molecules of H2O.
b. One mole of glucose reacts with 6 mol of O2 to yield 6 mol of CO2 and 6 mol of H2O.
c. To interpret the equation in terms of masses of reactants and products, we need their molar masses and the mole ratios from
part b. The molar masses in grams per mole are as follows: glucose, 180.16; O2, 31.9988; CO2, 44.010; and H2O, 18.015.

mass of reactants = mass of products

g glucose + g O2 = g C O2 + g H2 O

180.16 g 31.9988 g
1 mol glucose ( ) + 6 mol O2 ( ) (20)
1 mol glucose 1 mol O2

44.010 g 18.015 g
= 6 mol C O2 ( ) + 6 mol H2 O ( ) (21)
1 mol C O2 1 mol H2 O

372.15 g = 372.15 g (22)

C One mole of glucose contains Avogadro’s number (6.022 × 1023) of glucose molecules. Thus 6.022 × 1023 glucose molecules
react with (6 × 6.022 × 1023) = 3.613 × 1024 oxygen molecules to yield (6 × 6.022 × 1023) = 3.613 × 1024 molecules each of
CO2 and H2O.
In tabular form:

C6 H12 O6 (s) + 6O2 (g) → 6CO2 (g) 6H2 O(l)

a. 1 molecule 6 molecules 6 molecules 6 molecules

b. 1 mol 6 mol 6 mol 6 mol

c. 180.16 g 191.9928 g 264.06 g 108.09 g

6.022 × 1023 3.613 × 1024 3.613 × 1024 3.613 × 1024

d.
molecules molecules molecules molecule

7 [Link]
 Exercise 2 : Ammonium Nitrate Explosion
Ammonium nitrate is a common fertilizer, but under the wrong conditions it can be hazardous. In 1947, a ship loaded with
ammonium nitrate caught fire during unloading and exploded, destroying the town of Texas City, Texas.

Ammonium nitrate can be hazardous. This aerial photograph of Texas City, Texas, shows the devastation caused by the
explosion of a shipload of ammonium nitrate on April 16, 1947. For a video click here.
The explosion resulted from the following reaction:
2N H4 N O3 (s) → 2 N2 (g) + 4 H2 O(g) + O2 (g) (23)

Construct a table showing how to interpret the information in the equation in terms of
a. individual molecules and ions.
b. moles of reactants and products.
c. grams of reactants and products given 2 mol of ammonium nitrate.
d. numbers of molecules or formula units of reactants and products given 2 mol of ammonium nitrate.
Answer:

2N H4 N O3 (s) → 2N2 (g) + 4H2 O(g) + O2 (g)

2NH4+ ions
a. and 2NO3− 2 molecules 4 molecules 1 molecule
ions

b. 2 mol 2 mol 4 mol 1 mol

c. 160.0864 g 56.0268 g 72.0608 g 31.9988 g

1.204 × 1024 1.204 × 1024 2.409 × 1024 6.022 × 1023

d.
formula units molecules molecules molecules

Summary
A chemical reaction is described by a chemical equation that gives the identities and quantities of the reactants and the products. In
a chemical reaction, one or more substances are transformed to new substances. A chemical reaction is described by a chemical
equation, an expression that gives the identities and quantities of the substances involved in a reaction. A chemical equation shows
the starting compound(s)—the reactants—on the left and the final compound(s)—the products—on the right, separated by an
arrow. In a balanced chemical equation, the numbers of atoms of each element and the total charge are the same on both sides of

8 [Link]
the equation. The number of atoms, molecules, or formula units of a reactant or product in a balanced chemical equation is the
coefficient of that species. The mole ratio of two substances in a chemical reaction is the ratio of their coefficients in the balanced
chemical equation.

Modified by Tom Neils (Grand Rapids Community College)

5.4 Writing and Balancing Chemical Equations is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

9 [Link]
5.4a Example How Much Carbon Dioxide
Skills to Develop
Explain the concept of stoichiometry as it pertains to chemical reactions
Use balanced chemical equations to derive stoichiometric factors relating amounts of reactants and products
Perform stoichiometric calculations involving mass, moles, and solution molarity

A balanced chemical equation provides a great deal of information in a very succinct format. Chemical formulas provide the
identities of the reactants and products involved in the chemical change, allowing classification of the reaction. Coefficients
provide the relative numbers of these chemical species, allowing a quantitative assessment of the relationships between the
amounts of substances consumed and produced by the reaction. These quantitative relationships are known as the reaction’s
stoichiometry, a term derived from the Greek words stoicheion (meaning “element”) and metron (meaning “measure”). In this
module, the use of balanced chemical equations for various stoichiometric applications is explored.
The general approach to using stoichiometric relationships is similar in concept to the way people go about many common
activities. Cooking, for example, offers an appropriate comparison. Suppose a recipe for making eight pancakes calls for 1 cup
3
pancake mix, cup milk, and one egg. The “equation” representing the preparation of pancakes per this recipe is
4

3
1 cup mix + cup milk + 1 egg → 8 pancakes (1)
4

If two dozen pancakes are needed for a big family breakfast, the ingredient amounts must be increased proportionally according to
the amounts given in the recipe. For example, the number of eggs required to make 24 pancakes is
1 egg
24 pancakes × = 3 eggs (2)
8 pancakes

Balanced chemical equations are used in much the same fashion to determine the amount of one reactant required to react with a
given amount of another reactant, or to yield a given amount of product, and so forth. The coefficients in the balanced equation are
used to derive stoichiometric factors that permit computation of the desired quantity. To illustrate this idea, consider the production
of ammonia by reaction of hydrogen and nitrogen:
N (g) + 3 H (g) → 2 NH (g) (3)
2 2 3

This equation shows that ammonia molecules are produced from hydrogen molecules in a 2:3 ratio, and stoichiometric factors may
be derived using any amount (number) unit:
2 NH molecules 2 doz NH molecules 2 mol NH molecules
3 3 3
or or (4)
3H molecules 3 doz H molecules 3 mol H molecules
2 2 2

These stoichiometric factors can be used to compute the number of ammonia molecules produced from a given number of
hydrogen molecules, or the number of hydrogen molecules required to produce a given number of ammonia molecules. Similar
factors may be derived for any pair of substances in any chemical equation.

Example 1 : Moles of Reactant Required in a Reaction

How many moles of I2 are required to react with 0.429 mol of Al according to the following equation (see Figure 2)?

2 Al + 3 I → 2 AlI (5)
2 3

1 [Link]
 Figure 1 : Aluminum and iodine react to produce aluminum iodide. The heat of the reaction vaporizes some of the solid iodine
as a purple vapor. (credit: modification of work by Mark Ott)
Solution
3 mol I
Referring to the balanced chemical equation, the stoichiometric factor relating the two substances of interest is 2
. The
2 mol Al
molar amount of iodine is derived by multiplying the provided molar amount of aluminum by this factor:

3 mol I2
mol I2 = 0.429 mol Al ×
2 mol Al

= 0.644 mol I2

Exercise 1
How many moles of Ca(OH)2 are required to react with 1.36 mol of H3PO4 to produce Ca3(PO4)2 according to the equation
3 Ca (OH) + 2 H PO → Ca (PO ) + 6 H O ?
2 3 4 3 4 2 2

Answer
2.04 mol

Example 2 : Number of Product Molecules Generated by a Reaction

How many carbon dioxide molecules are produced when 0.75 mol of propane is combusted according to this equation?

C H +5 O → 3 CO +4 H O (6)
3 8 2 2 2

Solution
The approach here is the same as for Example 1, though the absolute number of molecules is requested, not the number of
moles of molecules. This will simply require use of the moles-to-numbers conversion factor, Avogadro’s number.
The balanced equation shows that carbon dioxide is produced from propane in a 3:1 ratio:
3 mol CO
2
(7)
1 mol C H
3 8

Using this stoichiometric factor, the provided molar amount of propane, and Avogadro’s number,

3 mol CO2 23
6.022 × 10 C O2 molecules
24
0.75 mol C3 H8 × × = 1.4 × 10 C O2 molecules (8)
1 mol C3 H8 mol CO2

Exercise 1
How many NH3 molecules are produced by the reaction of 4.0 mol of Ca(OH)2 according to the following equation:

(NH ) SO + Ca (OH) → 2 NH + CaSO +2 H O

4 2 4 2 3 4 2

Answer
4.8 × 1024 NH3 molecules

2 [Link]
These examples illustrate the ease with which the amounts of substances involved in a chemical reaction of known stoichiometry
may be related. Directly measuring numbers of atoms and molecules is, however, not an easy task, and the practical application of
stoichiometry requires that we use the more readily measured property of mass.

Example 3 : Relating Masses of Reactants and Products

What mass of sodium hydroxide, NaOH, would be required to produce 16 g of the antacid milk of magnesia [magnesium
hydroxide, Mg(OH)2] by the following reaction?
MgCl (aq) + 2 NaOH(aq) → Mg (OH) (s) + 2 NaCl(aq)
2 2

Solution
The approach used previously in Examples 1 and 2 is likewise used here; that is, we must derive an appropriate stoichiometric
factor from the balanced chemical equation and use it to relate the amounts of the two substances of interest. In this case,
however, masses (not molar amounts) are provided and requested, so additional steps of the sort learned in the previous chapter
are required. The calculations required are outlined in this flowchart:

1 mol Mg(OH)2 2 mol NaOH 40.0 g NaOH

16 g Mg(OH)2 × × × = 22 g NaOH (9)

58.3 g Mg(OH)2 1 mol Mg(OH)2 mol NaOH

Exercise 3
What mass of gallium oxide, Ga2O3, can be prepared from 29.0 g of gallium metal? The equation for the reaction is
4 Ga + 3 O → 2 Ga O .
2 2 3

Answer
39.0 g

Example 4 : Relating Masses of Reactants

What mass of oxygen gas, O2, from the air is consumed in the combustion of 702 g of octane, C8H18, one of the principal
components of gasoline?
2C H + 25 O → 16 CO + 18 H O
8 18 2 2 2

Solution
The approach required here is the same as for the Example 3, differing only in that the provided and requested masses are both
for reactant species.

3 [Link]
 1 mol C H 25 mol O 32.00 g O
8 18 2
2 3
702 g C H × × × = 2.46 × 10 g O
8 18 2
114.23 g C H 2 mol C H mol O
8 18 8 18 2

Exercise 4
What mass of CO is required to react with 25.13 g of Fe2O3 according to the equation Fe 2
O
3
+ 3 CO → 2 Fe + 3 CO
2
?

Answer
13.22 g

These examples illustrate just a few instances of reaction stoichiometry calculations. Numerous variations on the beginning and
ending computational steps are possible depending upon what particular quantities are provided and sought (volumes, solution
concentrations, and so forth). Regardless of the details, all these calculations share a common essential component: the use of
stoichiometric factors derived from balanced chemical equations. Figure 2 provides a general outline of the various computational
steps associated with many reaction stoichiometry calculations.

Figure 2 : The flowchart depicts the various computational steps involved in most reaction stoichiometry calculations.
Airbags
Airbags (Figure 3) are a safety feature provided in most automobiles since the 1990s. The effective operation of an airbag
requires that it be rapidly inflated with an appropriate amount (volume) of gas when the vehicle is involved in a collision. This
requirement is satisfied in many automotive airbag systems through use of explosive chemical reactions, one common choice

4 [Link]
 being the decomposition of sodium azide, NaN3. When sensors in the vehicle detect a collision, an electrical current is passed
through a carefully measured amount of NaN3 to initiate its decomposition:
2 NaN (s) → 3 N (g) + 2 Na(s) (10)
3 2

This reaction is very rapid, generating gaseous nitrogen that can deploy and fully inflate a typical airbag in a fraction of a second
(~0.03–0.1 s). Among many engineering considerations, the amount of sodium azide used must be appropriate for generating
enough nitrogen gas to fully inflate the air bag and ensure its proper function. For example, a small mass (~100 g) of NaN3 will
generate approximately 50 L of N2.

Figure 3 : Airbags deploy upon impact to minimize serious injuries to passengers. (credit: Jon Seidman)

Summary
A balanced chemical equation may be used to describe a reaction’s stoichiometry (the relationships between amounts of reactants
and products). Coefficients from the equation are used to derive stoichiometric factors that subsequently may be used for
computations relating reactant and product masses, molar amounts, and other quantitative properties.

Glossary

stoichiometric factor
ratio of coefficients in a balanced chemical equation, used in computations relating amounts of reactants and products
stoichiometry
relationships between the amounts of reactants and products of a chemical reaction

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).

5.4a Example How Much Carbon Dioxide is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

5 [Link]
5.5 Limiting Reactant and Theoretical Yield and Percent Yield
Skills to Develop
To understand the concept of limiting reactants and quantify incomplete reactions

In all the examples discussed thus far, the reactants were assumed to be present in stoichiometric quantities. Consequently, none of
the reactants was left over at the end of the reaction. This is often desirable, as in the case of a space shuttle, where excess oxygen
or hydrogen was not only extra freight to be hauled into orbit but also an explosion hazard. More often, however, reactants are
present in mole ratios that are not the same as the ratio of the coefficients in the balanced chemical equation. As a result, one or
more of them will not be used up completely but will be left over when the reaction is completed. In this situation, the amount of
product that can be obtained is limited by the amount of only one of the reactants. The reactant that restricts the amount of product
obtained is called the limiting reactant. The reactant that remains after a reaction has gone to completion is in excess.
Consider a nonchemical example. Assume you have invited some friends for dinner and want to bake brownies for dessert. You
find two boxes of brownie mix in your pantry and see that each package requires two eggs. The balanced equation for brownie
preparation is thus
1 box mix + 2 eggs → 1 batch brownies (1)

If you have a dozen eggs, which ingredient will determine the number of batches of brownies that you can prepare? Because each
box of brownie mix requires two eggs and you have two boxes, you need four eggs. Twelve eggs is eight more eggs than you need.
Although the ratio of eggs to boxes in is 2:1, the ratio in your possession is 6:1. Hence the eggs are the ingredient (reactant) present
in excess, and the brownie mix is the limiting reactant. Even if you had a refrigerator full of eggs, you could make only two batches
of brownies.

Figure 1 : The Concept of a Limiting Reactant in the Preparation of Brownies

Now consider a chemical example of a limiting reactant: the production of pure titanium. This metal is fairly light (45% lighter
than steel and only 60% heavier than aluminum) and has great mechanical strength (as strong as steel and twice as strong as
aluminum). Because it is also highly resistant to corrosion and can withstand extreme temperatures, titanium has many applications
in the aerospace industry. Titanium is also used in medical implants and portable computer housings because it is light and resistant
to corrosion. Although titanium is the ninth most common element in Earth’s crust, it is relatively difficult to extract from its ores.
In the first step of the extraction process, titanium-containing oxide minerals react with solid carbon and chlorine gas to form
titanium tetrachloride (TiCl ) and carbon dioxide.
4

TiO (s) + Cl (g) → TiCl (g) + CO (g) (2)

2 2 4 2

Titanium tetrachloride is then converted to metallic titanium by reaction with molten magnesium metal at high temperature:
TiCl (g) + 2 Mg(l) → Ti(s) + 2 MgCl (l) (3)
4 2

Because titanium ores, carbon, and chlorine are all rather inexpensive, the high price of titanium (about $100 per kilogram) is
largely due to the high cost of magnesium metal. Under these circumstances, magnesium metal is the limiting reactant in the
production of metallic titanium.

1 [Link]
Figure 2 : Medical use of titanium. Here is an example of its successful use in joint replacement implants. An A-P X-ray of a pelvis
showing a total hip joint replacement. The right hip joint (on the left in the photograph) has been replaced. A metal prostheses is
cemented in the top of the right femur and the head of the femur has been replaced by the rounded head of the prosthesis. Figure
courtesy of NIH (NIADDK) 9AO4 (Connie Raab)
With 1.00 kg of titanium tetrachloride and 200 g of magnesium metal, how much titanium metal can be produced according to
Equation 3?
Solving this type of problem requires that you carry out the following steps
1. Determine the number of moles of each reactant.
2. Compare the mole ratio of the reactants with the ratio in the balanced chemical equation to determine which reactant is
limiting.
3. Calculate the number of moles of product that can be obtained from the limiting reactant.
4. Convert the number of moles of product to mass of product.

Step 1: To determine the number of moles of reactants present, calculate or look up their molar masses: 189.679 g/mol for
titanium tetrachloride and 24.305 g/mol for magnesium. The number of moles of each is calculated as follows:
mass TiCl
4
moles TiCl =
4
molar mass TiCl
4

1 mol T iC l4
= 1000 g TiCl ×
4
189.679 g TiCl
4

= 5.272 mol TiCl (4)

4

mass Mg
moles Mg =
molar mass Mg

1 mol Mg
= 200 g Mg ×
24.305 g Mg

= 8.23 mol Mg (5)

Step 2: There are more moles of magnesium than of titanium tetrachloride, but the ratio is only the following:
mol Mg 8.23 mol
= = 1.56 (6)
mol TiCl 5.272 mol
4

Because the ratio of the coefficients in the balanced chemical equation is,
2 mol Mg
=2 (7)
1 mol TiCl
4

there is not have enough magnesium to react with all the titanium tetrachloride. If this point is not clear from the mole ratio,
calculate the number of moles of one reactant that is required for complete reaction of the other reactant. For example, there
are 8.23 mol of Mg, so (8.23 ÷ 2) = 4.12 mol of TiCl are required for complete reaction. Because there are 5.272 mol of
4

2 [Link]
 TiCl
4
, titanium tetrachloride is present in excess. Conversely, 5.272 mol of TiCl requires 2 × 5.272 = 10.54 mol of Mg, but
4

there are only 8.23 mol. Therefore, magnesium is the limiting reactant.
Step 3: Because magnesium is the limiting reactant, the number of moles of magnesium determines the number of moles of
titanium that can be formed:
1 mol Ti
mol Ti = 8.23 mol Mg = = 4.12 mol Ti (8)
2 mol Mg

Thus only 4.12 mol of Ti can be formed.

Step 4. To calculate the mass of titanium metal that can obtain, multiply the number of moles of titanium by the molar mass
of titanium (47.867 g/mol):
moles Ti = mass Ti × molar mass Ti

47.867 g Ti
= 4.12 mol Ti × (9)
1 mol Ti

= 197 g Ti

Here is a simple and reliable way to identify the limiting reactant in any problem of this sort:
1. Calculate the number of moles of each reactant present: 5.272 mol of TiCl and 8.23 mol of Mg.
4

2. Divide the actual number of moles of each reactant by its stoichiometric coefficient in the balanced chemical equation:
5.272 mol (actual)
T iC l4 : = 5.272
1 mol (stoich)

8.23 mol (actual)

Mg : = 4.12
2 mol (stoich)

3. The reactant with the smallest mole ratio is limiting. Magnesium, with a calculated stoichiometric mole ratio of 4.12, is the
limiting reactant.
Density is the mass per unit volume of a substance. If we are given the density of a substance, we can use it in stoichiometric
calculations involving liquid reactants and/or products, as Example 1 demonstrates.

Example 1 : Fingernail Polish Remover

Ethyl acetate (CH CO C H ) is the solvent in many fingernail polish removers and is used to decaffeinate coffee beans and
3 2 2 5

tea leaves. It is prepared by reacting ethanol (C H OH ) with acetic acid (CH CO H ); the other product is water. A small
2 5 3 2

amount of sulfuric acid is used to accelerate the reaction, but the sulfuric acid is not consumed and does not appear in the
balanced chemical equation. Given 10.0 mL each of acetic acid and ethanol, how many grams of ethyl acetate can be prepared
from this reaction? The densities of acetic acid and ethanol are 1.0492 g/mL and 0.7893 g/mL, respectively.

Given: reactants, products, and volumes and densities of reactants

Asked for: mass of product

3 [Link]
Strategy:
A. Balance the chemical equation for the reaction.
B. Use the given densities to convert from volume to mass. Then use each molar mass to convert from mass to moles.
C. Using mole ratios, determine which substance is the limiting reactant. After identifying the limiting reactant, use mole ratios
based on the number of moles of limiting reactant to determine the number of moles of product.
D. Convert from moles of product to mass of product.
Solution:
A Always begin by writing the balanced chemical equation for the reaction:

C H OH(l) + CH CO H(aq) → CH CO C H (aq) + H O(l)

2 5 3 2 3 2 2 5 2

B We need to calculate the number of moles of ethanol and acetic acid that are present in 10.0 mL of each. Recall that the
density of a substance is the mass divided by the volume:
mass
density =
volume

Rearranging this expression gives mass = (density)(volume). We can replace mass by the product of the density and the volume
to calculate the number of moles of each substance in 10.0 mL (remember, 1 mL = 1 cm3):
mass C H OH
2 5
moles C H OH =
2 5
molar mass C H OH
2 5

(volume C H OH) × (density C H OH)

2 5 2 5
=
molar mass C H OH
2 5

0.7893 g C H OH 1 mol C H OH
2 5
2 5
= 10.0 ml C H OH × ×
2 5
46.07 g C H OH
1 ml C H OH 2 5
2 5

= 0.171 mol C H OH
2 5

mass CH CO H
3 2
moles CH CO H =
3 2
molar mass CH CO H
3 2

(volume CH CO H) × (density CH CO H)
3 2 3 2
=
molar mass CH CO H
3 2

1.0492 g CH CO H 1 mol CH CO H
3 2 3 2
= 10.0 ml CH CO H × ×
3 2
1 ml CH CO H 60.05 g CH CO H
3 2
3 2

= 0.175 mol CH CO H
3 2

C The number of moles of acetic acid exceeds the number of moles of ethanol. Because the reactants both have coefficients of 1
in the balanced chemical equation, the mole ratio is 1:1. We have 0.171 mol of ethanol and 0.175 mol of acetic acid, so ethanol
is the limiting reactant and acetic acid is in excess. The coefficient in the balanced chemical equation for the product (ethyl
acetate) is also 1, so the mole ratio of ethanol and ethyl acetate is also 1:1. This means that given 0.171 mol of ethanol, the
amount of ethyl acetate produced must also be 0.171 mol:
1 mol ethyl acetate
moles ethyl acetate = mol ethanol ×
1 mol ethanol

1 mol CH CO C H
3 2 2 5
= 0.171 mol C H OH ×
2 5
1 mol C H OH
2 5

= 0.171 mol CH CO C H
3 2 2 5

D The final step is to determine the mass of ethyl acetate that can be formed, which we do by multiplying the number of moles
by the molar mass:

4 [Link]
 mass of ethyl acetate = mol ethyl acetate × molar mass ethyl acetate

88.11 g CH CO C H
3 2 2 5
= 0.171 mol CH CO C H ×
3 2 2 5
1 mol CH CO C H
3 2 2 5

= 15.1 g CH CO C H
3 2 2 5

Thus 15.1 g of ethyl acetate can be prepared in this reaction. If necessary, you could use the density of ethyl acetate (0.9003
g/cm3) to determine the volume of ethyl acetate that could be produced:
1 ml CH CO C H
3 2 2 5
volume of ethyl acetate = 15.1 g CH CO C H ×
3 2 2 5
0.9003 g CH CO C H
3 2 2 5

= 16.8 ml CH CO C H
3 2 2 5

Exercise 1
Under appropriate conditions, the reaction of elemental phosphorus and elemental sulfur produces the compound P4 S10 . How
much P S can be prepared starting with 10.0 g of P and 30.0 g of S ?
4 10 4 8

Answer
35.9 g

Limiting Reactants in Solutions

The concept of limiting reactants applies to reactions carried out in solution as well as to reactions involving pure substances. If all
the reactants but one are present in excess, then the amount of the limiting reactant may be calculated as illustrated in Example 2.

Example 2 : Breathalyzer reaction

Because the consumption of alcoholic beverages adversely affects the performance of tasks that require skill and judgment, in
most countries it is illegal to drive while under the influence of alcohol. In almost all US states, a blood alcohol level of 0.08%
by volume is considered legally drunk. Higher levels cause acute intoxication (0.20%), unconsciousness (about 0.30%), and
even death (about 0.50%). The Breathalyzer is a portable device that measures the ethanol concentration in a person’s breath,
which is directly proportional to the blood alcohol level. The reaction used in the Breathalyzer is the oxidation of ethanol by the
dichromate ion:
+
Ag
2 − + 3 +
3 CH CH OH(aq) + 2 Cr O (aq) + 16 H (aq) −−−−−→ 3 CH CO H(aq) + 4 Cr (aq) + 11 H O(l)
3 2 2 7 3 2 2
H SO (aq) green
yellow−orange 2 4

When a measured volume (52.5 mL) of a suspect’s breath is bubbled through a solution of excess potassium dichromate in
dilute sulfuric acid, the ethanol is rapidly absorbed and oxidized to acetic acid by the dichromate ions. In the process, the
chromium atoms in some of the Cr O ions are reduced from Cr6+ to Cr3+. In the presence of Ag+ ions that act as a catalyst,
2
2 −
7

the reaction is complete in less than a minute. Because the Cr O ion (the reactant) is yellow-orange and the Cr3+ ion (the
2
2 −

product) forms a green solution, the amount of ethanol in the person’s breath (the limiting reactant) can be determined quite
accurately by comparing the color of the final solution with the colors of standard solutions prepared with known amounts of
ethanol.

5 [Link]
A Breathalyzer reaction with a test tube before (a) and after (b) ethanol is added. When a measured volume of a suspect’s breath
is bubbled through the solution, the ethanol is oxidized to acetic acid, and the solution changes color from yellow-orange to
green. The intensity of the green color indicates the amount of ethanol in the sample.
A typical Breathalyzer ampul contains 3.0 mL of a 0.25 mg/mL solution of K2Cr2O7 in 50% H2SO4 as well as a fixed
concentration of AgNO3 (typically 0.25 mg/mL is used for this purpose). How many grams of ethanol must be present in 52.5
mL of a person’s breath to convert all the Cr6+ to Cr3+?
Given: volume and concentration of one reactant
Asked for: mass of other reactant needed for complete reaction
Strategy:
A. Calculate the number of moles of Cr O ion in 1 mL of the Breathalyzer solution by dividing the mass of K2Cr2O7 by its
2
2 −
7

molar mass.
B. Find the total number of moles of Cr O ion in the Breathalyzer ampul by multiplying the number of moles contained in 1
2
2 −
7

mL by the total volume of the Breathalyzer solution (3.0 mL).

C. Use the mole ratios from the balanced chemical equation to calculate the number of moles of C2H5OH needed to react
completely with the number of moles of Cr O ions present. Then find the mass of C2H5OH needed by multiplying the
2
2 −

number of moles of C2H5OH by its molar mass.

Solution:
A In any stoichiometry problem, the first step is always to calculate the number of moles of each reactant present. In this case,
we are given the mass of K2Cr2O7 in 1 mL of solution, which can be used to calculate the number of moles of K2Cr2O7
contained in 1 mL:
(0.25 mg K2 C r2 O7 ) 1 g
moles K2 C r2 O7 1 mol −7
= ( )( ) = 8.5 × 10 moles
1 mL mL 1000 mg 294.18 g K2 C r2 O7

B Because 1 mol of K2Cr2O7 produces 1 mol of Cr O when it dissolves, each milliliter of solution contains 8.5 × 10−7 mol
2
2 −

of Cr2O72−. The total number of moles of Cr2O72− in a 3.0 mL Breathalyzer ampul is thus
−7
8.5 × 10 mol −6
2− 2–
moles C r2 O =( ) (3.0 mL ) = 2.6 × 10 mol C r2 O
7 7
1 mL

C The balanced chemical equation tells us that 3 mol of C2H5OH is needed to consume 2 mol of Cr O
2
2 −

7
ion, so the total
number of moles of C2H5OH required for complete reaction is

⎛ ⎞
3 mol C H OH
−6 2 − 2 5 −6
moles of C H OH = (2.6 × 10 mol Cr O )⎜ ⎟ = 3.9 × 10 mol C H OH
2 5 2 7 2 5
2 −
⎝2 mol Cr O ⎠
2 7

As indicated in the strategy, this number can be converted to the mass of C2H5OH using its molar mass:

⎛ 46.07 g ⎞
−6 −4
mass C H OH = (3.9 × 10 mol C H OH ) = 1.8 × 10 g C H OH
2 5 2 5 2 5
⎝ mol C H OH ⎠
2 5

Thus 1.8 × 10−4 g or 0.18 mg of C2H5OH must be present. Experimentally, it is found that this value corresponds to a blood
alcohol level of 0.7%, which is usually fatal.

Exercise 2
The compound para-nitrophenol (molar mass = 139 g/mol) reacts with sodium hydroxide in aqueous solution to generate a
yellow anion via the reaction

6 [Link]
 Because the amount of para-nitrophenol is easily estimated from the intensity of the yellow color that results when excess
NaOH is added, reactions that produce para-nitrophenol are commonly used to measure the activity of enzymes, the catalysts

in biological systems. What volume of 0.105 M NaOH must be added to 50.0 mL of a solution containing 7.20 × 10−4 g of
para-nitrophenol to ensure that formation of the yellow anion is complete?

Answer
4.93 × 10−5 L or 49.3 μL

In Examples 1 and 2, the identities of the limiting reactants are apparent: [Au(CN)2]−, LaCl3, ethanol, and para-nitrophenol. When
the limiting reactant is not apparent, it can be determined by comparing the molar amounts of the reactants with their coefficients in
the balanced chemical equation. The only difference is that the volumes and concentrations of solutions of reactants, rather than the
masses of reactants, are used to calculate the number of moles of reactants, as illustrated in Example 3.

Example 3
When aqueous solutions of silver nitrate and potassium dichromate are mixed, an exchange reaction occurs, and silver
dichromate is obtained as a red solid. The overall chemical equation for the reaction is as follows:

2 AgNO (aq) + K Cr O (aq) → Ag Cr O (s) + 2 KNO (aq)

3 2 2 7 2 2 7 3

What mass of Ag2Cr2O7 is formed when 500 mL of 0.17 M K 2

Cr O
2 7
are mixed with 250 mL of 0.57 M AgNO3?
Given: balanced chemical equation and volume and concentration of each reactant
Asked for: mass of product
Strategy:
A. Calculate the number of moles of each reactant by multiplying the volume of each solution by its molarity.
B. Determine which reactant is limiting by dividing the number of moles of each reactant by its stoichiometric coefficient in the
balanced chemical equation.
C. Use mole ratios to calculate the number of moles of product that can be formed from the limiting reactant. Multiply the
number of moles of the product by its molar mass to obtain the corresponding mass of product.
Solution:
A The balanced chemical equation tells us that 2 mol of AgNO3(aq) reacts with 1 mol of K2Cr2O7(aq) to form 1 mol of
Ag2Cr2O7(s) (Figure 8.3.2). The first step is to calculate the number of moles of each reactant in the specified volumes:

1 L 0.17 mol K2 C r2 O7
moles K2 C r2 O7 = 500 mL ( )( ) = 0.085 mol K2 C r2 O7
1000 mL 1 L

1 L 0.57 mol AgN O3

moles AgN O3 = 250 mL ( )( ) = 0.14 mol AgN O3
1000 mL 1 L

B Now determine which reactant is limiting by dividing the number of moles of each reactant by its stoichiometric coefficient:
0.085 mol
K Cr O : = 0.085
2 2 7
1 mol

0.14 mol
AgNO : = 0.070
3
2 mol

Because 0.070 < 0.085, we know that AgNO is the limiting reactant.
3

7 [Link]
 C Each mole of Ag Cr O formed requires 2 mol of the limiting reactant (AgNO ), so we can obtain only 0.14/2 = 0.070 mol
2 2 7 3

of Ag Cr O . Finally, convert the number of moles of Ag Cr O to the corresponding mass:

2 2 7 2 2 7

431.72 g
mass of Ag2 C r2 O7 = 0.070 mol ( ) = 30 g Ag2 C r2 O7
1 mol

The Ag+ and Cr2O72− ions form a red precipitate of solid Ag Cr O , while the 2 2 7
K
+
and NO ions remain in solution. (Water
−
3

molecules are omitted from molecular views of the solutions for clarity.)

Exercise 3
Aqueous solutions of sodium bicarbonate and sulfuric acid react to produce carbon dioxide according to the following equation:

2 NaHCO (aq) + H SO (aq) → 2 CO (g) + Na SO (aq) + 2 H O(l)

3 2 4 2 2 4 2

If 13.0 mL of 3.0 M H2SO4 are added to 732 mL of 0.112 M NaHCO3, what mass of CO2 is produced?

Answer
3.4 g

Theoretical Yields
When reactants are not present in stoichiometric quantities, the limiting reactant determines the maximum amount of product that
can be formed from the reactants. The amount of product calculated in this way is the theoretical yield, the amount obtained if the
reaction occurred perfectly and the purification method were 100% efficient.
In reality, less product is always obtained than is theoretically possible because of mechanical losses (such as spilling), separation
procedures that are not 100% efficient, competing reactions that form undesired products, and reactions that simply do not run to
completion, resulting in a mixture of products and reactants; this last possibility is a common occurrence. Therefore, the actual
yield, the measured mass of products obtained from a reaction, is almost always less than the theoretical yield (often much less).
The percent yield of a reaction is the ratio of the actual yield to the theoretical yield, multiplied by 100 to give a percentage:
actual yield (g)
percent yield = × 100% (10)
theoretical yield (g)

The method used to calculate the percent yield of a reaction is illustrated in Example 4.

Example 4 : Novocain
Procaine is a key component of Novocain, an injectable local anesthetic used in dental work and minor surgery. Procaine can be
prepared in the presence of H2SO4 (indicated above the arrow) by the reaction
H SO
2 4

C H NO + C H NO −−−−→ C H N O +H O
7 7 2 6 15 13 20 2 2 2
p-amino benzoic acid 2-diethylaminoethanol procaine

If this reaction were carried out with 10.0 g of p-aminobenzoic acid and 10.0 g of 2-diethylaminoethanol, and 15.7 g of procaine
were isolated, what is the percent yield?

The preparation of procaine. A reaction of p-aminobenzoic acid with 2-diethylaminoethanol yields procaine and water.
Given: masses of reactants and product
Asked for: percent yield

8 [Link]
Strategy:
A. Write the balanced chemical equation.
B. Convert from mass of reactants and product to moles using molar masses and then use mole ratios to determine which is the
limiting reactant. Based on the number of moles of the limiting reactant, use mole ratios to determine the theoretical yield.
C. Calculate the percent yield by dividing the actual yield by the theoretical yield and multiplying by 100.
Solution:
A From the formulas given for the reactants and the products, we see that the chemical equation is balanced as written.
According to the equation, 1 mol of each reactant combines to give 1 mol of product plus 1 mol of water.
B To determine which reactant is limiting, we need to know their molar masses, which are calculated from their structural
formulas: p-aminobenzoic acid (C7H7NO2), 137.14 g/mol; 2-diethylaminoethanol (C6H15NO), 117.19 g/mol. Thus the reaction
used the following numbers of moles of reactants:
1 mol
mol p-aminobenzoic acid = 10.0 g × = 0.0729 mol p-aminbenzoic acid
137.14 g

1 mol
mol 2-diethylaminoethanol = 10.0 g × = 0.0853 mol 2-diethylaminoethanol
117.19 g

The reaction requires a 1:1 mole ratio of the two reactants, so p-aminobenzoic acid is the limiting reactant. Based on the
coefficients in the balanced chemical equation, 1 mol of p-aminobenzoic acid yields 1 mol of procaine. We can therefore obtain
only a maximum of 0.0729 mol of procaine. To calculate the corresponding mass of procaine, we use its structural formula
(C13H20N2O2) to calculate its molar mass, which is 236.31 g/mol.
236.31 g
theoretical yield of procaine = 0.0729 mol × = 17.2 g
1 mol

C The actual yield was only 15.7 g of procaine, so the percent yield (via Equation 10) is
15.7 g
percent yield = × 100 = 91.3%
17.2 g

(If the product were pure and dry, this yield would indicate very good lab technique!)

Exercise 4 : Extraction of Lead

Lead was one of the earliest metals to be isolated in pure form. It occurs as concentrated deposits of a distinctive ore called
galena (PbS ), which is easily converted to lead oxide (PbO) in 100% yield by roasting in air via the following reaction:

2 PbS(s) + 3 O → 2 PbO(s) + 2 SO (g)

2 2

The resulting PbO is then converted to the pure metal by reaction with charcoal. Because lead has such a low melting point
(327°C), it runs out of the ore-charcoal mixture as a liquid that is easily collected. The reaction for the conversion of lead oxide
to pure lead is as follows:

PbO(s) + C(s) → Pb(l) + CO(g)

If 93.3 kg of PbO is heated with excess charcoal and 77.3 kg of pure lead is obtained, what is the percent yield?

9 [Link]
 Electrolytically refined pure (99.989 %) superficially oxidized lead nodules and a high purity (99.989 %) 1 cm
3
lead cube for
comparison. Figure used with permission from Wikipedia.

Answer
89.2%

Percent yield can range from 0% to 100%. In the laboratory, a student will occasionally obtain a yield that appears to be greater
than 100%. This usually happens when the product is impure or is wet with a solvent such as water. If this is not the case, then the
student must have made an error in weighing either the reactants or the products. The law of conservation of mass applies even to
undergraduate chemistry laboratory experiments. A 100% yield means that everything worked perfectly, and the chemist obtained
all the product that could have been produced. Anyone who has tried to do something as simple as fill a salt shaker or add oil to a
car’s engine without spilling knows the unlikelihood of a 100% yield. At the other extreme, a yield of 0% means that no product
was obtained. A percent yield of 80%–90% is usually considered good to excellent; a yield of 50% is only fair. In part because of
the problems and costs of waste disposal, industrial production facilities face considerable pressures to optimize the yields of
products and make them as close to 100% as possible.

Summary
The stoichiometry of a balanced chemical equation identifies the maximum amount of product that can be obtained. The
stoichiometry of a reaction describes the relative amounts of reactants and products in a balanced chemical equation. A
stoichiometric quantity of a reactant is the amount necessary to react completely with the other reactant(s). If a quantity of a
reactant remains unconsumed after complete reaction has occurred, it is in excess. The reactant that is consumed first and limits the
amount of product(s) that can be obtained is the limiting reactant. To identify the limiting reactant, calculate the number of moles
of each reactant present and compare this ratio to the mole ratio of the reactants in the balanced chemical equation. The maximum
amount of product(s) that can be obtained in a reaction from a given amount of reactant(s) is the theoretical yield of the reaction.
The actual yield is the amount of product(s) actually obtained in the reaction; it cannot exceed the theoretical yield. The percent
yield of a reaction is the ratio of the actual yield to the theoretical yield, expressed as a percentage.

5.5 Limiting Reactant and Theoretical Yield and Percent Yield is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or
curated by LibreTexts.

10 [Link]
5.6 Representing Aqueous Reactions Molecular and Ionic and Complete Ionic
Equations
Learning Objectives
To understand what information is obtained by each type of ionic equation
The chemical equations discussed earlier showed the identities of the reactants and the products and gave the stoichiometries of the
reactions, but they told us very little about what was occurring in solution. In contrast, equations that show only the hydrated
species focus our attention on the chemistry that is taking place and allow us to see similarities between reactions that might not
otherwise be apparent.
Let’s consider the reaction of silver nitrate with potassium dichromate. When aqueous solutions of silver nitrate and potassium
dichromate are mixed, silver dichromate forms as a red solid. The overall chemical equation that shows all the reactants and
products as undissociated, electrically neutral compounds:
2AgN O3 (aq) + K2 C r2 O7 (aq) → Ag2 C r2 O7 (s) + 2KN O3 (aq) (1)

Although Equation 1 gives the identity of the reactants and the products, it does not show the identities of the actual species in
solution. Because ionic substances such as AgNO3 and K2Cr2O7 are strong electrolytes, they dissociate completely in aqueous
solution to form ions. In contrast, because Ag2Cr2O7 is not very soluble, it separates from the solution as a solid. To find out what
is actually occurring in solution, it is more informative to write the reaction as a complete ionic equation, showing which ions and
molecules are hydrated and which are present in other forms and phases:
+ − + 2− + −
2Ag (aq) + 2N O (aq) + 2 K (aq) + C r2 O (aq) → Ag2 C r2 O7 (s) + 2 K (aq) + 2N O (aq) (2)
3 7 3

Note that K+(aq) and NO3−(aq) ions are present on both sides of the equation, and their coefficients are the same on both sides.
These ions are called spectator ions because they do not participate in the actual reaction. Canceling the spectator ions gives the
net ionic equation, which shows only those species that participate in the chemical reaction:
+ 2−
2Ag (aq) + C r2 O (aq) → Ag2 C r2 O7 (s) (3)
7

Both mass and charge must be conserved in chemical reactions because the numbers of electrons and protons do not change. For
charge to be conserved, the sum of the charges of the ions multiplied by their coefficients must be the same on both sides of the
equation. In Equation 3, the charge on the left side is 2(+1) + 1(−2) = 0, which is the same as the charge of a neutral Ag2Cr2O7
formula unit.
By eliminating the spectator ions, we can focus on the chemistry that takes place in a solution. For example, the overall chemical
equation for the reaction between silver fluoride and ammonium dichromate is as follows:
2AgF (aq) + (N H4 )2 C r2 O7 (aq) → Ag2 C r2 O7 (s) + 2N H4 F (aq) (4)

The complete ionic equation for this reaction is as follows:

+ − + 2− + −
2Ag (aq) + 2 F (aq) + 2N H (aq) + C r2 O (aq) → Ag2 C r2 O7 (s) + 2N H (aq) + 2 F (aq) (5)
4 7 4

Because two NH4+(aq) and two F−(aq) ions appear on both sides of Equation 5, they are spectator ions. They can therefore be
canceled to give the net ionic equation (Equation 6), which is identical to Equation 3:
+ 2−
2Ag (aq) + C r2 O (aq) → Ag2 C r2 O7 (s) (6)
7

If we look at net ionic equations, it becomes apparent that many different combinations of reactants can result in the same net
chemical reaction. For example, we can predict that silver fluoride could be replaced by silver nitrate in the preceding reaction
without affecting the outcome of the reaction.
Only strong electrolytes can be separated into their component ions. To determine which compounds are strong electrolytes, you
first look to see if they are designated as aqueous, meaning their formula is followed by the symbol (aq).
*Not all aqueous species can be separated into ions, be no species that are not aqueous can be separated into ions.*
Once you have identified the aqueous species, you need to see if the substance is either

1 [Link]
 a) an ionically-bonded compound
or
b) one of the six strong acids: HCl, HBr, HI, HNO3, HClO4, or H2SO4.
*Only those aqueous compounds that fall into either category a) or b) can be separated into ions.*
Thus, as you learned previously, most covalently-bonded compounds, even if tehy are aqueous, will not be separated into ions.

Example 1
Write the overall chemical equation, the complete ionic equation, and the net ionic equation for the reaction of aqueous barium
nitrate with aqueous sodium phosphate to give solid barium phosphate and a solution of sodium nitrate.
Given: reactants and products
Asked for: overall, complete ionic, and net ionic equations
Strategy:
Write and balance the overall chemical equation. Write all the soluble reactants and products in their dissociated form to give
the complete ionic equation; then cancel species that appear on both sides of the complete ionic equation to give the net ionic
equation.
Solution:
From the information given, we can write the unbalanced chemical equation for the reaction:
Ba(N O3 )2 (aq) + N a3 P O4 (aq) → Ba3 (P O4 )2 (s) + N aN O3 (aq) (7)

2+
Because the product is Ba3(PO4)2, which contains three Ba ions and two PO43− ions per formula unit, we can balance the
equation by inspection:
3Ba(N O3 )2 (aq) + 2N a3 P O4 (aq) → Ba3 (P O4 )2 (s) + 6N aN O3 (aq) (8)

This is the overall balanced chemical equation for the reaction, showing the reactants and products in their undissociated form.
To obtain the complete ionic equation, we write each soluble reactant and product in dissociated form:
2+ − + 3− + −
3Ba (aq) + 6N O (aq) + 6N a (aq) + 2P O (aq) → Ba3 (P O4 )2 (s) + 6N a (aq) + 6N O (aq) (9)
3 4 3

The six NO3−(aq) ions and the six Na+(aq) ions that appear on both sides of the equation are spectator ions that can be canceled
to give the net ionic equation:
2+ 3−
3Ba (aq) + 2P O (aq) → Ba3 (P O4 )2 (s) (10)
4

Exercise 1
Write the overall chemical equation, the complete ionic equation, and the net ionic equation for the reaction of aqueous silver
fluoride with aqueous sodium phosphate to give solid silver phosphate and a solution of sodium fluoride.
Answer:
overall chemical equation:

3AgF (aq) + N a3 P O4 (aq) → Ag3 P O4 (s) + 3N aF (aq) (11)

complete ionic equation:

+ − + 3− + −
3Ag (aq) + 3 F (aq) + 3N a (aq) + P O (aq) → Ag3 P O4 (s) + 3N a (aq) + 3 F (aq) (12)
4

net ionic equation:

+ 3−
3Ag (aq) + P O (aq) → Ag3 P O4 (s) (13)
4

2 [Link]
Summary
The chemical equation for a reaction in solution can be written in three ways. The overall chemical equation shows all the
substances present in their undissociated forms; the complete ionic equation shows all the substances present in the form in which
they actually exist in solution; and the net ionic equation is derived from the complete ionic equation by omitting all spectator
ions, ions that occur on both sides of the equation with the same coefficients. Net ionic equations demonstrate that many different
combinations of reactants can give the same net chemical reaction.

Key Takeaway
A complete ionic equation consists of the net ionic equation and spectator ions.

Conceptual Problem
1. What information can be obtained from a complete ionic equation that cannot be obtained from the overall chemical equation?

Contributors
Modified by Joshua Halpern (Howard University)

5.6 Representing Aqueous Reactions Molecular and Ionic and Complete Ionic Equations is shared under a CC BY-NC-SA 4.0 license and was
authored, remixed, and/or curated by LibreTexts.

3 [Link]
5.7 Chemical Reactions and Aqueous Reactions (Exercises)
These are homework exercises to accompany the Textmap created for Chemistry: A Molecular Approach by Nivaldo Tro.
Complementary General Chemistry question banks can be found for other Textmaps and can be accessed here. In addition to these
publicly available questions, access to private problems bank for use in exams and homework is available to faculty only on an
individual basis; please contact Delmar Larsen for an account with access permission.

Additional Questions
1. The Kingston Steam Plant burns 14,000 tons of coal each day and generates 1010 kilowatts-hours of electricity each year
(enough for 700,000 homes). Coal is primarily carbon which undergoes combustion in the following reaction: C(s) + O2 (g) ->
CO2(g)
How many grams of oxygen is required for the combustion of 1 day's coal?
a. How much carbon dioxide is produced each day?
2. CO2 is removed from the atomsphere by trees and converted into cellulose. The basic reaction for this is: 6 CO2 (g) + 5 H2O (l)
-> C6H10O5 (s) + 6 O2 (g)
a. How many grams of water are required to process the CO2 from one day's electrical production at the Kingston Steam
Plant?
b. How much oxygen is produced by this process?
c. How much cellulose is produced?
d. If you assume that a tree weigh's 2 tons, how many trees are required to process the CO2 produced in one day?
3. A typical automobile gets 30 miles per gallon of gas and drives 12,000 miles every year. Assuming that octane (C8H18, density
0.7025 g cm-3) is a principal component of gasoline;
a. How much oxygen is required for a car to run for 1 year?
b. How much CO2 is produced by the car in 1 year?
c. How many trees are required to remove the CO2 produced by the car in 1 year?
4. Modern instrumental techniques are capable of detecting lead in a milliliter sample at picomolar concentration.
a. How many moles of lead are in the sample?
b. What is the mass of lead in this sample?
c. How many grams of sodium chloride would be required to precipitate all the lead in this sample as lead (II) chloride?
d. What would the mass of the lead (II) chloride precipitate be?
[Link] Kingston Steam Plant burns 14,000 tons of coal each day and generates 1010 kilowatts-hours of electricity each year
(enough for 700,000 homes). Coal is primarily carbon which undergoes combustion in the following reaction: C(s) + O2 (g) ->
CO2 (g) [Link] many grams of oxygen is required for the combustion of 1 day's coal? [Link] much carbon dioxide is produced
each day? Coal is the limiting reageint in this reaction (unless the earth runs out of oxygen, but then we are all in really big
trouble). So first calculate the number of moles of coal. Mass coal 14000. ton Mass = coal 1.4 104 . . ton 2000. lb 1. ton [Link]
lb Mass = coal 1.27 1010 gm MW C [Link] 1 Mole C Mass coal MW C Mole = C 1.057 109 mole From the balanced
reaction; for every mole of carbon, one mole of oxygen is required, and one mole of CO2 is produced. Mass of O2 Mole O2 Mole
C MW O2 [Link] 1 Mass O2 Mole . O2 MW O2 Mass = O2 3.384 1010 gm Mass of CO2 Mole CO2 Mole C MW
CO2 . . (12.011 ) 2.15.9994 gm mole 1 Mass CO2 Mole . CO2 MW CO2 Mass = CO2 4.654 1010 gm S.E. Van Bramer Widener
University 11/4/97 2.CO2 is removed from the atomsphere by trees and converted into cellulose. The basic reaction for this is: 6
CO2 (g) + 5 H2O (l) -> C6H10O5 (s) + 6 O2 (g) [Link] many grams of water are required to process the CO2 from one day's
electrical production at the Kingston Steam Plant? [Link] much oxygen is produced by this process? [Link] much cellulose is
produced? [Link] you assume that a tree weigh's 2 tons, how many trees are required to process the CO2 produced in one day? From
the balanced chemical reaction, five moles of water are required for 6 moles of carbon dioxide: Mole H2O Mole . CO2 5 6 Mole =
H2O 8.812 108 mole MW H2O . . ( ) 2.1.00794 15.9994 gm mole 1 Mass H2O Mole . H2O MW H2O Mass = H2O 1.587 1010 gm
Density H2O 1. gm mL Volume H2O Mass H2O Density H2O Volume = H2O 1.587 1010 mL Volume = H2O 4.194 106 gal From
the balanced chemical reaction, 6 moles of O2 are produced from 6 moles of carbon dioxide: Mole O2 Mole . CO2 6 6 Mole = O2
1.057 109 mole MW O2 . . ( ) 2.15.9994 gm mole 1 Mass O2 Mole . O2 MW O2 Mass = O2 3.384 1010 gm Notice that this is
identical to the mass of O2 used in the combustion reaction. All the oxygen is recovered by the tree. S.E. Van Bramer Widener
University 11/4/97 From the balanced chemical reaction, 1 mole of cellulose is produced from 6 moles of carbon dioxide: Mole

1 [Link]
cellulose Mole . CO2 1 6 Mole = cellulose 1.762 108 mole MW cellulose . . ( ) 12.011.6 1.00794.10 15.9994.5 gm mole 1 Mass
cellulose Mole . cellulose MW cellulose Mass = cellulose 2.858 1010 gm Assuming that a tree weighs 2 tons and is all cellulose:
tree 2. ton tree = 1.814 106 gm Mass = cellulose 2.857 107 kg 1. tree 1.814.10 . 6 gm Mass = cellulose 15749 tree So from this
"back of the envelope" calculation, about 16 thousand trees must be grown to absorb the carbon dioxide produced in one day by
this power plant. 3.A typical automobile gets 30 miles per gallon of gas and drives 12,000 miles every year. Assuming that octane
(C8H18, density 0.7025 g cm-1) is a principal component of gasoline; [Link] much oxygen is required for a car to run for 1 year?
[Link] much CO2 is produced by the car in 1 year? [Link] many trees are required to remove the CO2 produced by the car in 1
year? Let's start with a balanced reaction: 2 C8H18 + 25 O2 --> 16 CO2 + 18 H2O Next calculate the amout of octane used:
mileage [Link] 1 distance [Link] volume gas distance mileage volume = gas 4 102 gal volume = gas 1.514 106 mL S.E. Van
Bramer Widener University 11/4/97 density gas [Link] 3 Mass gas density . gas volume gas Mass = gas 1.064 106 gm MW
octane . . ( ) 12.011.8 1.00794.18 gm mole 1 Mole octane Mass gas MW octane Mole = octane 9.312 103 From the balanced
chemical reaction, 25 moles of O2 are required for 2 moles of octane: Mole O2 Mole . octane 25 2 Mole = O2 1.164 105 mole MW
O2 . . ( ) 2.15.9994 gm mole 1 Mass O2 Mole . O2 MW O2 Mass = O2 3.725 106 gm Mass = O2 4.106 ton From the balanced
chemical reaction, 16 moles of CO2 are produced by 2 moles of octane: Mole CO2 Mole . octane 16 2 Mass CO2 Mole . CO2 MW
CO2 Mass = CO2 3.278 106 gm Mass = CO2 3.614 ton From the balanced chemical reaction, 1 mole of cellulose is produced from
6 moles of carbon dioxide: Mole cellulose Mole . CO2 1 6 Mole = cellulose 1.242 104 mole Mass cellulose Mole . cellulose MW
cellulose Mass = cellulose 2.013 106 gm Mass = cellulose 1.1 tree S.E. Van Bramer Widener University 11/4/97 [Link]
instrumental techniques are capable of detecting lead in a milliliter sample at picomolar concentration. [Link] many moles of lead
are in the sample? [Link] is the mass of lead in this sample? [Link] many grams of sodium chloride would be required to
precipitate all the lead in this sample as lead (II) chloride? [Link] would the mass of the lead (II) chloride precipitate be? Calculate
the amount of lead in the sample from the concentration and the total volume Concentration Pb 10 . . 12 mole liter 1 Volume Pb
[Link] Volume = Pb 1 10 3 liter Mole Pb Concentration . Pb Volume Pb Mole = Pb 1 10 15 mole MW Pb [Link] 1 Mass Pb
MW . Pb Mole Pb Mass = Pb 2.072 10 13 gm First write out the balanced equation: Pb2+ + 2 NaCl --> PbCl2 + 2 Na1+ (Note: the
lead is an ion in aqueous solution) From the balanced reaction, 2 moles of NaCl are required for each mole of Pb2+ Mole NaCl
Mole . Pb 2 1 Mole = NaCl 2 10 15 mole MW NaCl . . ( 22.989768 35.4527) gm mole 1 MW = NaCl 58.442 [Link] 1 Mass
NaCl MW . NaCl Mole NaCl Mass = NaCl 1.169 10 13 gm From the balanced reaction, 1 mole of PbCl2 is produced for each mole
of Pb2+ Mole PbCl2 Mole . Pb 1 1 Mole = PbCl2 1 10 15 mole MW PbCl2 . . (107.2 ) 2.35.4527 gm mole 1 MW = PbCl2 1.781
102 [Link] 1 Mass NaCl MW . NaCl Mole NaCl Mass = NaCl 1.169 10 13 gm

Q1
When the following solutions are mixed, does a precipitate form? Write out the total, total ionic, and net ionic equations.
1. a. silver nitrate and rubidium chloride
2. b. lead nitrate and potassium chloride
3. c. mercury (I) nitrate and hydrochloric acid
4. d. calcium chloride and sodium carbonate
5. e. magnesium nitrate and calcium chloride
6. f. potassium sulfate and barium chloride

Q2
Precipitation Reactions and Solubility.
1. a. Step 1: 0.8765 g of silver (I) nitrate is placed in a 250 mL volumetric flask diluted to the mark with deionized water.
Determine the concentration of each ion in solution.
2. b. Step 2: 1.8793 g of potassium chloride is placed in a 250 mL volumetric flask diluted to the mark with deionized water.
Determine the concentration of each ion in solution.
3. c. Step 3: 50.0 mL of the silver (I) nitrate solution and 50.0 mL of the potassium chloride solution are mixed together in an
erlenmyer flask. Determine the mass of any precipitate formed and the concentration of each ion in solution.

5.7 Chemical Reactions and Aqueous Reactions (Exercises) is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or
curated by LibreTexts.

2 [Link]
 CHAPTER OVERVIEW

6: Reaction Kinetics
6.1: Chemical Kinetics
6.2 The Effect of Concentration on Reaction Rate
6.3: Reaction Mechanisms
6.4: The Effect of Temperature on Reaction Rate
6.5 Catalysts

6: Reaction Kinetics is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
6.1: Chemical Kinetics
Skills to Develop
To determine the reaction rate of a reaction.

Reaction rates are usually expressed as the concentration of reactant consumed or the concentration of product formed per unit
time. The units are thus moles per liter per unit time, written as M/s, M/min, or M/h. To measure reaction rates, chemists initiate the
reaction, measure the concentration of the reactant or product at different times as the reaction progresses, perhaps plot the
concentration as a function of time on a graph, and then calculate the change in the concentration per unit time.

Figure 6.1.1 : The Progress of a Simple Reaction (A → B). The mixture initially contains only A molecules (purple). Over time,
the number of A molecules decreases and more B molecules (green) are formed (top). The graph shows the change in the number of
A and B molecules in the reaction as a function of time over a 1 min period (bottom).
The progress of a simple reaction (A → B) is shown in Figure 6.1.1; the beakers are snapshots of the composition of the solution at
10 s intervals. The number of molecules of reactant (A) and product (B) are plotted as a function of time in the graph. Each point in
the graph corresponds to one beaker in Figure 6.1.1. The reaction rate is the change in the concentration of either the reactant or the
product over a period of time. The concentration of A decreases with time, while the concentration of B increases with time.
Δ[B] Δ[A]
rate = =− (6.1.1)
Δt Δt

Square brackets indicate molar concentrations, and the capital Greek delta (Δ) means “change in.” Because chemists follow the
convention of expressing all reaction rates as positive numbers, however, a negative sign is inserted in front of Δ[A]/Δt to convert
that expression to a positive number. The reaction rate calculated for the reaction A → B using Equation 6.1.1 is different for each
interval (this is not true for every reaction, as shown below). A greater change occurs in [A] and [B] during the first 10 s interval,
for example, than during the last, meaning that the reaction rate is greatest at first.

Reaction rates generally decrease with time as reactant concentrations decrease.

Determining the Reaction Rate of Hydrolysis of Aspirin

We can use Equation 6.1.1 to determine the reaction rate of hydrolysis of aspirin, probably the most commonly used drug in the
world (more than 25,000,000 kg are produced annually worldwide). Aspirin (acetylsalicylic acid) reacts with water (such as water
in body fluids) to give salicylic acid and acetic acid, as shown in Figure 6.1.2.

6.1.1 [Link]
 Figure 6.1.2 : Hydrolysis of Aspirin reaction.
Because salicylic acid is the actual substance that relieves pain and reduces fever and inflammation, a great deal of research has
focused on understanding this reaction and the factors that affect its rate. Data for the hydrolysis of a sample of aspirin are in Table
6.1.1 and are shown in the graph in Figure 6.1.3.

Table 6.1.1: Data for Aspirin Hydrolysis in Aqueous Solution at pH 7.0 and 37°C*
Time (h) [Aspirin] (M) [Salicylic Acid] (M)

0 5.55 × 10−3 0

2.0 5.51 × 10−3 0.040 × 10−3

5.0 5.45 × 10−3 0.10 × 10−3

10 5.35 × 10−3 0.20 × 10−3

20 5.15 × 10−3 0.40 × 10−3

30 4.96 × 10−3 0.59 × 10−3

40 4.78 × 10−3 0.77 × 10−3

50 4.61 × 10−3 0.94 × 10−3

100 3.83 × 10−3 1.72 × 10−3

200 2.64 × 10−3 2.91 × 10−3

300 1.82 × 10−3 3.73 × 10−3

*The reaction at pH 7.0 is very slow. It is much faster under acidic conditions, such as those found in the stomach.

The data in Table 6.1.1 were obtained by removing samples of the reaction mixture at the indicated times and analyzing them for
the concentrations of the reactant (aspirin) and one of the products (salicylic acid).

6.1.2 [Link]
 Figure 6.1.3 : The Hydrolysis of Aspirin. This graph shows the concentrations of aspirin and salicylic acid as a function of time,
based on the hydrolysis data in Table 14.1. The time dependence of the concentration of the other product, acetate, is not shown,
but based on the stoichiometry of the reaction, it is identical to the data for salicylic acid.

6.1: Chemical Kinetics is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

6.1.3 [Link]
6.2 The Effect of Concentration on Reaction Rate
Skills to Develop
To understand the meaning of the rate law.

The factors that affect the reaction rate of a chemical reaction, which may determine whether a desired product is formed. In this
section, we will show you how to quantitatively determine the reaction rate.

Rate Laws
Typically, reaction rates decrease with time because reactant concentrations decrease as reactants are converted to products.
Reaction rates generally increase when reactant concentrations are increased. This section examines mathematical expressions
called rate laws, which describe the relationships between reactant rates and reactant concentrations. Rate laws are mathematical
descriptions of experimentally verifiable data.

Reaction Orders
For a reaction with the general equation:

aA + bB → cC + dD (1)

the experimentally determined rate law usually has the following form:
m n
rate = k[A] [B] (2)

The proportionality constant (k) is called the rate constant, and its value is characteristic of the reaction and the reaction
conditions. A given reaction has a particular rate constant value under a given set of conditions, such as temperature, pressure, and
solvent; varying the temperature or the solvent usually changes the value of the rate constant. The numerical value of k, however,
does not change as the reaction progresses under a given set of conditions.

Under a given set of conditions, the value of the rate constant does not change as the
reaction progresses.
The reaction rate thus depends on the rate constant for the given set of reaction conditions and the concentration of A and B raised
to the powers m and n, respectively. The values of m and n are derived from experimental measurements of the changes in reactant
concentrations over time and indicate the reaction order, the degree to which the reaction rate depends on the concentration of
each reactant; m and n need not be integers, but often are. For example, Equation 2 tells us that Equation 1 is mth order in reactant
A and nth order in reactant B. It is important to remember that n and m are not related to the stoichiometric coefficients a and b in
the balanced chemical equation and must be determined experimentally. The overall reaction order is the sum of all the exponents
in the rate law: m + n.
It is important to realize that in kinetics, the term "order" is used in the mathematical sense, referring to the value of the exponent.
For example, the equation x + y + z = 0 , is said to be third order in x, first order in y, and second order in z. Thus "order", in
3 2

kinetics, does not refer to which substance reacts "first" or "second".

The orders of the reactions (e.g. n and m) are not related to the stoichiometric coefficients
in the balanced chemical (e.g., a and b).
To illustrate how chemists interpret a differential rate law, consider the experimentally derived rate law for the hydrolysis of t-butyl
bromide in 70% aqueous acetone.

This reaction produces t-butanol according to the following equation:

1 [Link]
 (C H3 )3 C Br(soln) + H2 O(soln) → (C H3 )3 C OH(soln) + H Br(soln) (3)

Combining the rate expression in Equation 2 with the definition of average reaction rate
Δ[A]
rate = − (4)
Δt

gives a general expression for the differential rate law:

Δ[A]
m n
rate = − = k[A] [B] (5)
Δt

Inserting the identities of the reactants into Equation 5 gives the following expression for the differential rate law for the reaction:
Δ[(C H3 )3 CBr]
m n
rate = − = k[(C H3 )3 CBr] [ H2 O] (6)
Δt

Experiments to determine the rate law for the hydrolysis of t-butyl bromide show that the reaction rate is directly proportional to
the concentration of (CH3)3CBr but is independent of the concentration of water. Therefore, m and n in Equation 5 are 1 and 0,
respectively, and,
1 0
rate = k[(C H3 )3 C Br] [ H2 O] = k[(C H3 )3 C Br] (7)

Because the exponent for the reactant is 1, the reaction is first order in (CH3)3CBr. It is zeroth order in water because the exponent
for [H2O] is 0. (Recall that anything raised to the zeroth power equals 1.) Thus, the overall reaction order is 1 + 0 = 1. The reaction
orders state in practical terms that doubling the concentration of (CH3)3CBr doubles the reaction rate of the hydrolysis reaction,
halving the concentration of (CH3)3CBr halves the reaction rate, and so on. Conversely, increasing or decreasing the concentration
of water has no effect on the reaction rate. (Again, when working with rate laws, there is no simple correlation between the
stoichiometry of the reaction and the rate law. The values of k, m, and n in the rate law must be determined experimentally.)
Experimental data show that k has the value 5.15 × 10−4 s−1 at 25°C. The rate constant has units of reciprocal seconds (s−1) because
the reaction rate is defined in units of concentration per unit time (M/s). The units of a rate constant depend on the rate law for a
particular reaction.
Under conditions identical to those for the t-butyl bromide reaction, the experimentally derived differential rate law for the
hydrolysis of methyl bromide (CH3Br) is as follows:
Δ[C H3 Br]
′
rate = − = k [C H3 Br] (8)
Δt

This reaction also has an overall reaction order of 1, but the rate constant in Equation 8 is approximately 106 times smaller than that
for t-butyl bromide. Thus, methyl bromide hydrolyzes about 1 million times more slowly than t-butyl bromide, and this information
tells chemists how the reactions differ on a molecular level.
Frequently, changes in reaction conditions also produce changes in a rate law. In fact, chemists often alter reaction conditions to
study the mechanics of a reaction. For example, when t-butyl bromide is hydrolyzed in an aqueous acetone solution containing
OH− ions rather than in aqueous acetone alone, the differential rate law for the hydrolysis reaction does not change. In contrast, for
methyl bromide, the differential rate law becomes
−
rate = k'' [C H3 Br][OH ] (9)

with an overall reaction order of 2. Although the two reactions proceed similarly in neutral solution, they proceed very differently
in the presence of a base, providing clues as to how the reactions differ on a molecular level.

Example 1 : Writing Rate Laws from Reaction Orders

An experiment shows that the reaction of nitrogen dioxide with carbon monoxide:

NO (g) + CO(g) ⟶ NO(g) + CO (g) (10)

2 2

is second order in NO2 and zero order in CO at 100 °C. What is the rate law for the reaction?
Solution
The reaction will have the form:

2 [Link]
 m n
rate = k[ NO ] [CO] (11)
2

The reaction is second order in NO2; thus m = 2. The reaction is zero order in CO; thus n = 0. The rate law is:
2 0 2
rate = k[ NO ] [CO] = k[ NO ] (12)
2 2

Remember that a number raised to the zero power is equal to 1, thus [CO]0 = 1, which is why we can simply drop the
concentration of CO from the rate equation: the rate of reaction is solely dependent on the concentration of NO2. When we
consider rate mechanisms later in this chapter, we will explain how a reactant’s concentration can have no effect on a reaction
despite being involved in the reaction.

Exercise 1A
The rate law for the reaction:
H (g) + 2 NO(g) ⟶ N O(g) + H O(g) (13)
2 2 2

has been experimentally determined to be 2

rate = k[N O] [ H2 ] . What are the orders with respect to each reactant, and what is
the overall order of the reaction?

Answer
order in NO = 2
order in H2 = 1
overall order = 3

Exercise 1B
In a transesterification reaction, a triglyceride reacts with an alcohol to form an ester and glycerol. Many students learn about
the reaction between methanol (CH3OH) and ethyl acetate (CH3CH2OCOCH3) as a sample reaction before studying the
chemical reactions that produce biodiesel:

CH OH + CH CH OCOCH ⟶ CH OCOCH + CH CH OH (14)

3 3 2 3 3 3 3 2

The rate law for the reaction between methanol and ethyl acetate is, under certain conditions, experimentally determined to be:

rate = k[ CH OH] (15)

3

What is the order of reaction with respect to methanol and ethyl acetate, and what is the overall order of reaction?

Answer
order in CH3OH = 1
order in CH3CH2OCOCH3 = 0
overall order = 1

Determining the Rate Law of a Reaction

The number of fundamentally different mechanisms (sets of steps in a reaction) is actually rather small compared to the large
number of chemical reactions that can occur. Thus understanding reaction mechanisms can simplify what might seem to be a
confusing variety of chemical reactions. The first step in discovering the reaction mechanism is to determine the reaction’s rate law.
This can be done by designing experiments that measure the concentration(s) of one or more reactants or products as a function of
time. For the reaction A + B → products , for example, we need to determine k and the exponents m and n in the following
equation:
m n
rate = k[A] [B] (16)

To do this, we might keep the initial concentration of B constant while varying the initial concentration of A and calculating the
initial reaction rate. This information would permit us to deduce the reaction order with respect to A. Similarly, we could determine
the reaction order with respect to B by studying the initial reaction rate when the initial concentration of A is kept constant while
the initial concentration of B is varied. In earlier examples, we determined the reaction order with respect to a given reactant by

3 [Link]
comparing the different rates obtained when only the concentration of the reactant in question was changed. An alternative way of
determining reaction orders is to set up a proportion using the rate laws for two different experiments. Rate data for a hypothetical
reaction of the type A + B → products are given in Table 1.
Table 1 : Rate Data for a Hypothetical Reaction of the Form A + B → products
Experiment [A] (M) [B] (M) Initial Rate (M/min)

1 0.50 0.50 8.5 × 10−3

2 0.75 0.50 19 × 10−3

3 1.00 0.50 34 × 10−3

4 0.50 0.75 8.5 × 10−3

5 0.50 1.00 8.5 × 10−3

The general rate law for the reaction is given in Equation 16. We can obtain m or n directly by using a proportion of the rate laws
for two experiments in which the concentration of one reactant is the same, such as Experiments 1 and 3 in Table 3.
m n
rate1 k[ A1 ] [ B1 ]
= (17)
m n
rate3 k[ A3 ] [ B3 ]

Inserting the appropriate values from Table 3,

−3 m n
8.5 × 10 M/min k[0.50 M] [0.50 M]
= (18)
−3 m n
34 × 10 M/min k[1.00 M] [0.50 M]

Because 1.00 to any power is 1, [1.00 M]m = 1.00 M. We can cancel like terms to give 0.25 = [0.50]m, which can also be written as
1/4 = [1/2]m. Thus we can conclude that m = 2 and that the reaction is second order in A. By selecting two experiments in which
the concentration of B is the same, we were able to solve for m.
Conversely, by selecting two experiments in which the concentration of A is the same (e.g., Experiments 5 and 1), we can solve for
n.
m n
rate1 k[ A1 ] [ B1 ]
=
m n
rate5 k[ A5 ] [ B5 ]

Substituting the appropriate values from Table 3,

−3 m n
8.5 × 10 M/min k[0.50 M] [0.50 M]
= (19)
−3 m n
8.5 × 10 M/min k[0.50 M] [1.00 M]

Canceling leaves 1.0 = [0.50]n, which gives n =0 ; that is, the reaction is zeroth order in B . The experimentally determined rate
law is therefore
rate = k[A]2[B]0 = k[A]2
We can now calculate the rate constant by inserting the data from any row of Table 3 into the experimentally determined rate law
and solving for k . Using Experiment 2, we obtain
19 × 10−3 M/min = k(0.75 M)2
3.4 × 10−2 M−1·min−1 = k
You should verify that using data from any other row of Table 1 gives the same rate constant. This must be true as long as the
experimental conditions, such as temperature and solvent, are the same.

Example 3
Nitric oxide is produced in the body by several different enzymes and acts as a signal that controls blood pressure, long-term
memory, and other critical functions. The major route for removing NO from biological fluids is via reaction with O to give 2

4 [Link]
N O2 , which then reacts rapidly with water to give nitrous acid and nitric acid:

These reactions are important in maintaining steady levels of NO. The following table lists kinetics data for the reaction of NO
with O2 at 25°C:

2N O(g) + O2 (g) → 2N O2 (g)

Determine the rate law for the reaction and calculate the rate constant.

Experiment [NO]0 (M) [O2]0 (M) Initial Rate (M/s)

1 0.0235 0.0125 7.98 × 10−3

2 0.0235 0.0250 15.9 × 10−3

3 0.0470 0.0125 32.0 × 10−3

4 0.0470 0.0250 63.5 × 10−3

Given: balanced chemical equation, initial concentrations, and initial rates

Asked for: rate law and rate constant
Strategy:
A. Compare the changes in initial concentrations with the corresponding changes in rates of reaction to determine the reaction
order for each species. Write the rate law for the reaction.
B. Using data from any experiment, substitute appropriate values into the rate law. Solve the rate equation for k.
Solution:
A Comparing Experiments 1 and 2 shows that as [O2] is doubled at a constant value of [NO2], the reaction rate approximately
doubles. Thus the reaction rate is proportional to [O2]1, so the reaction is first order in O2. Comparing Experiments 1 and 3
shows that the reaction rate essentially quadruples when [NO] is doubled and [O2] is held constant. That is, the reaction rate is
proportional to [NO]2, which indicates that the reaction is second order in NO. Using these relationships, we can write the rate
law for the reaction:
rate = k[NO]2[O2]
B The data in any row can be used to calculate the rate constant. Using Experiment 1, for example, gives
−3
rate 7.98 × 10 M/s
3 −2 −1
k = = = 1.16 × 10 M ⋅s (20)
2 2
[NO] [ O2 ] (0.0235 M) (0.0125 M)

Alternatively, using Experiment 2 gives

−3
rate 15.9 × 10 M/s
3 −2 −1
k = = = 1.15 × 10 M ⋅s (21)
2 2
[NO] [ O2 ] (0.0235 M) (0.0250 M)

The difference is minor and associated with significant digits and likely experimental error in making the table.
The overall reaction order (m + n) = 3 , so this is a third-order reaction whose rate is determined by three reactants. The units
of the rate constant become more complex as the overall reaction order increases.

Exercise 3
The peroxydisulfate ion (S2O82−) is a potent oxidizing agent that reacts rapidly with iodide ion in water:
2− − 2− −
S2 O + 3I → 2S O +I
8(aq) (aq) 4(aq) 3(aq)

The following table lists kinetics data for this reaction at 25°C. Determine the rate law and calculate the rate constant.

Experiment [S2O82−]0 (M) [I−]0 (M) Initial Rate (M/s)

5 [Link]
 Experiment [S2O82−]0 (M) [I−]0 (M) Initial Rate (M/s)

1 0.27 0.38 2.05

2 0.40 0.38 3.06

3 0.40 0.22 1.76

Answer:
rate = k[S2O82−][I−]; k = 20 M−1·s−1

Summary
The rate law for a reaction is a mathematical relationship between the reaction rate and the concentrations of species in solution.
The rate constant (k) of a rate law is a constant of proportionality between the reaction rate and the reactant concentration. The
exponent to which a concentration is raised in a rate law indicates the reaction order, the degree to which the reaction rate depends
on the concentration of a particular reactant.

6.2 The Effect of Concentration on Reaction Rate is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

6 [Link]
6.3: Reaction Mechanisms
Skills to Develop
To determine the individual steps of a simple reaction.

One of the major reasons for studying chemical kinetics is to use measurements of the macroscopic properties of a system, such as the rate of change in the concentration of reactants or products with
time, to discover the sequence of events that occur at the molecular level during a reaction. This molecular description is the mechanism of the reaction; it describes how individual atoms, ions, or
molecules interact to form particular products. The stepwise changes are collectively called the reaction mechanism.
In an internal combustion engine, for example, isooctane reacts with oxygen to give carbon dioxide and water:
2 C8 H18 (l) + 25 O2 (g) → 16C O2 (g) + 18 H2 O(g) (6.3.1)

For this reaction to occur in a single step, 25 dioxygen molecules and 2 isooctane molecules would have to collide simultaneously and be converted to 34 molecules of product, which is very unlikely.
It is more likely that a complex series of reactions takes place in a stepwise fashion. Each individual reaction, which is called an elementary reaction, involves one, two, or (rarely) three atoms,
molecules, or ions. The overall sequence of elementary reactions is the mechanism of the reaction. The sum of the individual steps, or elementary reactions, in the mechanism must give the balanced
chemical equation for the overall reaction.

The overall sequence of elementary reactions is the mechanism of the reaction.

Molecularity and the Rate-Determining Step

To demonstrate how the analysis of elementary reactions helps us determine the overall reaction mechanism, we will examine the much simpler reaction of carbon monoxide with nitrogen dioxide.
N O2 (g) + C O(g) → N O(g) + C O2 (g)
(6.3.2)

From the balanced chemical equation, one might expect the reaction to occur via a collision of one molecule of N O2 with a molecule of CO that results in the transfer of an oxygen atom from
nitrogen to carbon. The experimentally determined rate law for the reaction, however, is as follows:
2
rate = k[N O2 ] (6.3.3)

The fact that the reaction is second order in [N O ] and independent of [C O] tells us that it does not occur by the simple collision model outlined previously. If it did, its predicted rate law would be
2

rate = k[N O2 ][C O]. (6.3.4)

The following two-step mechanism is consistent with the rate law if step 1 is much slower than step 2:

slow
step 1 N O2 + N O2 −−→ N O3 + NO elementary reaction

step 2 N O3 + CO → N O2 + CO2 elementary reaction

––––––––––––––––––––––––––

sum N O2 + CO → NO + CO2 overall reaction

According to this mechanism, the overall reaction occurs in two steps, or elementary reactions. Summing steps 1 and 2 and canceling on both sides of the equation gives the overall balanced chemical
equation for the reaction. The N O molecule is an intermediate in the reaction, a species that does not appear in the balanced chemical equation for the overall reaction. It is formed as a product of
3

the first step but is consumed in the second step.

The sum of the elementary reactions in a reaction mechanism must give the overall balanced chemical equation of the reaction.

Using Molecularity to Describe a Rate Law

The molecularity of an elementary reaction is the number of molecules that collide during that step in the mechanism. If there is only a single reactant molecule in an elementary reaction, that step is
designated as unimolecular; if there are two reactant molecules, it is bimolecular; and if there are three reactant molecules (a relatively rare situation), it is termolecular. Elementary reactions that
involve the simultaneous collision of more than three molecules are highly improbable and have never been observed experimentally. (To understand why, try to make three or more marbles or pool
balls collide with one another simultaneously!)

Figure 6.3.1 : The Basis for Writing Rate Laws of Elementary Reactions. This diagram illustrates how the number of possible collisions per unit time between two reactant species, A and B, depends
on the number of A and B particles present. The number of collisions between A and B particles increases as the product of the number of particles, not as the sum. This is why the rate law for an
elementary reaction depends on the product of the concentrations of the species that collide in that step.
Writing the rate law for an elementary reaction is straightforward because we know how many molecules must collide simultaneously for the elementary reaction to occur; hence the order of the
elementary reaction is the same as its molecularity (Table 6.3.1). In contrast, the rate law for the reaction cannot be determined from the balanced chemical equation for the overall reaction. The
general rate law for a unimolecular elementary reaction (A → products) is rate = k[A]. For bimolecular reactions, the reaction rate depends on the number of collisions per unit time, which is
proportional to the product of the concentrations of the reactants, as shown in Figure 6.3.1. For a bimolecular elementary reaction of the form A + B → products, the general rate law is rate = k[A][B].
Table 6.3.1: Common Types of Elementary Reactions and Their Rate Laws
Elementary Reaction Molecularity Rate Law Reaction Order

A → products unimolecular rate = k[A] first

2A → products bimolecular rate = k[A]2 second

A + B → products bimolecular rate = k[A][B] second

2A + B → products termolecular rate = k[A]2[B] third

A + B + C → products termolecular rate = k[A][B][C] third

For elementary reactions, the order of the elementary reaction is the same as its molecularity. In contrast, the rate law cannot be determined from
the balanced chemical equation for the overall reaction (unless it is a single step mechanism and is therefore also an elementary step).

6.3.1 [Link]
Identifying the Rate-Determining Step
Note the important difference between writing rate laws for elementary reactions and the balanced chemical equation of the overall reaction. Because the balanced chemical equation does not
necessarily reveal the individual elementary reactions by which the reaction occurs, we cannot obtain the rate law for a reaction from the overall balanced chemical equation alone. In fact, it is the rate
law for the slowest overall reaction, which is the same as the rate law for the slowest step in the reaction mechanism, the rate-determining step, that must give the experimentally determined rate law
for the overall [Link] statement is true if one step is substantially slower than all the others, typically by a factor of 10 or more. If two or more slow steps have comparable rates, the
experimentally determined rate laws can become complex. Our discussion is limited to reactions in which one step can be identified as being substantially slower than any other. The reason for this is
that any process that occurs through a sequence of steps can take place no faster than the slowest step in the sequence. In an automotive assembly line, for example, a component cannot be used faster
than it is produced. Similarly, blood pressure is regulated by the flow of blood through the smallest passages, the capillaries. Because movement through capillaries constitutes the rate-determining
step in blood flow, blood pressure can be regulated by medications that cause the capillaries to contract or dilate. A chemical reaction that occurs via a series of elementary reactions can take place no
faster than the slowest step in the series of reactions.

Rate-determining step. The phenomenon of a rate-determining step can be compared to a succession of funnels. The smallest-diameter funnel controls the rate at which the bottle is filled, whether it
is the first or the last in the series. Pouring liquid into the first funnel faster than it can drain through the smallest results in an overflow.
Look at the rate laws for each elementary reaction in our example as well as for the overall reaction.

k1
2
step 1 N O2 + N O2 −
→ N O3 + NO rate = k1 [N O2 ] (predicted)

k2

step 2 N O3 + CO − → N O2 + CO2 rate = k2 [N O3 ][CO] (predicted)

––––––––––––––––––––––––––

k
2
sum N O2 + CO → NO + CO2 rate = k[N O2 ] (observed)

The experimentally determined rate law for the reaction of N O with C O is the same as the predicted rate law for step 1. This tells us that the first elementary reaction is the rate-determining step, so
2

k for the overall reaction must equal k . That is, NO3 is formed slowly in step 1, but once it is formed, it reacts very rapidly with CO in step 2.
1

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data. If a proposed mechanism predicts the wrong experimental rate law, however, the
mechanism must be incorrect.

Example 6.3.1 : A Reaction with an Intermediate

In an alternative mechanism for the reaction of NO2 with CO, N2O4 appears as an intermediate.

k1
step 1 N O2 + N O2 −
→ N2 O4

k2

step 2 N2 O4 + CO − → NO + N O2 + CO2
–––––––––––––––––––––––––––––––––

sum N O2 + CO → NO + CO2

Write the rate law for each elementary reaction. Is this mechanism consistent with the experimentally determined rate law (rate = k[NO2]2)?
Given: elementary reactions
Asked for: rate law for each elementary reaction and overall rate law
Strategy:
A. Determine the rate law for each elementary reaction in the reaction.
B. Determine which rate law corresponds to the experimentally determined rate law for the reaction. This rate law is the one for the rate-determining step.
Solution:
A The rate law for step 1 is rate = k1[NO2]2; for step 2, it is rate = k2[N2O4][CO].
B If step 1 is slow (and therefore the rate-determining step), then the overall rate law for the reaction will be the same: rate = k1[NO2]2. This is the same as the experimentally determined rate law.
Hence this mechanism, with N2O4 as an intermediate, and the one described previously, with NO3 as an intermediate, are kinetically indistinguishable. In this case, further experiments are needed
to distinguish between them. For example, the researcher could try to detect the proposed intermediates, NO3 and N2O4, directly.

Exercise 6.3.1
Iodine monochloride (ICl) reacts with H2 as follows:

2I C l(l) + H2 (g) → 2H C l(g) + I2 (s)

The experimentally determined rate law is rate = k[ICl][H2]. Write a two-step mechanism for this reaction using only bimolecular elementary reactions and show that it is consistent with the
experimental rate law. (Hint: HI is an intermediate.)
Answer

6.3.2 [Link]
 k1
step 1 rate = k1 [ICl][H2 ] (slow)
ICl + H2 −
→ HCl + HI

k2
step 2 HI + ICl −→ HCl + I2 rate = k2 [HI][ICl] (fast)
–––––––––––––––––––––

sum 2ICl + H2 → 2HCl + I2

This mechanism is consistent with the experimental rate law if the first step is the rate-determining step.

Example 6.3.2 : N O with H 2

Assume the reaction between N O and H occurs via a three-step process:

2

k1
step 1
NO + NO −
→ N2 O2

k2
step 2
N2 O2 + H2 −
→ N2 O + H2 O

k3
step 3
N2 O + H2 −
→ N2 + H2 O

Write the rate law for each elementary reaction, write the balanced chemical equation for the overall reaction, and identify the rate-determining step. Is the rate law for the rate-determining step
consistent with the experimentally derived rate law for the overall reaction: rate = k[N O] [H ]? 2 2

Answer:
Step 1: rate = k 1 [N O]
2

Step 2: rate = k 2 [ N2 O2 ][ H2 ]

Step 3: rate = k 3 [ N2 O][ H2 ]

The overall reaction is then

2N O(g) + 2 H2 (g) → N2 (g) + 2 H2 O(g) (6.3.5)

Rate Determining Step : #2

Yes, because the rate of formation of [N 2 O2 ]
2
= k1 [N O] . Substituting k
1 [N O]
2
for [N 2 O2 ] in the rate law for step 2 gives the experimentally derived rate law for the overall chemical
reaction, where k = k k .1 2

Summary
A balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law. A reaction mechanism is the microscopic path by which
reactants are transformed into products. Each step is an elementary reaction. Species that are formed in one step and consumed in another are intermediates. Each elementary reaction can be described
in terms of its molecularity, the number of molecules that collide in that step. The slowest step in a reaction mechanism is the rate-determining step.

6.3: Reaction Mechanisms is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

6.3.3 [Link]
6.4: The Effect of Temperature on Reaction Rate
Skills to Develop
The Learning Objective of this Module is to understand why and how chemical reactions occur.

It is possible to use kinetics studies of a chemical system, such as the effect of changes in reactant concentrations, to deduce events
that occur on a microscopic scale, such as collisions between individual particles. Such studies have led to the collision model of
chemical kinetics, which is a useful tool for understanding the behavior of reacting chemical species. According to the collision
model, a chemical reaction can occur only when the reactant molecules, atoms, or ions collide with more than a certain amount of
kinetic energy and in the proper orientation. The collision model explains why, for example, most collisions between molecules do
not result in a chemical reaction. Nitrogen and oxygen molecules in a single liter of air at room temperature and 1 atm of pressure
collide about 1030 times per second. If every collision produced two molecules of NO, the atmosphere would have been converted
to NO and then NO2 a long time ago. Instead, in most collisions, the molecules simply bounce off one another without reacting,
much as marbles bounce off each other when they collide. The collision model also explains why such chemical reactions occur
more rapidly at higher temperatures. For example, the reaction rates of many reactions that occur at room temperature
approximately double with a temperature increase of only 10°C. In this section, we will use the collision model to analyze this
relationship between temperature and reaction rates.

Activation Energy
Previously, we discussed that the average kinetic energy of the particles of a gas increases with increasing temperature. Because the
speed of a particle is proportional to the square root of its kinetic energy, increasing the temperature will also increase the number
of collisions between molecules per unit time. The simple observation that the molecules travel faster as they get warmer does not
explain why the reaction rate of most reactions approximately doubles with a 10°C temperature increase. This result is surprisingly
large considering that a 10°C increase in the temperature of a gas from 300 K to 310 K increases the kinetic energy of the particles
by only about 4%, leading to an increase in molecular speed of only about 2% and a correspondingly small increase in the number
of bimolecular collisions per unit time.
The collision model of chemical kinetics explains this behavior by introducing the concept of activation energy (Ea). We will
define this concept using the reaction of N O with ozone, which plays an important role in the depletion of ozone in the ozone
layer:
N O(g) + O3 (g) → N O2 (g) + O2 (g) (6.4.1)

Increasing the temperature from 200 K to 350 K causes the rate constant for this particular reaction to increase by a factor of more
than 10, whereas the increase in the frequency of bimolecular collisions over this temperature range is only 30%. Thus something
other than an increase in the collision rate must be affecting the reaction rate.
The reaction rate, not the rate constant, will vary with concentration. The rate constant, however, does vary with temperature.
Figure Table 6.4.1 shows a plot of the rate constant of the reaction of NO with O3 at various temperatures. The relationship is not
linear but instead resembles the relationships seen in graphs of vapor pressure versus temperature. In all three cases, the shape of
the plots results from a distribution of kinetic energy over a population of particles (electrons in the case of conductivity; molecules
in the case of vapor pressure; and molecules, atoms, or ions in the case of reaction rates). Only a fraction of the particles have
sufficient energy to overcome an energy barrier.

6.4.1 [Link]
Figure 6.4.1 : Rate Constant versus Temperature for the Reaction of N O with O The nonlinear shape of the curve is caused by a
3

distribution of kinetic energy over a population of molecules. Only a fraction of the particles have enough energy to overcome an
energy barrier, but as the temperature is increased, the size of that fraction increases.
In the case of vapor pressure, particles must overcome an energy barrier to escape from the liquid phase to the gas phase. This
barrier corresponds to the energy of the intermolecular forces that hold the molecules together in the liquid. In conductivity, the
barrier is the energy gap between the filled and empty bands. In chemical reactions, the energy barrier corresponds to the amount of
energy the particles must have to react when they collide. This energy threshold, called the activation energy, was first postulated in
1888 by the Swedish chemist Svante Arrhenius (1859–1927; Nobel Prize in Chemistry 1903). It is the minimum amount of energy
needed for a reaction to occur. Reacting molecules must have enough energy to overcome electrostatic repulsion, and a minimum
amount of energy is required to break chemical bonds so that new ones may be formed. Molecules that collide with less than the
threshold energy bounce off one another chemically unchanged, with only their direction of travel and their speed altered by the
collision. Molecules that are able to overcome the energy barrier are able to react and form an arrangement of atoms called the
activated complex or the transition state of the reaction. The activated complex is not a reaction intermediate; it does not last long
enough to be detected readily.

Any phenomenon that depends on the distribution of thermal energy in a population of

particles has a nonlinear temperature dependence.

Graphing Energy Changes during a Reaction

We can graph the energy of a reaction by plotting the potential energy of the system as the reaction progresses. Figure 6.4.2 shows
a plot for the NO–O3 system, in which the vertical axis is potential energy and the horizontal axis is the reaction coordinate, which
indicates the progress of the reaction with time. The activated complex is shown in brackets with an asterisk. The overall change in
potential energy for the reaction (ΔH, if the reaction is carried out at constant pressure) is negative, which means that the reaction
releases energy. (In this case, ΔH is −200.8 kJ/mol.) To react, however, the molecules must overcome the energy barrier to reaction
(Ea is 9.6 kJ/mol). That is, 9.6 kJ/mol must be put into the system as the activation energy. Below this threshold, the particles do not
have enough energy for the reaction to occur.

6.4.2 [Link]
Figure 6.4.2 : Energy of the Activated Complex for the NO–O3 System. The diagram shows how the energy of this system varies as
the reaction proceeds from reactants to products. Note the initial increase in energy required to form the activated complex.
Part (a) in Figure 6.4.3 illustrates the general situation in which the products have a lower potential energy than the reactants. In
contrast, part (b) in Figure 6.4.3 illustrates the case in which the products have a higher potential energy than the reactants, so the
overall reaction requires an input of energy; that is, it is energetically uphill, and ΔH > 0. Although the energy changes that result
from a reaction can be positive, negative, or even zero, in all cases an energy barrier must be overcome before a reaction can occur.
This means that the activation energy is always positive.

Figure 6.4.3 : Differentiating between Ea and ΔH. The potential energy diagrams for a reaction with (a) ΔH < 0 and (b) ΔH > 0
illustrate the change in the potential energy of the system as reactants are converted to products. Ea is always positive. For a
reaction such as the one shown in (b), Ea must be greater than ΔH.

For similar reactions under comparable conditions, the one with the smallest Ea will
occur most rapidly.
Whereas ΔH is related to the tendency of a reaction to occur spontaneously, Ea gives us information about the reaction rate and how
rapidly the reaction rate changes with temperature. For two similar reactions under comparable conditions, the reaction with the
smallest Ea will occur more rapidly.
Even when the energy of collisions between two reactant species is greater than Ea, however, most collisions do not produce a
reaction. The probability of a reaction occurring depends not only on the collision energy but also on the spatial orientation of the
molecules when they collide. For NO and O3 to produce NO2 and O2, a terminal oxygen atom of O3 must collide with the nitrogen
atom of NO at an angle that allows O3 to transfer an oxygen atom to NO to produce NO2 (Figure 6.4.4). All other collisions
produce no reaction. Because fewer than 1% of all possible orientations of NO and O3 result in a reaction at kinetic energies greater
than Ea, most collisions of NO and O3 are unproductive. The fraction of orientations that result in a reaction is called the steric
factor (p), and, in general, its value can range from 0 (no orientations of molecules result in reaction) to 1 (all orientations result in
reaction).

Figure 6.4.4 : The Effect of Molecular Orientation on the Reaction of NO and O3. Most collisions of NO and O3 molecules occur
with an incorrect orientation for a reaction to occur. Only those collisions in which the N atom of NO collides with one of the

6.4.3 [Link]
 terminal O atoms of O3 are likely to produce NO2 and O2, even if the molecules collide with E > Ea.

The Arrhenius Equation

Figure 14.5.5 shows both the kinetic energy distributions and a potential energy diagram for a reaction. The shaded areas show that
at the lower temperature (300 K), only a small fraction of molecules collide with kinetic energy greater than Ea; however, at the
higher temperature (500 K) a much larger fraction of molecules collide with kinetic energy greater than Ea. Consequently, the
reaction rate is much slower at the lower temperature because only a relatively few molecules collide with enough energy to
overcome the potential energy barrier.

Figure 6.4.5 : Surmounting the Energy Barrier to a Reaction. This chart juxtaposes the energy distributions of lower-temperature
(300 K) and higher-temperature (500 K) samples of a gas against the potential energy diagram for a reaction. Only those
molecules in the shaded region of the energy distribution curve have E > E and are therefore able to cross the energy barrier
a

separating reactants and products. The fraction of molecules with E > E is much greater at 500 K than at 300 K, so the reaction
a

will occur much more rapidly at 500 K.

For an A + B elementary reaction, all the factors that affect the reaction rate can be summarized in a single series of relationships:
rate = (collision frequency)(steric factor)(fraction of collisions with E > Ea)
where
rate = k[A][B] (6.4.2)

Arrhenius used these relationships to arrive at an equation that relates the magnitude of the rate constant for a reaction to the
temperature, the activation energy, and the constant, A, called the frequency factor:
−Ea /RT
k = Ae (6.4.3)

The frequency factor is used to convert concentrations to collisions per second. Because the frequency of collisions depends on the
temperature, A is actually not constant. Instead, A increases slightly with temperature as the increased kinetic energy of molecules
at higher temperatures causes them to move slightly faster and thus undergo more collisions per unit time. Equation 6.4.3 is known
as the Arrhenius equation and summarizes the collision model of chemical kinetics, where T is the absolute temperature (in K)
and R is the ideal gas constant [8.314 J/(K·mol)]. E indicates the sensitivity of the reaction to changes in temperature. The
a

reaction rate with a large Ea increases rapidly with increasing temperature, whereas the reaction rate with a smaller E increases a

much more slowly with increasing temperature.

If we know the reaction rate at various temperatures, we can use the Arrhenius equation to calculate the activation energy. Taking
the natural logarithm of both sides of Equation 6.4.3,
Ea Ea 1
ln k = ln A + (− ) = ln A + [(− )( )] (6.4.4)
RT R T

6.4.4 [Link]
Equation 6.4.4is the equation of a straight line, y = mx + b, where y = ln k and x = 1/T. This means that a plot of ln k versus 1/T is a
straight line with a slope of −Ea/R and an intercept of ln A. In fact, we need to measure the reaction rate at only two temperatures to
estimate Ea.
Knowing the E at one temperature allows us to predict the reaction rate at other temperatures. This is important in cooking and
a

food preservation, for example, as well as in controlling industrial reactions to prevent potential disasters.

Summary
For a chemical reaction to occur, an energy threshold must be overcome, and the reacting species must also have the correct spatial
orientation. A minimum energy (activation energy,Ea) is required for a collision between molecules to result in a chemical reaction.
Plots of potential energy for a system versus the reaction coordinate show an energy barrier that must be overcome for the reaction
to occur. The arrangement of atoms at the highest point of this barrier is the activated complex, or transition state, of the reaction.
At a given temperature, the higher the Ea, the slower the reaction. The fraction of orientations that result in a reaction is the steric
factor. The frequency factor, steric factor, and activation energy are related to the rate constant in the Arrhenius equation:
k = Ae
−Ea /RT
.

6.4: The Effect of Temperature on Reaction Rate is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

6.4.5 [Link]
6.5 Catalysts
Skills to Develop
To understand how catalysts increase the reaction rate and the selectivity of chemical reactions.

Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. A catalyst, therefore,
does not appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the
mechanism for the catalyzed reaction. The catalyzed pathway has a lower Ea, but the net change in energy that results from the reaction (the
difference between the energy of the reactants and the energy of the products) is not affected by the presence of a catalyst (Figure 1).
Nevertheless, because of its lower Ea, the reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at
the same temperature. Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the
forward and the reverse reactions by the same amount. In this section, we will examine the three major classes of catalysts: heterogeneous
catalysts, homogeneous catalysts, and enzymes.

Figure 1 : Lowering the Activation Energy of a Reaction by a Catalyst. This graph compares potential energy diagrams for a single-step
reaction in the presence and absence of a catalyst. The only effect of the catalyst is to lower the activation energy of the reaction. The
catalyst does not affect the energy of the reactants or products (and thus does not affect ΔH).

A catalyst affects Ea, not ΔH.

Heterogeneous Catalysis
In heterogeneous catalysis, the catalyst is in a different phase from the reactants. At least one of the reactants interacts with the solid
surface in a physical process called adsorption in such a way that a chemical bond in the reactant becomes weak and then breaks. Poisons
are substances that bind irreversibly to catalysts, preventing reactants from adsorbing and thus reducing or destroying the catalyst’s
efficiency.
An example of heterogeneous catalysis is the interaction of hydrogen gas with the surface of a metal, such as Ni, Pd, or Pt. As shown in part
(a) in Figure 2, the hydrogen–hydrogen bonds break and produce individual adsorbed hydrogen atoms on the surface of the metal. Because
the adsorbed atoms can move around on the surface, two hydrogen atoms can collide and form a molecule of hydrogen gas that can then
leave the surface in the reverse process, called desorption. Adsorbed H atoms on a metal surface are substantially more reactive than a
hydrogen molecule. Because the relatively strong H–H bond (dissociation energy = 432 kJ/mol) has already been broken, the energy barrier
for most reactions of H2 is substantially lower on the catalyst surface.

1 [Link]
Figure 2 : Hydrogenation of Ethylene on a Heterogeneous Catalyst. When a molecule of hydrogen adsorbs to the catalyst surface, the H–H
bond breaks, and new M–H bonds are formed. The individual H atoms are more reactive than gaseous H2. When a molecule of ethylene
interacts with the catalyst surface, it reacts with the H atoms in a stepwise process to eventually produce ethane, which is released.
Figure 2 shows a process called hydrogenation, in which hydrogen atoms are added to the double bond of an alkene, such as ethylene, to
give a product that contains C–C single bonds, in this case ethane. Hydrogenation is used in the food industry to convert vegetable oils,
which consist of long chains of alkenes, to more commercially valuable solid derivatives that contain alkyl chains. Hydrogenation of some
of the double bonds in polyunsaturated vegetable oils, for example, produces margarine, a product with a melting point, texture, and other
physical properties similar to those of butter.
Several important examples of industrial heterogeneous catalytic reactions are in Table 1. Although the mechanisms of these reactions are
considerably more complex than the simple hydrogenation reaction described here, they all involve adsorption of the reactants onto a solid
catalytic surface, chemical reaction of the adsorbed species (sometimes via a number of intermediate species), and finally desorption of the
products from the surface.
Table 1 : Some Commercially Important Reactions that Employ Heterogeneous Catalysts
F
i
n
a
l
C
o
m
m
e
r
Commercial Process Catalyst Initial Reaction
c
i
a
l
P
r
o
d
u
c
t

H
2
contact process V2O5 or Pt 2SO2 + O2 → 2SO3 S
O
4

N
Haber process Fe, K2O, Al2O3 N2 + 3H2 → 2NH3 H
3

H
N
Ostwald process Pt and Rh 4NH3 + 5O2 → 4NO + 6H2O
O
3

2 [Link]
 H
2
f
o
r
N
H
3
,
C
H
3
O
H
water–gas shift reaction Fe, Cr2O3, or Cu CO + H2O → CO2 + H2
,
a
n
d
o
t
h
e
r
f
u
e
l
s
H
steam reforming Ni CH4 + H2O → CO + 3H2
2

C
H
methanol synthesis ZnO and Cr2O3 CO + 2H2 → CH3OH 3
O
H

Sohio process bismuth phosphomolybdate CH 2 =CHCH3 + N H3 +

3

2
CH
O2 → CH2 =CHCN + 3 H2
2
ac

3 [Link]
 p
a
r
t
i
a
l
l
y
h
y
d
r
o
g
e
n
a
t
e
d
o
i
l
catalytic hydrogenation Ni, Pd, or Pt RCH=CHR′ + H2 → RCH2—CH2R′
s
f
o
r
m
a
r
g
a
r
i
n
e
,
a
n
d
s
o
f
o
r
t
h

Homogeneous Catalysis
In homogeneous catalysis, the catalyst is in the same phase as the reactant(s). The number of collisions between reactants and catalyst is at
a maximum because the catalyst is uniformly dispersed throughout the reaction mixture. Many homogeneous catalysts in industry are
transition metal compounds (Table 2), but recovering these expensive catalysts from solution has been a major challenge. As an added
barrier to their widespread commercial use, many homogeneous catalysts can be used only at relatively low temperatures, and even then
they tend to decompose slowly in solution. Despite these problems, a number of commercially viable processes have been developed in
recent years. High-density polyethylene and polypropylene are produced by homogeneous catalysis.
Table 2 : Some Commercially Important Reactions that Employ Homogeneous Catalysts

4 [Link]
 F
i
n
a
l
P
Commercial Process Catalyst Reactants
r
o
d
u
c
t

C
H
3
Union Carbide [Rh(CO)2I2]− CO + CH3OH C
O
2
H

hydroperoxide process Mo(VI) complexes CH3CH=CH2 + R–O–O–H

R
C
H
2
C
hydroformylation Rh/PR3 complexes RCH=CH2 + CO + H2
H
2
C
H
O

5 [Link]
 N
C
C
H
2
C
H
2
C
H
2
C
H
2
C
N
u
s
adiponitrile process Ni/PR3complexes 2HCN + CH2=CHCH=CH2 e
d
t
o
s
y
n
t
h
e
s
i
z
e
n
y
l
o
n

6 [Link]
 –
(
C
H
2
C
H
2
–
)
n
:
h
i
g
h
-
d
olefin polymerization (RC5H5)2ZrCl2 CH2=CH2
e
n
s
i
t
y
p
o
l
y
e
t
h
y
l
e
n
e

Enzymes
Enzymes, catalysts that occur naturally in living organisms, are almost all protein molecules with typical molecular masses of 20,000–
100,000 amu. Some are homogeneous catalysts that react in aqueous solution within a cellular compartment of an organism. Others are
heterogeneous catalysts embedded within the membranes that separate cells and cellular compartments from their surroundings. The reactant
in an enzyme-catalyzed reaction is called a substrate.
Because enzymes can increase reaction rates by enormous factors (up to 1017 times the uncatalyzed rate) and tend to be very specific,
typically producing only a single product in quantitative yield, they are the focus of active research. At the same time, enzymes are usually
expensive to obtain, they often cease functioning at temperatures greater than 37 °C, have limited stability in solution, and have such high
specificity that they are confined to turning one particular set of reactants into one particular product. This means that separate processes
using different enzymes must be developed for chemically similar reactions, which is time-consuming and expensive. Thus far, enzymes
have found only limited industrial applications, although they are used as ingredients in laundry detergents, contact lens cleaners, and meat

7 [Link]
tenderizers. The enzymes in these applications tend to be proteases, which are able to cleave the amide bonds that hold amino acids together
in proteins. Meat tenderizers, for example, contain a protease called papain, which is isolated from papaya juice. It cleaves some of the long,
fibrous protein molecules that make inexpensive cuts of beef tough, producing a piece of meat that is more tender. Some insects, like the
bombadier beetle, carry an enzyme capable of catalyzing the decomposition of hydrogen peroxide to water (Figure 3).

Figure 3 : A Catalytic Defense Mechanism. The scalding, foul-smelling spray emitted by this bombardier beetle is produced by the catalytic
decomposition of \(\ce{H2O2}\).
Enzyme inhibitors cause a decrease in the reaction rate of an enzyme-catalyzed reaction by binding to a specific portion of an enzyme and
thus slowing or preventing a reaction from occurring. Irreversible inhibitors are therefore the equivalent of poisons in heterogeneous
catalysis. One of the oldest and most widely used commercial enzyme inhibitors is aspirin, which selectively inhibits one of the enzymes
involved in the synthesis of molecules that trigger inflammation. The design and synthesis of related molecules that are more effective, more
selective, and less toxic than aspirin are important objectives of biomedical research.

Summary
Catalysts participate in a chemical reaction and increase its rate. They do not appear in the reaction’s net equation and are not consumed
during the reaction. Catalysts allow a reaction to proceed via a pathway that has a lower activation energy than the uncatalyzed reaction. In
heterogeneous catalysis, catalysts provide a surface to which reactants bind in a process of adsorption. In homogeneous catalysis, catalysts
are in the same phase as the reactants. Enzymes are biological catalysts that produce large increases in reaction rates and tend to be specific
for certain reactants and products. The reactant in an enzyme-catalyzed reaction is called a substrate. Enzyme inhibitors cause a decrease in
the reaction rate of an enzyme-catalyzed reaction.

6.5 Catalysts is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

8 [Link]
 CHAPTER OVERVIEW

7: Equilibrium and Thermodynamics

7.1: The Concept of Dynamic Equilibrium
7.2 The Equilibrium Constant
7.3: Calculating the Equilibrium Constant From Measured Equilibrium Concentrations
7.4 Predicting the Direction of a Reaction
7.5 Le Châtelier’s Principle: How a System at Equilibrium Responds to Disturbances
7.6: The First Law of Thermodynamics
7.7: Enthalpy: The Heat Evolved in a Chemical Reaction at Constant Pressure
7.8 Quantifying Heat
7.9: Entropy and the Second Law of Thermodynamics
7.10: Gibbs Free Energy
7.11 Gibbs Free Energy and Equilibrium
What we are studying

7: Equilibrium and Thermodynamics is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
7.1: The Concept of Dynamic Equilibrium
Skills to Develop
To understand what is meant by chemical equilibrium.

Two Methods to Describe the Likely Result of a Chemical Reaction

In the previous chapter, we discussed the principles of chemical kinetics, which deal with the rate of change, or how quickly a
given chemical reaction occurs. We now turn our attention to the extent to which a reaction occurs and how reaction conditions
affect the final concentrations of reactants and products. We will learn two "languages" to describe the extent of a reaction. First we
will describe the final, likely state of a chemical reaction in terms of the ratio of the amount of products to the amount of reactants
at equilibrium. Then we will apply the principles of thermodynamics to show how energy flow determines the likely amount of
product made by a reaction when it reaches dynamic equilibrium.
Equilibrium
For most of the reactions that we have discussed so far, you may have assumed that once reactants are converted to products, they
are likely to remain that way. In fact, however, virtually all chemical reactions are reversible to some extent. That is, an opposing
reaction occurs in which the products react, to a greater or lesser degree, to re-form the reactants. Eventually, the forward and
reverse reaction rates become the same, and the system reaches chemical equilibrium, the point at which the composition of the
system no longer changes with time.

Figure 7.1.1 : Dinitrogen tetroxide is a powerful oxidizer that reacts spontaneously upon contact with various forms of hydrazine,
which makes the pair a popular propellant combination for rockets. Nitrogen dioxide at −196 °C, 0 °C, 23 °C, 35 °C, and 50 °C.
(NO2) converts to the colorless dinitrogen tetroxide (N2O4) at low temperatures, and reverts to NO2 at higher temperatures. Figure
used with permission from Wikipedia (CC BY-SA 3.0; Eframgoldberg).
Chemical equilibrium is a dynamic process that consists of a forward reaction, in which reactants are converted to products, and a
reverse reaction, in which products are converted to reactants. At equilibrium, the forward and reverse reactions proceed at equal
rates. Consider, for example, a simple system that contains only one reactant and one product, the reversible dissociation of
dinitrogen tetroxide (N O ) to nitrogen dioxide (NO ). You may recall that NO is responsible for the brown color we associate
2 4 2 2

with smog. When a sealed tube containing solid N O (mp = −9.3°C; bp = 21.2°C) is heated from −78.4°C to 25°C, the red-brown
2 4

color of NO appears (Figure 7.1.1). The reaction can be followed visually because the product (NO ) is colored, whereas the
2 2

reactant (N O ) is colorless:
2 4

kf

N O (g) ⇌ 2 NO (g) (7.1.1)

2 4 2
colorless kr red−brown

The double arrow indicates that both the forward reaction

kf

N O (g) −
→ 2 NO (g) (7.1.2)
2 4 2

and reverse reaction

7.1.1 [Link]
 kr

2 NO (g) −
→ N O (g) (7.1.3)
2 2 4

occurring simultaneously (i.e, the reaction is reversible). However, this does not necessarily mean the system is equilibrium, as
section 7. 4 demonstrates.
Figure 7.1.2 shows how the composition of this system would vary as a function of time at a constant temperature. If the initial
concentration of NO were zero, then it increases as the concentration of N O decreases. Eventually the composition of the
2 2 4

system stops changing with time, and chemical equilibrium is achieved. Conversely, if we start with a sample that contains no
N O
2 4
but an initial NO concentration twice the initial concentration of N O (Figure 7.1.2a), in accordance with the
2 2 4

stoichiometry of the reaction, we reach exactly the same equilibrium composition (Figure 7.1.2b). Thus equilibrium can be
approached from either direction in a chemical reaction.

Figure 7.1.2 : The Composition of N O /NO Mixtures as a Function of Time at Room Temperature. (a) Initially, this idealized
2 4 2

system contains 0.0500 M gaseous N O and no gaseous NO . The concentration of N O decreases with time as the
2 4 2 2 4

concentration of NO increases. (b) Initially, this system contains 0.1000 M NO and no N O . The concentration of NO
2 2 2 4 2

decreases with time as the concentration of N O increases. In both cases, the final concentrations of the substances are the same:
2 4

[N O ] = 0.0422 M and [NO ] = 0.0156 M at equilibrium.

2 4 2

Figure 7.1.3 shows the forward and reverse reaction rates for a sample that initially contains pure NO . Because the initial 2

concentration of N O is zero, the forward reaction rate (dissociation of N O ) is initially zero as well. In contrast, the reverse
2 4 2 4

reaction rate (dimerization of NO ) is initially very high (2.0 × 10 M /s ), but it decreases rapidly as the concentration of NO
2
6
2

decreases. As the concentration of N O increases, the rate of dissociation of N O increases. Eventually, the forward and reverse
2 4 2 4

reaction rates become identical, and the system has reached chemical equilibrium. If the forward and reverse reactions occur at
different rates, then the system is not at equilibrium.

7.1.2 [Link]
Figure 7.1.3 : The Forward and Reverse Reaction Rates as a Function of Time for the N 2 O4(g) ⇌2N O 2(g) System Shown in Part
(b) in Figure 7.1.2
Initially, the rate of dimerization of NO (reverse reaction) is quite rapid, but this rate decreases over time as the concentration of
2

NO decreases. Because the initial concentration of N O is zero, the rate of the dissociation reaction (forward reaction) at t = 0
2 2 4

is also zero. As the dimerization reaction proceeds, the N O concentration increases, and its rate of dissociation also increases.
2 4

Eventually the rates of the two reactions are equal: chemical equilibrium has been reached, and the concentrations of N O and 2 4

NO no longer change.
2

At equilibrium, the forward reaction rate is equal to the reverse reaction rate.
Example 7.1.1
The three reaction systems (1, 2, and 3) depicted in the accompanying illustration can all be described by the equation:
2A ⇌ B (7.1.4)

where the blue circles are A and the purple ovals are B . Each set of panels shows the changing composition of one of the three
reaction mixtures as a function of time. Which system took the longest to reach chemical equilibrium?

Given: three reaction systems

Asked for: relative time to reach chemical equilibrium
Strategy:
Compare the concentrations of A and B at different times. The system whose composition takes the longest to stabilize took the
longest to reach chemical equilibrium.
Solution:
In systems 1 and 3, the concentration of A decreases from t through t but is the same at both t and t . Thus systems 1 and 3
0 2 2 3

are at equilibrium by t . In system 2, the concentrations of A and B are still changing between t and t , so system 2 may not
3 2 3

yet have reached equilibrium by t . Thus system 2 took the longest to reach chemical equilibrium.
3

Exercise 7.1.1
In the following illustration, A is represented by blue circles, B by purple squares, and C by orange ovals; the equation for the
reaction is A + B ⇌ C. The sets of panels represent the compositions of three reaction mixtures as a function of time. Which, if
any, of the systems shown has reached equilibrium?

Answer
system 2

Summary
At equilibrium, the forward and reverse reactions of a system proceed at equal rates. Chemical equilibrium is a dynamic process
consisting of forward and reverse reactions that proceed at equal rates. At equilibrium, the composition of the system no longer

7.1.3 [Link]
changes with time. The composition of an equilibrium mixture is independent of the direction from which equilibrium is
approached.

7.1: The Concept of Dynamic Equilibrium is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

7.1.4 [Link]
7.2 The Equilibrium Constant
Skills to Develop
To write an equilibrium constant expression for any reaction.

Because an equilibrium state is achieved when the forward reaction rate equals the reverse reaction rate, under a given set of
conditions there must be a relationship between the composition of the system at equilibrium and the kinetics of a reaction
(represented by rate constants). We can show this relationship using the decomposition reaction of N O to N O . Both the 2 4 2

forward and reverse reactions for this system consist of a single elementary reaction, so the reaction rates are as follows:

forward rate = kf [ N2 O4 ] (1)

and
2
reverse rate = kr [N O2 ] (2)

At equilibrium, the forward rate equals the reverse rate (definition of equilibrium):
2
kf [ N2 O4 ] = kr [N O2 ] (3)

so
2
kf [N O2 ]
= (4)
kr [ N2 O4 ]

The ratio of the rate constants gives us a new constant, the equilibrium constant (K ), which is defined as follows:
kf
K = (5)
kr

Hence there is a fundamental relationship between chemical kinetics and chemical equilibrium: under a given set of conditions, the
composition of the equilibrium mixture is determined by the magnitudes of the rate constants for the forward and the reverse
reactions.
Many reactions occur by a multi-step mechanism, and so the equilibrium composition can not be so easily derived as shown
in the above example. However it is universally true that the numerical value of the equilibrium constant of a system at
equilibrium at a specific temperature will always have a constant value, as shown below.

Table 1 lists the initial and equilibrium concentrations from five different experiments using the reaction system described by
Equation 3. At equilibrium the magnitude of the quantity [N O ] /[N O ] is essentially the same for all five experiments. In fact,
2
2
2 4

no matter what the initial concentrations of N O and N O are, at equilibrium the quantity [N O ] /[N O ] will always be
2 2 4 2
2
2 4

6.53 ± 0.03 × 10
−3
at 25°C, which corresponds to the ratio of the rate constants for the forward and reverse reactions. That is, at a
given temperature, the equilibrium constant for a reaction always has the same value, even though the specific concentrations of the
reactants and products vary depending on their initial concentrations.
Table 1 : Initial and Equilibrium Concentrations for N O 2 : N2 O4 Mixtures at 25°C
Initial Concentrations Concentrations at Equilibrium

Experiment [N 2 O4 ] (M) [N O ] (M)

2 [N 2 O4 ] (M) [N O ] (M)
2
2
K = [N O2 ] /[N2 O4 ]

1 0.0500 0.0000 0.0417 0.0165 6.54 × 10

−3

2 0.0000 0.1000 0.0417 0.0165 6.54 × 10

−3

3 0.0750 0.0000 0.0647 0.0206 6.56 × 10

−3

4 0.0000 0.0750 0.0304 0.0141 6.54 × 10

−3

5 0.0250 0.0750 0.0532 0.0186 6.50 × 10

−3

1 [Link]
Developing an Equilibrium Constant Expression
In 1864, the Norwegian chemists Cato Guldberg (1836–1902) and Peter Waage (1833–1900) carefully measured the compositions
of many reaction systems at equilibrium. They discovered that for any reversible reaction of the general form
aA + bB ⇌ cC + dD (6)

where A and B are reactants, C and D are products, and a, b, c, and d are the stoichiometric coefficients in the balanced chemical
equation for the reaction, the ratio of the product of the equilibrium concentrations of the products (raised to their coefficients in the
balanced chemical equation) to the product of the equilibrium concentrations of the reactants (raised to their coefficients in the
balanced chemical equation) is always a constant under a given set of conditions. This relationship is known as the law of mass
action and can be stated as follows:
c d
[C ] [D]
K = (7)
a b
[A] [B]

where K is the equilibrium constant for the reaction. Equation 6 is called the equilibrium equation, and the right side of Equation 7
is called the equilibrium constant expression. The relationship shown in Equation 7 is true for any pair of opposing reactions
regardless of the mechanism of the reaction or the number of steps in the mechanism.
The equilibrium constant can vary over a wide range of values. The values of K shown in Table 2, for example, vary by 60 orders
of magnitude. Because products are in the numerator of the equilibrium constant expression and reactants are in the denominator,
values of K greater than 1 indicate a reaction that is product-favored at equilibrium (-ΔG ). If K is greater than 10 , the reaction
o 3

has a strong tendency for the reactants to form products. In this case, chemists say that equilibrium lies far to the right as written,
favoring the formation of a great deal of products. An example is the reaction between H and C l to produce H C l, which has an
2 2

equilibrium constant of 1.6 × 10 at 300 K. Because H is a good reductant and C l is a good oxidant, the reaction proceeds
33
2 2

essentially to completion. In contrast, values of K less than 1 indicate a reaction that is reactant-favored at equilibrium (+ΔG ). If o

K is less than 10 the reaction has a very slight tendency for the reactants to form products, so that the ratio of products to
−3

reactants at equilibrium is very small. That is, reactants do not tend to form products readily, and the equilibrium lies to the left as
written, favoring the formation of reactants.
Table 2 : Equilibrium Constants for Selected Reactions*
Reaction Temperature (K) Equilibrium Constant (K)

S(s) + O2(g) ⇌ S O2(g) 300 4.4 × 10

53

2 H2(g) + O2(g) ⇌ 2H2 O(g) 500 2.4 × 10

47

H2(g) + C l2(g) ⇌ 2HC l(g) 300 1.6 × 10

33

H2(g) + B r2(g) ⇌ 2HB r(g) 300 4.1 × 10

18

2N O(g) + O2(g) ⇌ 2N O2(g) 300 4.2 × 10

13

3 H2(g) + N2(g) ⇌ 2N H3(g) 300 2.7 × 10

8

H2(g) + D2(g) ⇌ 2H D(g) 100 1.92

H2(g) + I2(g) ⇌ 2H I(g) 300 2.9 × 10

−1

I2(g) ⇌ 2 I(g) 800 4.6×

10−7

B r2(g) ⇌ 2B r(g) 1000 4.0 × 10

−7

C l2(g) ⇌ 2C l(g) 1000 1.8 × 10

−9

F2(g) ⇌ 2 F(g) 500 7.4 × 10

−13

*Equilibrium constants vary with temperature. The K values shown are for systems at the indicated temperatures.

2 [Link]
You will also notice in Table 2 that equilibrium constants have no units, even though Equation 7 suggests that the units of
concentration might not always cancel because the exponents may vary. In fact, equilibrium constants are calculated using
“effective concentrations,” or activities, of reactants and products, which are the ratios of the measured concentrations to a
standard state of 1 M. As shown in Equation 8, the units of concentration cancel, which makes K unitless as well:
mol

[A]measured M L

= = (8)
[A]standard state M mol

In fact, equilibrium constants are calculated using “effective concentrations,” or

activities, of reactants and products, which are the ratios of the measured concentrations
to a standard state of 1 M.
Many reactions have equilibrium constants between 1000 and 0.001 (10 ≥ K ≥ 10 ), neither very large nor very small. At
3 −3

equilibrium, these systems tend to contain significant amounts of both products and reactants, indicating that there is not a strong
tendency to form either products from reactants or reactants from products. An example of this type of system is the reaction of
gaseous hydrogen and deuterium, a component of high-stability fiber-optic light sources used in ocean studies, to form H D:
H2(g) + D2(g) ⇌ 2H D(g) (9)

The equilibrium constant expression for this reaction is

2
[H D]
K = (10)
[ H2 ][ D2 ]

with K varying between 1.9 and 4 over a wide temperature range (100–1000 K). Thus an equilibrium mixture of H , D , and H D
2 2

contains significant concentrations of both product and reactants.

Figure 3 summarizes the relationship between the magnitude of K and the relative concentrations of reactants and products at
equilibrium for a general reaction, written as reactants ⇌ products.

Figure 3 : The Relationship between the Composition of the Mixture at Equilibrium and the Magnitude of the Equilibrium
Constant. The larger the K, the farther the reaction proceeds to the right before equilibrium is reached, and the greater the ratio of
products to reactants at equilibrium.

A large value of the equilibrium constant K means that products predominate at

equilibrium; a small value means that reactants predominate at equilibrium.
Example 1 : equilibrium constant expressionS
Write the equilibrium constant expression for each reaction.
N2(g) + 3 H2(g) ⇌ 2N H3(g)
1
C O(g) + O2(g) ⇌ C O2(g)
2

2C O2(g) ⇌ 2C O(g) + O2(g)

Given: balanced chemical equations

3 [Link]
Asked for: equilibrium constant expressions
Strategy:
Refer to Equation 7. Place the arithmetic product of the concentrations of the products (raised to their stoichiometric
coefficients) in the numerator and the product of the concentrations of the reactants (raised to their stoichiometric coefficients)
in the denominator.
Solution:
The only product is ammonia, which has a coefficient of 2. For the reactants, N has a coefficient of 1 and H has a coefficient
2 2

of 3. The equilibrium constant expression is as follows:

2
[N H3 ]
(11)
3
[ N2 ][ H2 ]

The only product is carbon dioxide, which has a coefficient of 1. The reactants are C O, with a coefficient of 1, and O , with a 2

coefficient of . Thus the equilibrium constant expression is as follows:

1

[C O2 ]
(12)
1/2
[C O][O2 ]

This reaction is the reverse of the reaction in part b, with all coefficients multiplied by 2 to remove the fractional coefficient for
O . The equilibrium constant expression is therefore the inverse of the expression in part b, with all exponents multiplied by 2
2

2
[C O] [ O2 ]
(13)
2
[C O2 ]

Exercise 1
Write the equilibrium constant expression for each reaction.
a. N O ⇌ N
2 +
(g) O 2(g)
1

2
2(g)

b. 2C H + 25 O
8 ⇌ 16C O
18(g) 2(g) 2(g) + 18 H2 O(g)

c. H +I
2(g)
⇌ 2H I 2(g) (g)

Answer a
1/2
[ N2 ][ O2 ]
K =
[ N2 O]

Answer b
16 18
[C O2 ] [ H2 O]
K =
2 25
[ C8 H18 ] [ O2 ]

Answer c
2
[H I ]
K =
[ H2 ][ I2 ]

Example 2
Predict which systems at equilibrium will (a) contain essentially only products, (b) contain essentially only reactants, and (c)
contain appreciable amounts of both products and reactants.
1. H +I
2(g)
⇌ 2H I 2(g) (g)
K(700K) = 54

2. 2C O ⇌ 2C O
2(g) +O (g) 2(g) K(1200K) = 3.1 × 10
−18

3. P C l ⇌ P Cl
5(g)
+ Cl 3(g) 2(g)
K(613K) = 97

4. 2O ⇌ 3O
3(g)
K 2(g) (298K)
= 5.9 × 10
55

Given: systems and values of K

4 [Link]
 Asked for: composition of systems at equilibrium
Strategy:
Use the value of the equilibrium constant to determine whether the equilibrium mixture will contain essentially only products,
essentially only reactants, or significant amounts of both.
Solution:
a. Only system 4 has K ≫ 10 , so at equilibrium it will consist of essentially only products.
3

b. System 2 has K ≪ 10 , so the reactants have little tendency to form products under the conditions specified; thus, at
−3

equilibrium the system will contain essentially only reactants.

c. Both systems 1 and 3 have equilibrium constants in the range 10 ≥ K ≥ 10 , indicating that the equilibrium mixtures
3 −3

will contain appreciable amounts of both products and reactants.

Exercise 2
Hydrogen and nitrogen react to form ammonia according to the following balanced chemical equation:
3 H2(g) + N2(g) ⇌ 2N H3(g) (14)

Values of the equilibrium constant at various temperatures were reported as

K25°C = 3.3 × 10
8
,
K177°C = 2.6 × 10
3
, and
K327°C = 4.1 .
a. At which temperature would you expect to find the highest proportion of H and N in the equilibrium mixture?
2 2

b. Assuming that the reaction rates are fast enough so that equilibrium is reached quickly, at what temperature would you
design a commercial reactor to operate to maximize the yield of ammonia?

Answer a
327°C, where K is smallest
Answer b
25°C

Variations in the Form of the Equilibrium Constant Expression

Because equilibrium can be approached from either direction in a chemical reaction, the equilibrium constant expression and thus
the magnitude of the equilibrium constant depend on the form in which the chemical reaction is written. For example, if we write
the reaction described in Equation 6 in reverse, we obtain the following:

cC + dD ⇌ aA + bB (15)

The corresponding equilibrium constant K' is as follows:

a b
[A] [B]
′
K = (16)
c d
[C ] [D]

This expression is the inverse of the expression for the original equilibrium constant, so K' = 1/K . That is, when we write a
reaction in the reverse direction, the equilibrium constant expression is inverted. For instance, the equilibrium constant for the
reaction N O ⇌ 2N O is as follows:
2 4 2

2
[N O2 ]
K = (17)
[ N2 O4 ]

but for the opposite reaction, 2N O 2 ⇌ N2 O4 , the equilibrium constant K′ is given by the inverse expression:
[ N2 O4 ]
′
K = (18)
2
[N O2 ]

5 [Link]
Consider another example, the formation of water: 2H +O2(g) ⇌ 2H O 2(g). Because H is a good reductant and O is a good
2 (g) 2 2

oxidant, this reaction has a very large equilibrium constant (K = 2.4 × 10 at 500 K). Consequently, the equilibrium constant for
47

the reverse reaction, the decomposition of water to form O and H , is very small: K' = 1/K = 1/(2.4 × 10 ) = 4.2 × 10
2 2 . 47 −48

As suggested by the very small equilibrium constant, and fortunately for life as we know it, a substantial amount of energy is
indeed needed to dissociate water into H and O .
2 2

The equilibrium constant for a reaction written in reverse is the inverse of the equilibrium
constant for the reaction as written originally.
Example 3 : The Haber Process
At 745 K, K is 0.118 for the following reaction:
N2(g) + 3 H2(g) ⇌ 2N H3(g) (19)

What is the equilibrium constant for 2N H 3(g) ⇌ N 2(g) + 3 H2(g) at 745 K?

Given: balanced equilibrium equation, K at a given temperature, and equations of related reactions
Asked for: values of K for the reverse reaction
Strategy:
Write the equilibrium constant expression for the given reaction and for the reverse reaction. From these expressions, calculate
K for each reaction.

Solution:
The equilibrium constant expression for the given reaction of N 2(g) with H 2(g) to produce N H3(g) at 745 K is as follows:
2
[N H3 ]
K = = 0.118 (20)
3
[ N2 ][ H2 ]

This reaction is the reverse of the one given, so its equilibrium constant expression is as follows:
3
1 [ N2 ][ H2 ] 1
′
K = = = = 8.47 (21)
K [N H3 ]2 0.118

Exercise 3
At 527°C, the equilibrium constant for the reaction

2S O2(g) + O2(g) ⇌ 2S O3(g)

is 7.90 × 10 . Calculate the equilibrium constant for the following reaction at the same temperature:
4

2S O3(g) ⇌ 2S O2(g) + O2(g)

Answer
−5
1.27 × 10

Heterogeneous Equilibria
When the products and reactants of an equilibrium reaction form a single phase, whether gas or liquid, the system is a
homogeneous equilibrium. In such situations, the concentrations of the reactants and products can vary over a wide range. In
contrast, a system whose reactants, products, or both are in more than one phase is a heterogeneous equilibrium, such as the
reaction of a gas with a solid or liquid, or the reaction of a solute with the solvent to form a new, different solute. In these
heterogeneous equilibria, the pure liquids and pure solids are assigned an activity of 1.
This standard convention causes quite a bit of confusion because the treatment of the activity of a pure solid, pure liquid, or solvent
differs from the treatment of the activity of a gas or a solute in a mixture. The true law of mass action is a ratio of activities of all

6 [Link]
the reactants and products. However, to simplify measurements and calculations, the activity of any gas or any solute can be
approximated by its molarity. The activity of a pure solid or a pure liquid or a solvent is never approximated by its concentration.
Instead, the activity of the pure solid, or pure liquid, or solvent is defined as having a value of 1.
Consider the following reaction, which is used in the final firing of some types of pottery to produce brilliant metallic glazes:

C O2(g) + C(s) ⇌ 2C O(g) (22)

The glaze is created when metal oxides are reduced to metals by the product, carbon monoxide. The equilibrium constant
expression for this reaction is as follows:
2 2 2
a [C O] [C O]
CO
K = = = (23)
aC O2 aC [C O2 ][1] [C O2 ]

Although the concentrations of pure liquids or solids are not written explicitly in the equilibrium constant expression, these
substances must be present in the reaction mixture for chemical equilibrium to occur. Whatever the concentrations of C O and
C O , the system described above will reach chemical equilibrium only if excess solid carbon has been added so that some solid
2

carbon is still present once the system has reached equilibrium. As shown in Figure 4, it does not matter whether 1 g or 100 g of
solid carbon is present; in either case, the composition of the gaseous components of the system will be the same at equilibrium.

Figure 4: Effect of the Amount of Solid Present on Equilibrium in a Heterogeneous Solid–Gas System. In the system, the
equilibrium composition of the gas phase at a given temperature, 1000 K in this case, is the same whether a small amount of solid
carbon (left) or a large amount (right) is present.

Example 4
Write each expression for K for the following equilibrium reactions.
P C l3(l) + C l2(g) ⇌ P C l5(s) (24)

F e3 O4(s) + 4 H2(g) ⇌ 3F e(s) + 4 H2 O(g) (25)

Given: balanced equilibrium equations

Asked for: expression for K
Strategy:
Find K by writing each equilibrium constant expression as the ratio of the activities of the products and reactants, each raised to
its coefficient in the chemical equation. Then substitute the appropriate concentration or activity to arrive at the common form

7 [Link]
 of the law of mass action
Solution:
The first reaction contains a pure solid P C l and a pure liquid P C l . As pure substances, their activities are defined as "1", so
5 3

they do not appear explicitly in the equilibrium constant expression. So

aP C l 1 1
5
K = = = (26)
aP C l aC l (1)[C l2 ] [C l2 ]
3 2

The second reaction contains two pure solids F e O and F e, which both have an activity defined as "1", and so do not appear
3 4

explicitly in the equilibrium constant expressions. The concentrations of the two gases do, however, appear in the expressions:
3 4 3 4 4
a a (1 ) [ H2 O] [ H2 O]
Fe H2 O
K = = = (27)
4 4 4
aF e O4 a (1)[H2 ] [H2 ]
3 H2

Exercise 4
EXERCISE 7
Write the expression for K for the following reactions.

C aC O3(s) ⇌ C aO(s) + C O2(g) (28)

C6 H12 O6(s) + 6 O2(g) ⇌ 6C O2(g) + 6 H2 O(g) (29)

Answer
aC aO aC O2 (1)[C O2 ]
K = = = [C O2 ] (30)
aC aC O 1
3

6 6
a a 6 6 6 6
C O2 H2 O [C O2 ] [ H2 O] [C O2 ] [ H2 O]
K = = = (31)
6 6 6
aC6 H1 2 O6 a (1)[O2 ] [O2 ]
O2

For reactions carried out in solution, the solvent is assumed to be pure, and therefore is assigned an activity equal to 1 in the
equilibrium constant expression. The activities of the solutes are approximated by their molarities. The result is that the equilibrium
constant expressions appear to only depend upon the concentrations of the solutes.

The activities of pure solids, pure liquids, and solvents are defined as having a value of
'1'. Often, it is said that these activities are "left out" of equilibrium constant expressions.
This is an unfortunate use of words. The activities are not "left out" of equilibrium
constant expressions. Rather, because they have a value of '1', they do not change the
value of the equilibrium constant when they are multiplied together with the other terms.

Summary
The ratio of the rate constants for the forward and reverse reactions at equilibrium is the equilibrium constant (K ), a unitless
quantity. The composition of the equilibrium mixture is therefore determined by the magnitudes of the forward and reverse rate
constants at equilibrium. Under a given set of conditions, a reaction will always have the same K . For a system at equilibrium, the
law of mass action relates K to the ratio of the equilibrium concentrations of the products to the concentrations of the reactants
raised to their respective powers to match the coefficients in the equilibrium equation. The ratio is called the equilibrium constant
expression. When a reaction is written in the reverse direction, K and the equilibrium constant expression are inverted. An
equilibrium system that contains products and reactants in a single phase is a homogeneous equilibrium; a system whose reactants,
products, or both are in more than one phase is a heterogeneous equilibrium.
The law of mass action describes a system at equilibrium in terms of the concentrations of the products and the reactants.
Equilibrium constant expression (law of mass action):

8 [Link]
 c d
[C ] [D]
K = (32)
a b
[A] [B]

Contributors
Modified by Tom Neils (Grand Rapids Community College)

7.2 The Equilibrium Constant is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

9 [Link]
7.3: Calculating the Equilibrium Constant From Measured Equilibrium
Concentrations
Skills to Develop
To solve quantitative problems involving chemical equilibriums.

There are two fundamental kinds of equilibrium problems:

1. those in which we are given the concentrations of the reactants and the products at equilibrium (or, more often, information that
allows us to calculate these concentrations), and we are asked to calculate the equilibrium constant for the reaction; and
2. those in which we are given the equilibrium constant and the initial concentrations of reactants, and we are asked to calculate
the concentration of one or more substances at equilibrium. In this section, we describe methods for solving both kinds of
problems.

Calculating an Equilibrium Constant from Equilibrium Concentrations

We saw earlier that the equilibrium constant for the decomposition of C aC O 3(s)
to C aO and C O
(s)
is K = [C O ] . At 800°C,
2(g) 2

the concentration of C O in equilibrium with solid C aC O and C aO is

2 3 2.5 × 10
−3
M . Thus K at 800°C is 2.5 × 10 . −3

(Remember that equilibrium constants are unitless.)

A more complex example of this type of problem is the conversion of n-butane, an additive used to increase the volatility of
gasoline, into isobutane (2-methylpropane).

This reaction can be written as follows:

n−butane ⇌ isobutane (7.3.1)
(g) (g)

and the equilibrium constant K = [isobutane]/[n-butane] . At equilibrium, a mixture of n-butane and isobutane at room
temperature was found to contain 0.041 M isobutane and 0.016 M n-butane. Substituting these concentrations into the equilibrium
constant expression,
[isobutane] 0.041 M
K = = = 2.6 (7.3.2)
[n-butane] 0.016 M

Thus the equilibrium constant for the reaction as written is 2.6.

Example 7.3.1
The reaction between gaseous sulfur dioxide and oxygen is a key step in the industrial synthesis of sulfuric acid:
2S O2(g) + O2(g) ⇌ 2S O3(g)

A mixture of SO and O was maintained at 800 K until the system reached equilibrium. The equilibrium mixture contained
2 2

5.0 × 10
−2
M S O3 ,
3.5 × 10
−3
M O2 , and
SO .
−3
3.0 × 10 M 2

Calculate K at this temperature.

Given: balanced equilibrium equation and composition of equilibrium mixture

7.3.1 [Link]
 Asked for: equilibrium constant
Strategy
Write the equilibrium constant expression for the reaction. Then substitute the appropriate equilibrium concentrations into this
equation to obtain K .
SOLUTION
Substituting the appropriate equilibrium concentrations into the equilibrium constant expression,
2 −2 2
[SO3 ] (5.0 × 10 )
4
K = = = 7.9 × 10
2 −3 2 −3
[S O2 ] [ O2 ] (3.0 × 10 ) (3.5 × 10 )

Exercise 7.3.1
Hydrogen gas and iodine react to form hydrogen iodide via the reaction
H2(g) + I2(g) ⇌ 2H I(g)

A mixture of H and I was maintained at 740 K until the system reached equilibrium. The equilibrium mixture contained
2 2

1.37 × 10
−2
M HI ,
6.47 × 10
−3
M H2 , and
5.94 × 10
−4
M I2 .
Calculate K for this reaction.

Answer
K = 48.8

Chemists are not often given the concentrations of all the substances, and they are not likely to measure the equilibrium
concentrations of all the relevant substances for a particular system. In such cases, we can obtain the equilibrium concentrations
from the initial concentrations of the reactants and the balanced chemical equation for the reaction, as long as the equilibrium
concentration of one of the substances is known. Example 7.3.2 shows one way to do this.

Example 7.3.2
A 1.00 mol sample of N OC l was placed in a 2.00 L reactor and heated to 227°C until the system reached equilibrium. The
contents of the reactor were then analyzed and found to contain 0.056 mol of C l . Calculate K at this temperature. The equation
2

for the decomposition of N OC l to N O and C l is as follows:

2

2N OC l(g) ⇌ 2N O(g) + C l2(g)

Given: balanced equilibrium equation, amount of reactant, volume, and amount of one product at equilibrium
Asked for: K
Strategy:
A. Write the equilibrium constant expression for the reaction. Construct a table showing the initial concentrations, the changes
in concentrations, and the final concentrations (as initial concentrations plus changes in concentrations).
B. Calculate all possible initial concentrations from the data given and insert them in the table.
C. Use the coefficients in the balanced chemical equation to obtain the changes in concentration of all other substances in the
reaction. Insert those concentration changes in the table.
D. Obtain the final concentrations by summing the columns. Calculate the equilibrium constant for the reaction.
SOLUTION
A The first step in any such problem is to balance the chemical equation for the reaction (if it is not already balanced) and use it
to derive the equilibrium constant expression. In this case, the equation is already balanced, and the equilibrium constant
expression is as follows:

7.3.2 [Link]
 2
[N O] [C l2 ]
K =
2
[N OC l]

To obtain the concentrations of N OC l, N O , and C l at equilibrium, we construct a table showing what is known and what
2

needs to be calculated. We begin by writing the balanced chemical equation at the top of the table, followed by three lines
corresponding to the initial concentrations, the changes in concentrations required to get from the initial to the final state, and
the final concentrations.

2N OC l(g) ⇌ 2N O(g) + C l2(g)

ICE [N OCl] [N O] [C l2 ]

Initial

Change

Final

B Initially, the system contains 1.00 mol of N OC l in a 2.00 L container. Thus [N OC l] = 1.00 mol/2.00 L = 0.500 M. The
i

initial concentrations of N O and C l are 0 M because initially no products are present. Moreover, we are told that at
2

equilibrium the system contains 0.056 mol of C l in a 2.00 L container, so [C l ] = 0.056 mol/2.00 L = 0.028 M. We insert
2 2 f

these values into the following table:

2N OC l(g) ⇌ 2N O(g) + C l2(g)

ICE [N OCl] [N O] [C l2 ]

Initial 0.500 0 0

Change

Final 0.028

C We use the stoichiometric relationships given in the balanced chemical equation to find the change in the concentration of
C l , the substance for which initial and final concentrations are known:
2

Δ[C l2 ] = 0.028 M(f inal) − 0.00 M(initial) ] = +0.028 M

According to the coefficients in the balanced chemical equation, 2 mol of NO are produced for every 1 mol of C l2 , so the
change in the N O concentration is as follows:

0.028 mol C l2 2 mol N O

Δ[N O] = ( )( ) = 0.056 M
L 1 mol C l2

Similarly, 2 mol of N OC l are consumed for every 1 mol of C l2 produced, so the change in the N OC l concentration is as
follows:

0.028 mol C l2 −2 mol N OC l

Δ[N OC l] = ( )( ) = −0.056 M
L
1 mol C l2

We insert these values into our table:

2N OC l(g) ⇌ 2N O(g) + C l2(g)

ICE [N OCl] [N O] [C l2 ]

Initial 0.500 0 0

Change −0.056 +0.056 +0.028

Final 0.028

7.3.3 [Link]
 D We sum the numbers in the [N OC l] and [N O] columns to obtain the final concentrations of N O and N OC l:

[N O]f = 0.000 M + 0.056 M = 0.056 M

[N OC l]f = 0.500 M + (−0.056 M ) = 0.444M

We can now complete the table:

2N OC l(g) ⇌ 2N O(g) + C l2(g)

ICE \([NOCl] [N O] [C l2 ]

initial 0.500 0 0

change −0.056 +0.056 +0.028

final 0.444 0.056 0.028

We can now calculate the equilibrium constant for the reaction:

2 2
[N O] [C l2 ] (0.056 ) (0.028)
−4
K = = = 4.5 × 10
2 2
[N OC l] (0.444)

Exercise 7.3.2
The German chemist Fritz Haber (1868–1934; Nobel Prize in Chemistry 1918) was able to synthesize ammonia (N H ) by 3

reacting 0.1248 M H and 0.0416 M N at about 500°C. At equilibrium, the mixture contained 0.00272 M N H . What is K
2 2 3

for the reaction

N2 + 3 H2 ⇌ 2N H3

at this temperature?

Answer
K = 0.105

Calculating Equilibrium Concentrations from the Equilibrium Constant

To describe how to calculate equilibrium concentrations from an equilibrium constant, we first consider a system that contains only
a single product and a single reactant, the conversion of n-butane to isobutane (Equation 7.3.1), for which K = 2.6 at 25°C. If we
begin with a 1.00 M sample of n-butane, we can determine the concentration of n-butane and isobutane at equilibrium by
constructing a table showing what is known and what needs to be calculated, just as we did in Example 7.3.2.
n-butane (g) ⇌ isobutane (g) (7.3.3)

ICE [n-butane (g) ] [isobutane (g) ]

Initial

Change

Final

The initial concentrations of the reactant and product are both known: [n-butane]i = 1.00 M and [isobutane]i = 0 M. We need to
calculate the equilibrium concentrations of both n-butane and isobutane. Because it is generally difficult to calculate final
concentrations directly, we focus on the change in the concentrations of the substances between the initial and the final
(equilibrium) conditions. If, for example, we define the change in the concentration of isobutane (Δ[isobutane]) as +x, then the
change in the concentration of n-butane is Δ[n-butane] = −x. This is because the balanced chemical equation for the reaction tells
us that 1 mol of n-butane is consumed for every 1 mol of isobutane produced. We can then express the final concentrations in terms
of the initial concentrations and the changes they have undergone.

n-butane (g) ⇌ isobutane (g) (7.3.4)

7.3.4 [Link]
 ICE [n-butane (g) ] [isobutane (g) ]

Initial 1.00 0

Change −x +x

Final (1.00 − x) (0 + x) = x

Substituting the expressions for the final concentrations of n-butane and isobutane from the table into the equilibrium equation,
[isobutane] x
K = = = 2.6 (7.3.5)
[n-butane] 1.00 − x

Rearranging and solving for x,

x = 2.6(1.00 − x) = 2.6 − 2.6x (7.3.6)

x + 2.6x = 2.6 (7.3.7)

x = 0.72 (7.3.8)

We obtain the final concentrations by substituting this x value into the expressions for the final concentrations of n-butane and
isobutane listed in the table:

[n-butane]f = (1.00 − x)M = (1.00 − 0.72)M = 0.28 M (7.3.9)

[isobutane]f = (0.00 + x)M = (0.00 + 0.72)M = 0.72 M (7.3.10)

We can check the results by substituting them back into the equilibrium constant expression to see whether they give the same K
that we used in the calculation:

[isobutane] 0.72 M
K = =( ) = 2.6 (7.3.11)
[n-butane] 0.28 M

This is the same K we were given, so we can be confident of our results.

Example 7.3.3 illustrates a common type of equilibrium problem that you are likely to encounter.

Example 7.3.3 : The water–gas shift reaction

The water–gas shift reaction is important in several chemical processes, such as the production of H2 for fuel cells. This reaction
can be written as follows:

H2(g) + C O2(g) ⇌ H2 O(g) + C O(g)

K = 0.106 at 700 K. If a mixture of gases that initially contains 0.0150 M H and 0.0150 M C O is allowed to equilibrate at
2 2

700 K, what are the final concentrations of all substances present?

Given: balanced equilibrium equation, K , and initial concentrations
Asked for: final concentrations
Strategy:
A. Construct a table showing what is known and what needs to be calculated. Define x as the change in the concentration of one
substance. Then use the reaction stoichiometry to express the changes in the concentrations of the other substances in terms
of x. From the values in the table, calculate the final concentrations.
B. Write the equilibrium equation for the reaction. Substitute appropriate values from the ICE table to obtain x.
C. Calculate the final concentrations of all species present. Check your answers by substituting these values into the equilibrium
constant expression to obtain K .
SOLUTION
A The initial concentrations of the reactants are [H ] = [C O ] = 0.0150 M . Just as before, we will focus on the change in
2 i 2 i

the concentrations of the various substances between the initial and final states. If we define the change in the concentration of
H O as x, then Δ[ H O] = +x . We can use the stoichiometry of the reaction to express the changes in the concentrations of the
2 2

7.3.5 [Link]
other substances in terms of x. For example, 1 mol of C O is produced for every 1 mol of H O, so the change in the C O 2

concentration can be expressed as Δ[C O] = +x. Similarly, for every 1 mol of H O produced, 1 mol each of H and C O are
2 2 2

consumed, so the change in the concentration of the reactants is Δ[H ] = Δ[C O ] = −x . We enter the values in the following
2 2

table and calculate the final concentrations.

H2(g) + C O2(g) ⇌ H2 O(g) + C O(g)

ICE [ H2 ] [CO2 ] [ H2 O] [CO]

Initial 0.0150 0.0150 0 0

Change −x −x +x +x

Final (0.0150 − x) (0.0150 − x) x x

B We can now use the equilibrium equation and the given K to solve for x:
2
[ H2 O][C O] (x)(x) x
K = = = = 0.106
2
[ H2 ][C O2 ] (0.0150 − x)(0.0150 − x (0.0150 − x)

We could solve this equation with the quadratic formula, but it is far easier to solve for x by recognizing that the left side of the
equation is a perfect square; that is,
2 2
x x
=( ) = 0.106
2
(0.0150 − x) 0.0150 − x

Taking the square root of the middle and right terms,

x 1/2
= (0.106 ) = 0.326
(0.0150 − x)

x = (0.326)(0.0150) − 0.326x

1.326x = 0.00489

−3
x = 0.00369 = 3.69 × 10

C The final concentrations of all species in the reaction mixture are as follows:
[ H2 ]f = [ H2 ]i + Δ[ H2 ] = (0.0150 − 0.00369) M = 0.0113 M

[C O2 ]f = [C O2 ]i + Δ[C O2 ] = (0.0150 − 0.00369) M = 0.0113 M

[ H2 O]f = [ H2 O]i + Δ[ H2 O] = (0 + 0.00369) M = 0.00369 M

[C O]f = [C O]i + Δ[C O] = (0 + 0.00369) M = 0.00369 M

We can check our work by inserting the calculated values back into the equilibrium constant expression:
2
[ H2 O][C O] (0.00369)
K = = = 0.107
2
[ H2 ][C O2 ] (0.0113)

To two significant figures, this K is the same as the value given in the problem, so our answer is confirmed.

Exercise 7.3.3
Hydrogen gas reacts with iodine vapor to give hydrogen iodide according to the following chemical equation:
H2(g) + I2(g) ⇌ 2H I(g)

K = 54 at 425°C. If 0.172 M H and I are injected into a reactor and maintained at 425°C until the system equilibrates, what
2 2

is the final concentration of each substance in the reaction mixture?

Answer
[H I ]f = 0.270 M

7.3.6 [Link]
 [ H2 ]f = [ I2 ]f = 0.037 M

In Example 7.3.3, the initial concentrations of the reactants were the same, which gave us an equation that was a perfect square and
simplified our calculations. Often, however, the initial concentrations of the reactants are not the same, and/or one or more of the
products may be present when the reaction starts. Under these conditions, there is usually no way to simplify the problem, and we
must determine the equilibrium concentrations with other means. Such a case is described in Example 7.3.4.

Example 7.3.4
In the water–gas shift reaction shown in Example 7.3.3, a sample containing 0.632 M CO2 and 0.570 M H is allowed to 2

equilibrate at 700 K. At this temperature, K = 0.106 . What is the composition of the reaction mixture at equilibrium?
Given: balanced equilibrium equation, concentrations of reactants, and K
Asked for: composition of reaction mixture at equilibrium
Strategy:
A. Write the equilibrium equation. Construct a table showing the initial concentrations of all substances in the mixture.
Complete the table showing the changes in the concentrations (\(x) and the final concentrations.
B. Write the equilibrium constant expression for the reaction. Substitute the known K value and the final concentrations to
solve for x.
C. Calculate the final concentration of each substance in the reaction mixture. Check your answers by substituting these values
into the equilibrium constant expression to obtain K .
SOLUTION
A [C O ] = 0.632 M and [H ] = 0.570 M . Again, x is defined as the change in the concentration of H O: Δ[H O] = +x .
2 i 2 i 2 2

Because 1 mol of C O is produced for every 1 mol of H O, the change in the concentration of C O is the same as the change in
2

the concentration of H2O, so Δ[CO] = +x. Similarly, because 1 mol each of H and C O are consumed for every 1 mol of H O
2 2 2

produced, Δ[H ] = Δ[C O ] = −x . The final concentrations are the sums of the initial concentrations and the changes in
2 2

concentrations at equilibrium.

H2(g) + C O2(g) ⇌ H2 O(g) + C O(g)

ICE H2(g) CO2(g) H2 O(g) CO(g)

Initial 0.570 0.632 0 0

Change −x −x +x +x

Final (0.570 − x) (0.632 − x) x x

B We can now use the equilibrium equation and the known K value to solve for x:
2
[ H2 O][C O] x
K = = = 0.106
[ H2 ][C O2 ] (0.570 − x)(0.632 − x)

In contrast to Example 7.3.3, however, there is no obvious way to simplify this expression. Thus we must expand the expression
and multiply both sides by the denominator:
2 2
x = 0.106(0.360 − 1.202x + x )

Collecting terms on one side of the equation,

2
0.894 x + 0.127x − 0.0382 = 0

This equation can be solved using the quadratic formula:

− − −−−−− − −−−−−−−−−−−−−−−−−−−−− −
2 2
−b ± √ b − 4ac −0.127 ± √ (0.127 ) − 4(0.894)(−0.0382)
x = =
2a 2(0.894)

7.3.7 [Link]
 x = 0.148 and − 0.290

Only the answer with the positive value has any physical significance, so Δ[ H2 O] = Δ[C O] = +0.148M , and
Δ[ H ] = Δ[C O ] = −0.148 M .
2 2

C The final concentrations of all species in the reaction mixture are as follows:
[ H2 ]f [= [ H2 ]i + Δ[ H2 ] = 0.570 M − 0.148 M = 0.422M

[C O2 ]f = [C O2 ]i + Δ[C O2 ] = 0.632 M − 0.148 M = 0.484M

[ H2 O]f = [ H2 O]i + Δ[ H2 O] = 0 M + 0.148 M = 0.148 M

[C O]f = [C O]i + Δ[C O] = 0M + 0.148 M = 0.148M

We can check our work by substituting these values into the equilibrium constant expression:
2
[ H2 O][C O] (0.148)
K = = = 0.107
[ H2 ][C O2 ] (0.422)(0.484)

Because K is essentially the same as the value given in the problem, our calculations are confirmed.

Exercise 7.3.4
The exercise in Example 7.3.1 showed the reaction of hydrogen and iodine vapor to form hydrogen iodide, for which K = 54
at 425°C. If a sample containing 0.200 M H and 0.0450 M I is allowed to equilibrate at 425°C, what is the final concentration
2 2

of each substance in the reaction mixture?

Answer
[ HI ]f = 0.0882 M

[ H2 ]f = 0.156 M
−4
[ I2 ]f = 9.2 × 10 M

Summary
Various methods can be used to solve the two fundamental types of equilibrium problems: (1) those in which we calculate the
concentrations of reactants and products at equilibrium and (2) those in which we use the equilibrium constant and the initial
concentrations of reactants to determine the composition of the equilibrium mixture. When an equilibrium constant is calculated
from equilibrium concentrations, molar concentrations are substituted into the equilibrium constant expression for the reaction.
Equilibrium constants can be used to calculate the equilibrium concentrations of reactants and products by using the quantities or
concentrations of the reactants, the stoichiometry of the balanced chemical equation for the reaction, and a tabular format to obtain
the final concentrations of all species at equilibrium.

Contributors
Modified by Tom Neils (Grand Rapids Community College)

7.3: Calculating the Equilibrium Constant From Measured Equilibrium Concentrations is shared under a CC BY-NC-SA 4.0 license and was
authored, remixed, and/or curated by LibreTexts.

7.3.8 [Link]
7.4 Predicting the Direction of a Reaction
Skills to Develop
To predict in which direction a reaction will proceed.

We previously saw that knowing the magnitude of the equilibrium constant under a given set of conditions allows chemists to
predict the extent of a reaction. Often, however, chemists must decide whether a system has reached equilibrium or if the
composition of the mixture will continue to change with time. In this section, we describe how to quantitatively analyze the
composition of a reaction mixture to make this determination.

The Reaction Quotient

To determine whether a system has reached equilibrium, chemists use a Quantity called the reaction Quotient (Q). The expression
for the reaction Quotient has precisely the same form as the equilibrium constant expression, except that Q may be derived from a
set of values measured at any time during the reaction of any mixture of the reactants and the products, regardless of whether the
system is at equilibrium. Therefore, for the following general reaction:
aA + bB ⇌ cC + dD (1)

the reaction quotient is defined as follows:

c d
[C ] [D]
Q = (2)
a b
[A] [B]

To understand how information is obtained using a reaction Quotient, consider the dissociation of dinitrogen tetroxide to nitrogen
dioxide,
N2 O4(g) ⇌ 2N O2(g) (3)

for which K = 4.65 × 10 −3

at 298 K. We can write Q for this reaction as follows:
2
[N O2 ]
Q = (4)
[ N2 O4 ]

The following table lists data from three experiments in which samples of the reaction mixture were obtained and analyzed at
equivalent time intervals, and the corresponding values of Q were calculated for each. Each experiment begins with different
proportions of product and reactant:
2 2
[NO ]
Experiment [N O2 ] (M ) [N2 O4 ] (M ) Q =
2 4
[N O ]

2
0
1 0 0.0400 = 0
0.0400

2
(0.0600)
2 0.0600 0 = undefined
0

2
(0.0200)
3 0.0200 0.0600 = 6.67 × 10
−3

0.0600

As these calculations demonstrate, Q can have any numerical value between 0 and infinity (undefined); that is, K can be greater
than, less than, or equal to Q.
Comparing the magnitudes of K and Q enables us to determine whether a reaction mixture is already at equilibrium and, if it is not,
predict how its composition will change with time to reach equilibrium (i.e., whether the reaction will proceed to the right or to the
left as written). All you need to remember is that the composition of a system not at equilibrium will change in a way that makes Q
approach K. If K = Q , for example, then the system is already at equilibrium, and no further change in the composition of the
system will occur unless the conditions are changed. If K > Q , then the ratio of the concentrations of products to the

1 [Link]
concentrations of reactants is less than the ratio at equilibrium. Therefore, the reaction will proceed to the right as written, forming
products at the expense of reactants. Conversely, if K < Q , then the ratio of the concentrations of products to the concentrations of
reactants is greater than at equilibrium, so the reaction will proceed to the left as written, forming reactants at the expense of
products. These points are illustrated graphically in Figure 1.

Figure 1 : Two Different Ways of Illustrating How the Composition of a System Will Change Depending on the Relative Values of Q
and K.(a) Both Q and K are plotted as points along a number line: the system will always react in the way that causes Q to
approach K. (b) The change in the composition of a system with time is illustrated for systems with initial values of K < Q ,
K > Q , and K = Q .

If K > Q , the reaction will proceed to the right as written. If K < Q , the reaction will
proceed to the left as written.
If K = Q , then the system is at equilibrium.
Example 1
At elevated temperatures, methane (C H ) reacts with water to produce hydrogen and carbon monoxide in what is known as a
4

steam-reforming reaction:

C H4(g) + H2 O(g) ⇌ C O(g) + 3 H2(g) (5)

K = 2.4 × 10
−4
at 900 K. Huge amounts of hydrogen are produced from natural gas in this way and are then used for the
industrial synthesis of ammonia. If 1.2 × 10 mol of C H , 8.0 × 10−3 mol of H O, 1.6 × 10 mol of C O, and 6.0 × 10
−2
4 2
−2 −3

mol of H are placed in a 2.0 L steel reactor and heated to 900 K, will the reaction be at equilibrium or will it proceed to the
2

right to produce C O and H or to the left to form C H and H O?

2 4 2

Given: balanced chemical equation, K, amounts of reactants and products, and volume
Asked for: direction of reaction
Strategy:
A. Calculate the molar concentrations of the reactants and the products.
B. Use Equation 2 to determine Q . Compare Q and K to determine in which direction the reaction will proceed.
Solution:
A We must first find the initial concentrations of the substances present. For example, we have 1.2 × 10 −2
mol of C H in a 2.0
4

L container, so
−2
1.2 × 10 mol −3
[C H4 ] = = 6.0 × 10 M (6)
2.0 L

We can calculate the other concentrations in a similar way:

[ H2 O] = 4.0 × 10
−3
M ,

2 [Link]
 [C O] = 8.0 × 10
−3
M , and
[ H2 ] = 3.0 × 10
−3
M .
B We now compute Q and compare it with K :
3 −3 −3 3
[C O][H2 ] (8.0 × 10 )(3.0 × 10 )
−6
Q = = = 9.0 × 10 (7)
−3 −3
[C H4 ][ H2 O (6.0 × 10 )(4.0 × 10 )

Because K = 2.4 × 10 , we see that K > Q . Thus the ratio of the concentrations of products to the concentrations of
−4

reactants is less than the ratio for an equilibrium mixture. The reaction will therefore proceed to the right as written, forming H 2

and C O at the expense of H O and C H . 2 4

Exercise 2
In the water–gas shift reaction introduced in Example 1, carbon monoxide produced by steam-reforming reaction of methane
reacts with steam at elevated temperatures to produce more hydrogen:
C O(g) + H2 O(g) ⇌ C O2(g) + H2(g) (8)

K = 0.64 at 900 K. If 0.010 mol of both C O and H O, 0.0080 mol of C O , and 0.012 mol of
2 2 H2 are injected into a 4.0 L
reactor and heated to 900 K, will the reaction proceed to the left or to the right as written?

Answer
Q = 0.96 . Since K < Q , the reaction will proceed to the left, and C O and H 2O will form.

Predicting the Direction of a Reaction with a Graph

By graphing a few equilibrium concentrations for a system at a given temperature and pressure, we can readily see the range of
reactant and product concentrations that correspond to equilibrium conditions, for which K = Q . Such a graph allows us to predict
what will happen to a reaction when conditions change so that Q no longer equals K , such as when a reactant concentration or a
product concentration is increased or decreased.
Lead carbonate decomposes to lead oxide and carbon dioxide according to the following equation:
P bC O3(s) ⇌ P b O(s) + C O2(g) (9)

Because P bC O and P bO are solids, the equilibrium constant is simply K = [C O ] . At a given temperature, therefore, any
3 2

system that contains solid P bC O and solid P bO will have exactly the same concentration of C O at equilibrium, regardless of
3 2

the ratio or the amounts of the solids present. This situation is represented in Figure 3, which shows a plot of [C O ] versus the 2

amount of P bC O added. Initially, the added P bC O decomposes completely to C O because the amount of P bC O is not
3 3 2 3

sufficient to give a C O concentration equal to K . Thus the left portion of the graph represents a system that is not at equilibrium
2

because it contains only CO2(g) and PbO(s). In contrast, when just enough P bC O has been added to give [C O ] = K , the 3 2

system has reached equilibrium, and adding more P bC O has no effect on the C O concentration: the graph is a horizontal line.
3 2

Thus any C O concentration that is not on the horizontal line represents a nonequilibrium state, and the system will adjust its
2

composition to achieve equilibrium, provided enough P bC O and P bO are present. For example, the point labeled A in Figure 2
3

lies above the horizontal line, so it corresponds to a [C O ] that is greater than the equilibrium concentration of C O (K < Q). To
2 2

reach equilibrium, the system must decrease [C O ], which it can do only by reacting C O with solid P bO to form solid P bC O .
2 2 3

Thus the reaction in Equation 9 will proceed to the left as written, until [C O ] = K . Conversely, the point labeled B in Figure 2
2

lies below the horizontal line, so it corresponds to a [C O ] that is less than the equilibrium concentration of C O (K > Q). To reach
2 2

equilibrium, the system must increase [C O ], which it can do only by decomposing solid P bC O to form C O and solid P bO.
2 3 2

The reaction in Equation 9 will therefore proceed to the right as written, until [C O ] = K . 2

3 [Link]
 Figure 2 : The Concentration of Gaseous C O in a Closed System at Equilibrium as a Function of the Amount of Solid P bC O
2 3

Added. Initially the concentration of CO2(g) increases linearly with the amount of solid P bC O added, as P bC O decomposes to
3 3

CO2(g) and solid PbO. Once the C O concentration reaches the value that corresponds to the equilibrium concentration, however,
2

adding more solid P bC O has no effect on [C O ], as long as the temperature remains constant.
3 2

In contrast, the reduction of cadmium oxide by hydrogen gives metallic cadmium and water vapor:
C dO(s) + H2(g) ⇌ C d(s) + H2 O(g) (10)

and the equilibrium constant K is [H O]/[H ]. If [H O] is doubled at equilibrium, then [H2] must also be doubled for the system
2 2 2

to remain at equilibrium. A plot of [H O] versus [H ] at equilibrium is a straight line with a slope of K (Figure 3). Again, only
2 2

those pairs of concentrations of H O and H that lie on the line correspond to equilibrium states. Any point representing a pair of
2 2

concentrations that does not lie on the line corresponds to a nonequilibrium state. In such cases, the reaction in Equation 10 will
proceed in whichever direction causes the composition of the system to move toward the equilibrium line. For example, point A in
Figure 3 lies below the line, indicating that the [H O]/[H ] ratio is less than the ratio of an equilibrium mixture (K > Q). Thus the
2 2

reaction in Equation 10 will proceed to the right as written, consuming H and producing H O, which causes the concentration
2 2

ratio to move up and to the left toward the equilibrium line. Conversely, point B in Figure 3 lies above the line, indicating that the
[ H O]/[ H ] ratio is greater than the ratio of an equilibrium mixture (K < Q). Thus the reaction in Equation 10 will proceed to the
2 2

left as written, consuming H O and producing H , which causes the concentration ratio to move down and to the right toward the
2 2

equilibrium line.

Figure 3 : The Concentration of Water Vapor versus the Concentration of Hydrogen for the C dO + H (s)
⇌ Cd2(g)
+H O (s) 2 (g)

System at Equilibrium. For any equilibrium concentration of H O , there is only one equilibrium concentration of H .
2 (g) 2(g)

Because the magnitudes of the two concentrations are directly proportional, a large [H O] at equilibrium requires a large [H
2 2]

and vice versa. In this case, the slope of the line is equal to K.
In another example, solid ammonium iodide dissociates to gaseous ammonia and hydrogen iodide at elevated temperatures:
N H4 I(s) ⇌ N H3(g) + H I(g) (11)

4 [Link]
For this system, K is equal to the product of the concentrations of the two products: [N H ][H I ]. If we double the concentration of
3

NH3, the concentration of HI must decrease by approximately a factor of 2 to maintain equilibrium, as shown in Figure 4. As a
result, for a given concentration of either H I or N H , only a single equilibrium composition that contains equal concentrations of
3

both N H and HI is possible, for which [N H ] = [H I ] = K . Any point that lies below and to the left of the equilibrium curve
3 3
1/2

(such as point A in Figure 4) corresponds to K > Q , and the reaction in Equation 11 will therefore proceed to the right as written,
causing the composition of the system to move toward the equilibrium line. Conversely, any point that lies above and to the right of
the equilibrium curve (such as point B in Figure 11) corresponds to K < Q , and the reaction in Equation 11 will therefore proceed
to the left as written, again causing the composition of the system to move toward the equilibrium line. By graphing equilibrium
concentrations for a given system at a given temperature and pressure, we can predict the direction of reaction of that mixture when
the system is not at equilibrium.

Figure 4 : The Concentration of N H versus the Concentration of H I for the N H I ⇌ N H

3(g) (g) 4 (s) + HI System at
3(g) (g)

Equilibrium. Only one equilibrium concentration of N H is possible for any given equilibrium concentration of HI(g). In this
3(g)

case, the two are inversely proportional. Thus a large [H I ] at equilibrium requires a small [N H ] at equilibrium and vice versa.
3

Summary
The reaction quotient (Q) is used to determine whether a system is at equilibrium and if it is not, to predict the direction of reaction.
The reaction Quotient (Q) has the same form as the equilibrium constant expression, but it is derived from concentrations obtained
at any time. When a reaction system is at equilibrium, K = Q . Graphs derived by plotting a few equilibrium concentrations for a
system at a given temperature and pressure can be used to predict the direction in which a reaction will proceed. Points that do not
lie on the line or curve represent nonequilibrium states, and the system will adjust, if it can, to achieve equilibrium.

Contributors
Modified by Tom Neils (Grand Rapids Community College)

7.4 Predicting the Direction of a Reaction is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

5 [Link]
7.5 Le Châtelier’s Principle: How a System at Equilibrium Responds to Disturbances
Skills to Develop
Describe the ways in which an equilibrium system can be stressed
Predict the response of a stressed equilibrium using Le Chatelier’s principle

As we saw in the previous section, reactions proceed in both directions (reactants go to products and products go to reactants). We
can tell a reaction is at equilibrium if the reaction quotient (Q) is equal to the equilibrium constant (K). We next address what
happens when a system at equilibrium is disturbed so that Q is no longer equal to K. If a system at equilibrium is subjected to a
perturbance or stress (a change in concentration of one of the species in the law of mass action) the position of equilibrium
changes. Since this stress affects the concentrations of the reactants and the products, the value of Q will no longer equal the value
of K. To re-establish equilibrium, the system will either shift toward the products (if K > Q) or the reactants (if K < Q) until Q
returns to the same value as K. This process is described by Le Chatelier's principle.
Le Chatelier's principle
When a chemical system at equilibrium is disturbed, it returns to equilibrium by counteracting the disturbance. As described in
the previous paragraph, the disturbance causes a change in the value of Q; the reaction will shift to re-establish K = Q

Predicting the Direction of a Reversible Reaction

Le Chatelier's principle can be used to predict changes in equilibrium concentrations when a system that is at equilibrium is
subjected to a stress. However, if we have a mixture of reactants and products that have not yet reached equilibrium, the changes
necessary to reach equilibrium may not be so obvious. In such a case, we can compare the values of Q and K for the system to
predict the changes.

A chemical system at equilibrium can be temporarily shifted out of equilibrium by adding

or removing one or more of the reactants or products. The concentrations of both
reactants and products then undergo additional changes to return the system to
equilibrium.
The stress on the system in Figure 7.9.1 is the reduction of the equilibrium concentration of SCN− (lowering the concentration of
one of the reactants would cause K to be larger than Q). As a consequence, Le Chatelier's principle leads us to predict that the
concentration of Fe(SCN)2+ should decrease, increasing the concentration of SCN− part way back to its original concentration, and
increasing the concentration of Fe3+ above its initial equilibrium concentration.

Figure 7.9.1: (a) The test tube contains 0.1 M Fe3+. (b) Thiocyanate ion has been added to solution in (a), forming the red
Fe(SCN)2+ ion: F e 2+

(aq)
+ SC N
−

(aq)
⇌ F e(SC N )
2+
(c) Silver nitrate has been added to the solution in (b), precipitating some of
(aq)

the SCN− as the white solid AgSCN: Ag +

(aq)
+ SC N
−

(aq)
⇌ AgSC N(s) . The decrease in the SCN− concentration shifts the first
equilibrium in the solution to the left, decreasing the concentration of the Fe(SCN)2+, and lightening color. (credit: modification of
work by Mark Ott).
The effect of a change in concentration on a system at equilibrium is illustrated further by the equilibrium of this chemical reaction:
H2(g) + I2(g) ⇌ 2H Ig

7.5 Le Châtelier’s Principle.1 [Link]

 K = 50.0 at 400oC
The numeric values for this example have been determined experimentally. A mixture of gases at 400 °C with [H2] = [I2] = 0.221
M and [HI] = 1.563 M is at equilibrium; for this mixture, K = Q. If H2 is introduced into the system so quickly that its
concentration doubles before it begins to react (new [H2] = 0.442 M), the reaction will shift so that equilibrium is reattained with
new concentrations of [H2], [I2], and [HI]:
[H2] = 0.374 M

[I2] = 0.153 M

[HI] = 1.692 M

This gives
2
[H I ]
Q =
[ H2 ][ I2 ]

2
[1.692]
Q =
[0.374][0.153]

Q = 50.0 = K

Even though we have stressed this system by introducing additional H2, the stress is relieved as the reaction shifts to the right,
using up some (but not all) of the excess H2, reducing the amount of unreacted I2, and forming additional HI. There are new
concentrations of all three substances, but the ratio of these concentrations, as described by the law of mass action, is once again
equal to 50.0, because that is the fixed value of K for this reaction at this temperature.

Effect of Change in Pressure on Equilibrium

Sometimes we can change the position of equilibrium by changing the pressure of a system. However, changes in pressure have a
measurable effect only in systems in which gases are involved, and then only when the chemical reaction produces a change in the
total number of gas molecules in the system. In addition, the change in pressure must cause a change in concentration of the
substances involved in the reaction. The only practical way to cause a concentration change by making a pressure change is to
change the size of the container holding the gases. Some changes to total pressure, such as adding an inert gas that is not part of the
equilibrium, will change the total pressure but not the partial pressures of the gases in the equilibrium constant expression. Thus,
addition of a gas not involved in the equilibrium will not perturb the equilibrium.
As we increase the pressure of a gaseous system at equilibrium, either by decreasing the volume of the system or by adding more of
one of the components of the equilibrium mixture, we introduce a stress by increasing the partial pressures of one or more of the
components. In accordance with Le Chatelier's principle, a shift in the equilibrium that reduces the total number of molecules per
unit of volume will be favored because this relieves the stress. The reverse reaction would be favored by a decrease in pressure.
Consider what happens if we shrink the flask, thus increasing the pressure on a system in which NO, O2, and NO2 are at
equilibrium:
2N O(g) + O2(g) ⇌ N O2(g)

Increasing the pressure causes the concentration of all of the gases to increase (because molarity is moles per Liter, and you just
decreased the volume). To reattain equilibrium, the reaction will shift to the right, the side with fewer moles of gas. This shift to the
right happens because it decreases the total number of molecules in the system because each time two molecules of NO2 form, a
total of three molecules of NO and O2 are consumed. Thus, the shift to the right reduces the total pressure exerted by the system
and leads to new concentrations of all of the gases that, when plugged into the law of mass action, result in K = Q.
On the other hand, expanding the flask will cause a decrease in the pressure on the system, which means that the concentrations of
all the gases decrease. To reattain equilibrium, the reaction will shift to the left, the side with more moles of gas. This shift to the
left happens because it increases the total number of molecules in the system because each time two molecules of NO2 are
consumed, a total of three molecules of NO and O2 are formed. Thus, the shift to the left increases the total pressure exerted by the
system and and leads to new concentrations of all of the gases that, when plugged into the law of mass action, result in K = Q.
Now consider this reaction:
N2(g) + O2(g) ⇌ 2N O(g)

7.5 Le Châtelier’s Principle.2 [Link]

Because there is no change in the total number of molecules in the system during reaction, a change in pressure does not cause a
shift away from equilibrium, because the value of Q will equal K throughout any pressure change.

Effect of Change in Temperature on Equilibrium

Changing concentration perturbs an equilibrium because the reaction quotient is shifted away from the equilibrium value. In other
words, Q will not equal K at the instant of the change. Changing the temperature of a system at equilibrium has a different effect: A
change in temperature actually changes the value of the equilibrium constant. However, we can qualitatively predict the effect of
the temperature change by treating it as a stress on the system and applying Le Chatelier's principle.
When hydrogen reacts with gaseous iodine, heat is evolved.
o
H2(g) + I2(g) ⇌ 2H I(g) ΔH = −9.4 kJ

Because this reaction is exothermic, we can write it with heat as a product:

H2(g) + I2(g) ⇌ 2H I(g) + heat

Increasing the temperature of the reaction increases the internal energy of the system. Thus, increasing the temperature has the
effect of increasing the amount of heat, one of the products of this reaction. The reaction shifts to the left to relieve the stress, and
there is an increase in the concentration of H2 and I2 and a reduction in the concentration of HI. Lowering the temperature of this
system reduces the amount of energy present, favors the production of heat, and favors the formation of hydrogen iodide.
When we change the temperature of a system at equilibrium, the equilibrium constant for the reaction changes. Lowering the
temperature in the HI system increases the equilibrium constant: At the new equilibrium the concentration of HI has increased and
the concentrations of H2 and I2 decreased. Raising the temperature decreases the value of the equilibrium constant, from 67.5 at
357 °C to 50.0 at 400 °C.
Temperature affects the equilibrium between NO2 and N2O4 in the reaction:
o
N2 O4(g) ⇌ 2N O2(g) ΔH = 57.2 kJ

The positive ΔH value tells us that the reaction is endothermic and could be written:
heat + N2 O4(g) ⇌ 2N O2(g)

At higher temperatures, the gas mixture has a deep brown color, indicative of a significant amount of brown NO2 molecules. If,
however, we put a stress on the system by cooling the mixture (withdrawing energy), the equilibrium shifts to the left to supply
some of the energy lost by cooling. The concentration of colorless N2O4 increases, and the concentration of brown NO2 decreases,
causing the brown color to fade.
The overview of how different disturbances affect the reaction equilibrium properties is tabulated in Table 7.9.1
Table 7.9.1: Effects of Disturbances of Equilibrium and K
Observed Change as
Disturbance Direction of Shift Effect on K
Equilibrium is Restored

added reactant is partially

reactant added toward products none
consumed

added product is partially

product added toward reactants none
consumed

decrease in volume/increase in gas toward side with fewer moles of

pressure decreases none
pressure gas

increase in volume/decrease in gas toward side with fewer moles of

pressure increases none
pressure gas

toward products for endothermic,

temperature increase heat is absorbed changes
toward reactants for exothermic

toward reactants for endothermic,

temperature decrease heat is given off changes
toward products for exothermic

Example 7.5LeChâtelier sP rinciple. 1 ′

7.5 Le Châtelier’s Principle.3 [Link]

 Write an equilibrium constant expression for each reaction and use this expression to predict in which direction the reaction will
shift to reattain equilibrium.
a. 2H gO ⇌ 2H g + O
(s)
: the amount of HgO is doubled.
(l) 2(g)

b. N H H S ⇌ N H
4 +H S
(s) : the concentration of H2S is tripled
3(g) 2 (g)

c. n − butane ⇌ isobutane : the concentration of isobutane is halved.

(g) (g)

Given: equilibrium systems and changes

Asked for: equilibrium constant expressions and effects of changes
Strategy:
Write the equilibrium constant expression, remembering that pure liquids and solids do not appear in the expression. From this
expression, predict the change that must occur to maintain equilibrium when the indicated changes are made.
Solution:
a. Because HgO is a pure solid and Hg is a pure liquid, they both are assigned an activity of '1' and their amounts do not appear
in the equilibrium constant expression. Thus, for this reaction, K = [O2]. The equilibrium concentration of O2 is a constant and
does not depend on the amount of HgO present. Hence adding more HgO will not affect the equilibrium concentration of O2 so
no compensatory change is necessary. The reaction does not shift from equilibrium.
b. NH4HS is assign a value of '1' in the equilibrium constant expression because it is a solid. Thus K = [NH3][H2S], which
means that the concentrations of the products are inversely proportional. If the concentration of H2S triples, for example, then
the concentration of NH3 must decrease by about a factor of 3 for the system to remain at equilibrium so that the product of the
concentrations (Q) equals K. The reaction must shift left to reach equilibrium.
[isobutane]
c. For this reaction K = , so halving the concentration of isobutane means that the n-butane concentration must
[n − butane]

also decrease by about half if the system is to maintain equilibrium. The reaction must shift to the right to reach equilibrium.

Exercise 7.5LeChâtelier sP rinciple. 1 ′

In which direction will the reaction shift if the stated stress is placed on the reaction at equilibrium?
a. H Br (g)
+ N aH(s) ⇌ N aBr(s) + H2(g) : the concentration of HBr is decreased by a factor of 3.
b. 6Li (s) + N2(g) ⇌ 2Li3 N(s) : the amount of Li is tripled.
c. SO 2(g) + C l2(g) ⇌ S O2 C l2(l) : the concentration of Cl2 is doubled.

Answer
a. The reaction will shift left to reattain equilibrium because you removed reactant.
b. The reaction will not shift because Li is a solid
c. The reaction will shift to the right because you added a reactant.

Catalysts Do Not Affect Equilibrium

As we learned during our study of kinetics, a catalyst can speed up the rate of a reaction. Though this increase in reaction rate may
cause a system to reach equilibrium more quickly (by speeding up the forward and reverse reactions), a catalyst has no effect on the
value of an equilibrium constant nor on equilibrium concentrations. The interplay of changes in concentration or pressure,
temperature, and the lack of an influence of a catalyst on a chemical equilibrium is illustrated in the industrial synthesis of
ammonia from nitrogen and hydrogen according to the equation:
N2(g) + 3 H2(g) ⇌ 2N H3(g)

A large quantity of ammonia is manufactured by this reaction. Each year, ammonia is among the top 10 chemicals, by mass,
manufactured in the world. About 2 billion pounds are manufactured in the United States each year. Ammonia plays a vital role in
our global economy. It is used in the production of fertilizers and is, itself, an important fertilizer for the growth of corn, cotton, and
other crops. Large quantities of ammonia are converted to nitric acid, which plays an important role in the production of fertilizers,
explosives, plastics, dyes, and fibers, and is also used in the steel industry.

7.5 Le Châtelier’s Principle.4 [Link]

 Fritz Haber
Haber was born in Breslau, Prussia (presently Wroclaw, Poland) in December 1868. He went on to study chemistry and, while at
the University of Karlsruhe, he developed what would later be known as the Haber process: the catalytic formation of ammonia
from hydrogen and atmospheric nitrogen under high temperatures and pressures. For this work, Haber was awarded the 1918
Nobel Prize in Chemistry for synthesis of ammonia from its elements as shown above. The Haber process was a boon to
agriculture, as it allowed the production of fertilizers to no longer be dependent on mined feed stocks such as sodium nitrate.

Figure 7.9.2: The work of Nobel Prize recipient Fritz Haber revolutionized agricultural practices in the early 20th century. His
work also affected wartime strategies, adding chemical weapons to the artillery.
Currently, the annual production of synthetic nitrogen fertilizers exceeds 100 million tons and synthetic fertilizer production has
increased the number of humans that arable land can support from 1.9 persons per hectare in 1908 to 4.3 in 2008. The
availability of nitrogen is a strong limiting factor to the growth of plants. Despite accounting for 78% of air, diatomic nitrogen
(N2) is nutritionally unavailable to a majority of plants due the tremendous stability of the nitrogen-nitrogen triple bond.
Therefore, the nitrogen must be converted to a more bioavailable form (this conversion is called nitrogen fixation). Legumes
achieve this conversion at ambient temperature by exploiting bacteria equipped with suitable enzymes.
In addition to his work in ammonia production, Haber is also remembered by history as one of the fathers of chemical warfare.
During World War I, he played a major role in the development of poisonous gases used for trench warfare. Regarding his role
in these developments, Haber said, “During peace time a scientist belongs to the World, but during war time he belongs to his
country.”1 Haber defended the use of gas warfare against accusations that it was inhumane, saying that death was death, by
whatever means it was inflicted. He stands as an example of the ethical dilemmas that face scientists in times of war and the
double-edged nature of the sword of science.
Like Haber, the products made from ammonia can be multifaceted. In addition to their value for agriculture, nitrogen
compounds can also be used to achieve destructive ends. Ammonium nitrate has also been used in explosives, including
improvised explosive devices. Ammonium nitrate was one of the components of the bomb used in the attack on the Alfred P.
Murrah Federal Building in downtown Oklahoma City on April 19, 1995.

Summary
Systems at equilibrium can be disturbed by changes to temperature, concentration, and, in some cases, volume and pressure;
volume and pressure changes will disturb equilibrium if the number of moles of gas is different on the reactant and product sides of
the reaction. The system's response to these disturbances is described by Le Chatelier's principle: The system will respond in a way
that counteracts the disturbance. Not all changes to the system result in a disturbance of the equilibrium. Adding a catalyst affects
the rates of the reactions but does not alter the equilibrium, and changing pressure or volume will not significantly disturb systems
with no gases or with equal numbers of moles of gas on the reactant and product side.

Footnotes
1. 1 Herrlich, P. “The Responsibility of the Scientist: What Can History Teach Us About How Scientists Should Handle Research
That Has the Potential to Create Harm?” EMBO Reports 14 (2013): 759–764.

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed

7.5 Le Châtelier’s Principle.5 [Link]

 under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).
Modified by Tom Neils (Grand Rapids Community College)

7.5 Le Châtelier’s Principle: How a System at Equilibrium Responds to Disturbances is shared under a CC BY-NC-SA 4.0 license and was
authored, remixed, and/or curated by LibreTexts.

7.5 Le Châtelier’s Principle.6 [Link]

7.6: The First Law of Thermodynamics
Skills to Develop
To calculate changes in internal energy

Thermodynamics
We will now apply the principles of thermodynamics to show how energy flow determines the likely amount of product made by a
reaction when it reaches dynamic equilibrium. To do so, we will need to do a bit of a review of definitions.

System versus Surrounding

To study the flow of energy during a chemical reaction, we need to distinguish between a system, the small, well-defined part of the
universe in which we are interested (such as a chemical reaction), and its surroundings, the rest of the universe, including the
container in which the reaction is carried out (Figure 7.6.1). In the discussion that follows, the mixture of chemical substances that
undergoes a reaction is always the system, and the flow of heat can be from the system to the surroundings or vice versa.

Figure 7.6.1 : A System and Its Surroundings. The system is that part of the universe we are interested in studying, such as a
chemical reaction inside a flask. The surroundings are the rest of the universe, including the container in which the reaction is
carried out.
Three kinds of systems are important in chemistry. An open system can exchange both matter and energy with its surroundings. A
pot of boiling water is an open system because a burner supplies energy in the form of heat, and matter in the form of water vapor
is lost as the water boils. A closed system can exchange energy but not matter with its surroundings. The sealed pouch of a ready-
made dinner that is dropped into a pot of boiling water is a closed system because thermal energy is transferred to the system from
the boiling water but no matter is exchanged (unless the pouch leaks, in which case it is no longer a closed system). An isolated
system exchanges neither energy nor matter with the surroundings. A truly isolated system does not actually exist, however,
because energy is always exchanged between a system and its surroundings, although this process may take place very slowly. An
insulated thermos containing hot coffee approximates an isolated system, but eventually the coffee cools as heat is transferred to
the surroundings. In all cases, the amount of heat lost by a system is equal to the amount of heat gained by its surroundings and
vice versa. That is, the total energy of a system plus its surroundings is constant, which must be true if energy is conserved.
The state of a system is a complete description of a system at a given time, including its temperature and pressure, the amount of
matter it contains, its chemical composition, and the physical state of the matter. A state function is a property of a system whose
magnitude depends on only the present state of the system, not its previous history. Temperature, pressure, volume, and potential
energy are all state functions. The temperature of an oven, for example, is independent of however many steps it may have taken
for it to reach that temperature. Similarly, the pressure in a tire is independent of how often air is pumped into the tire for it to reach
that pressure, as is the final volume of air in the tire. Heat and work, on the other hand, are not state functions because they are path
dependent. For example, a car sitting on the top level of a parking garage has the same potential energy whether it was lifted by a
crane, set there by a helicopter, driven up, or pushed up by a group of students (Figure 7.6.2). The amount of work expended to get
it there, however, can differ greatly depending on the path chosen. If the students decided to carry the car to the top of the ramp,
they would perform a great deal more work than if they simply pushed the car up the ramp (unless, of course, they neglected to
release the parking brake, in which case the work expended would increase substantially!). The potential energy of the car is the
same, however, no matter which path they choose.

7.6.1 [Link]
Figure 7.6.2 : Elevation as an Example of a State Function. The change in elevation between state 1 (at the bottom of the parking
garage) and state 2 (at the top level of the parking garage) is the same for both paths A and B; it does not depend on which path is
taken from the bottom to the top. In contrast, the distance traveled and the work needed to reach the top do depend on which path
is taken. Elevation is a state function, but distance and work are not state functions.

Direction of Heat Flow

The reaction of powdered aluminum with iron(III) oxide, known as the thermite reaction, generates an enormous amount of heat—
enough, in fact, to melt steel (Figure 7.6.3). The balanced chemical equation for the reaction is as follows:

2Al(s) + F e2 O3 (s) → 2F e(s) + Al2 O3 (s) (7.6.1)

Figure 7.6.3 : The thermite reaction produces so much heat that the iron it produces comes out molten, a property that makes this
reaction useful in welding. Image by Kingfisher [CC BY-SA 3.0 ([Link] from Wikimedia
Commons.
We can also write this chemical equation as
2Al(s) + F e2 O3 (s) → 2F e(s) + Al2 O3 (s) + heat (7.6.2)

to indicate that heat is one of the products. Chemical equations in which heat is shown as either a reactant or a product are called
thermochemical equations. In this reaction, the system consists of aluminum, iron, and oxygen atoms; everything else, including
the container, makes up the surroundings. During the reaction, so much heat is produced that the iron liquefies. Eventually, the
system cools; the iron solidifies as heat is transferred to the surroundings. A process in which heat (q) is transferred from a system
to its surroundings is described as exothermic. By convention, q < 0 for an exothermic reaction.
When you hold an ice cube in your hand, heat from the surroundings (including your hand) is transferred to the system (the ice),
causing the ice to melt and your hand to become cold. We can describe this process by the following thermochemical equation:
heat + H2 O(s) → H2 O(l) (7.6.3)

When heat is transferred to a system from its surroundings, the process is endothermic. By convention, q >0 for an endothermic
reaction.
Heat is technically not a component in Chemical Reactions

7.6.2 [Link]
 Technically, it is poor form to have a heat term in the chemical reaction like in Equations 7.6.2 and 7.6.3 since is it not a true
species in the reaction. However, this is a convenient approach to represent exothermic and endothermic behavior and is
commonly used by chemists.

The First Law

The relationship between the energy change of a system and that of its surroundings is given by the first law of thermodynamics,
which states that the energy of the universe is constant. We can express this law mathematically as follows:
Uuniv = ΔUsys + ΔUsurr = 0 (7.6.4)

ΔUsys = −ΔUsurr (7.6.5)

where U represents energy, and the subscripts univ, sys, and surr refer to the universe, the system, and the surroundings,
respectively. Thus the change in energy of a system is identical in magnitude but opposite in sign to the change in energy of its
surroundings.

The tendency of all systems, chemical or otherwise, is to move toward the state with the lowest possible energy.

An important factor that determines the outcome of a chemical reaction is the tendency of all systems, chemical or otherwise, to
move toward the lowest possible overall energy state. As a brick dropped from a rooftop falls, its potential energy is converted to
kinetic energy; when it reaches ground level, it has achieved a state of lower potential energy. Anyone nearby will notice that
energy is transferred to the surroundings as the noise of the impact reverberates and the dust rises when the brick hits the ground.
Similarly, if a spark ignites a mixture of isooctane and oxygen in an internal combustion engine, carbon dioxide and water form,
while potential energy (in the form of the relative positions of atoms in the molecules) is released to the surroundings as heat and
work. The internal energy content of the C O /H O product mixture is less than that of the isooctane/ O reactant mixture. The
2 2 2

two cases differ, however, in the form in which the energy is released to the surroundings. In the case of the falling brick, the
energy is transferred as work done on whatever happens to be in the path of the brick; in the case of burning isooctane, the energy
can be released as solely heat (if the reaction is carried out in an open container) or as a mixture of heat and work (if the reaction is
carried out in the cylinder of an internal combustion engine). Because heat and work are the only two ways in which energy can be
transferred between a system and its surroundings, any change in the internal energy of the system is the sum of the heat transferred
(q) and the work done (w):

ΔUsys = q + w (7.6.6)

Although q and w are not state functions on their own, their sum (ΔU ) is independent of the path taken and is therefore a state
sys

function. A major task for the designers of any machine that converts energy to work is to maximize the amount of work obtained
and minimize the amount of energy released to the environment as heat. An example is the combustion of coal to produce
electricity. Although the maximum amount of energy available from the process is fixed by the energy content of the reactants and
the products, the fraction of that energy that can be used to perform useful work is not fixed.
Because of the first law, we can determine ΔU for any process if we can measure both q and w. Heat, q, may be calculated by
measuring a change in temperature of the surroundings. Work, w, may come in different forms, but it too can be measured.

Summary
In chemistry, the small part of the universe that we are studying is the system, and the rest of the universe is the surroundings.
Open systems can exchange both matter and energy with their surroundings, closed systems can exchange energy but not matter
with their surroundings, and isolated systems can exchange neither matter nor energy with their surroundings. A state function is
a property of a system that depends on only its present state, not its history. A reaction or process in which heat is transferred from
a system to its surroundings is exothermic. A reaction or process in which heat is transferred to a system from its surroundings is
endothermic. The first law of thermodynamics states that the energy of the universe is constant. The change in the internal energy
of a system is the sum of the heat transferred and the work done.

Contributors
Modified by Tom Neils (Grand Rapids Community College)

7.6.3 [Link]
7.6: The First Law of Thermodynamics is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

7.6.4 [Link]
7.7: Enthalpy: The Heat Evolved in a Chemical Reaction at Constant Pressure
Skills to Develop
To understand how enthalpy pertains to chemical reactions

We have stated that the change in energy (ΔU ) is equal to the sum of the heat produced and the work performed. Work done by an
expanding gas is called pressure-volume work, (or just P V work). Consider, for example, a reaction that produces a gas, such as
dissolving a piece of copper in concentrated nitric acid. The chemical equation for this reaction is as follows:

Cu(s) + 4 HNO (aq) → Cu(NO ) (aq) + 2 H O(l) + 2 NO (g) (7.7.1)

3 3 2 2 2

If the reaction is carried out in a closed system that is maintained at constant pressure by a movable piston, the piston will rise as
nitrogen dioxide gas is formed (Figure 7.7.1). The system is performing work by lifting the piston against the downward force
exerted by the atmosphere (i.e., atmospheric pressure). We find the amount of P V work done by multiplying the external pressure
P by the change in volume caused by movement of the piston (ΔV ). At a constant external pressure (here, atmospheric pressure),

w = −P ΔV (7.7.2)

The negative sign associated with P V work done indicates that the system loses energy when the volume increases. If the volume
increases at constant pressure (ΔV > 0 ), the work done by the system is negative, indicating that a system has lost energy by
performing work on its surroundings. Conversely, if the volume decreases (ΔV < 0 ), the work done by the system is positive,
which means that the surroundings have performed work on the system, thereby increasing its energy.

Figure 7.7.1 : An Example of Work Performed by a Reaction Carried Out at Constant Pressure. (a) Initially, the system (a copper
penny and concentrated nitric acid) is at atmospheric pressure. (b) When the penny is added to the nitric acid, the volume of NO2
gas that is formed causes the piston to move upward to maintain the system at atmospheric pressure. In doing so, the system is
performing work on its surroundings. (CC BY-NC-SA; anonymous)
The internal energy U of a system is the sum of the kinetic energy and potential energy of all its components. It is the change in
internal energy that produces heat plus work. To measure the energy changes that occur in chemical reactions, chemists usually use
a related thermodynamic quantity called enthalpy (H ) (from the Greek enthalpein, meaning “to warm”). The enthalpy of a system
is defined as the sum of its internal energy U plus the product of its pressure P and volume V :
H = U +PV (7.7.3)

Because internal energy, pressure, and volume are all state functions, enthalpy is also a state function. So we can define a change in
enthalpy (ΔH ) accordingly

ΔH = Hf inal − Hinitial

If a chemical change occurs at constant pressure (i.e., for a given P , ΔP =0 ), the change in enthalpy (ΔH ) is

ΔH = Δ(U + P V ) (7.7.4)

= ΔU + ΔP V (7.7.5)

= ΔU + P ΔV (7.7.6)

7.7.1 [Link]
Substituting q + w for ΔU (First Law of Thermodynamics) and −w for P ΔV (Equation 7.7.2) into Equation 7.7.6, we obtain
ΔH = ΔU + P ΔV (7.7.7)

= qp + w − w (7.7.8)

= qp (7.7.9)

The subscript p is used here to emphasize that this equation is true only for a process that occurs at constant pressure. From
Equation 7.7.9 we see that at constant pressure the change in enthalpy, ΔH of the system, is equal to the heat gained or lost.
ΔH = Hf inal − Hinitial (7.7.10)

= qp (7.7.11)

Just as with ΔU , because enthalpy is a state function, the magnitude of ΔH depends on only the initial and final states of the
system, not on the path taken. Most important, the enthalpy change is the same even if the process does not occur at constant
pressure.

The ΔH for a reaction is equal to the heat gained or lost at constant pressure, q . p

When we study energy changes in chemical reactions, the most important quantity is usually the enthalpy of reaction (ΔH ), the rxn

change in enthalpy that occurs during a reaction (such as the dissolution of a piece of copper in nitric acid). If heat flows from a
system to its surroundings, the enthalpy of the system decreases, so ΔH rxnis negative. Conversely, if heat flows from the
surroundings to a system, the enthalpy of the system increases, so ΔH is positive. Thus:
rxn

ΔHrxn < 0 for an exothermic reaction, and

ΔHrxn > 0 for an endothermic reaction.
Bond breaking always requires an input of energy and is therefore an endothermic process, whereas bond making always releases
energy, which is an exothermic process. The sign conventions for heat flow and enthalpy changes are summarized in the following
table:

Reaction Type q ΔHrxn

< 0 (heat flows from a system to its

exothermic <0
surroundings)
> 0 (heat flows from the surroundings to a
endothermic >0
system)

If ΔHrxn is negative, then the enthalpy of the products is less than the enthalpy of the reactants; that is, an exothermic reaction is
energetically downhill (Figure 7.7.2a). Conversely, if ΔHrxn is positive, then the enthalpy of the products is greater than the
enthalpy of the reactants; thus, an endothermic reaction is energetically uphill (Figure 7.7.2b). Two important characteristics of
enthalpy and changes in enthalpy are summarized in the following discussion.

Bond breaking ALWAYS requires an input of energy; bond making ALWAYS releases
energy.y.

7.7.2 [Link]
Figure 7.7.2 : The Enthalpy of Reaction. Energy changes in chemical reactions are usually measured as changes in enthalpy. (a)
If heat flows from a system to its surroundings, the enthalpy of the system decreases, ΔHrxn is negative, and the reaction is
exothermic; it is energetically downhill. (b) Conversely, if heat flows from the surroundings to a system, the enthalpy of the system
increases, ΔHrxn is positive, and the reaction is endothermic; it is energetically uphill. (CC BY-NC-SA; anonymous)
Reversing a reaction or a process changes the sign of ΔH. Ice absorbs heat when it melts (electrostatic interactions are
broken), so liquid water must release heat when it freezes (electrostatic interactions are formed):
heat + H2 O(s) → H2 O(l) ΔH > 0

H2 O(l) → H2 O(s) + heat ΔH < 0

In both cases, the magnitude of the enthalpy change is the same; only the sign is different.
Enthalpy is an extensive property (like mass). The magnitude of ΔH for a reaction is proportional to the amounts of the
substances that react. For example, a large fire produces more heat than a single match, even though the chemical reaction—the
combustion of wood—is the same in both cases. For this reason, the enthalpy change for a reaction is usually given in kilojoules
per mole of a particular reactant or product. Consider Equation 7.7.12, which describes the reaction of aluminum with iron(III)
oxide (Fe2O3) at constant pressure. According to the reaction stoichiometry, 2 mol of Fe, 1 mol of Al2O3, and 851.5 kJ of heat
are produced for every 2 mol of Al and 1 mol of Fe2O3 consumed:
2Al (s) + F e2 O3 (s) → 2F e (s) + Al2 O3 (s) + 815.5 kJ (7.7.12)

Thus ΔH = −851.5 kJ/mol of Fe2O3. We can also describe ΔH for the reaction as −425.8 kJ/mol of Al: because 2 mol of Al are
consumed in the balanced chemical equation, we divide −851.5 kJ by 2. When a value for ΔH, in kilojoules rather than
kilojoules per mole, is written after the reaction, as in Equation 7.7.13, it is the value of ΔH corresponding to the reaction of the
molar quantities of reactants as given in the balanced chemical equation:
2Al (s) + F e2 O3 (s) → 2F e (s) + Al2 O3 (s) ΔHrxn = −851.5 kJ (7.7.13)

If 4 mol of Al and 2 mol of Fe2O3 react, the change in enthalpy is 2 × (−851.5 kJ) = −1703 kJ. We can summarize the
relationship between the amount of each substance and the enthalpy change for this reaction as follows:
851.5 kJ 425.8 kJ 1703 kJ
− =− =− (7.7.14)
2 mol Al 1 mol Al 4 mol Al

The relationship between the magnitude of the enthalpy change and the mass of reactants is illustrated in Example 7.7.1.

Example 7.7.1 : Melting Icebergs

Certain parts of the world, such as southern California and Saudi Arabia, are short of freshwater for drinking. One possible
solution to the problem is to tow icebergs from Antarctica and then melt them as needed. If ΔH is 6.01 kJ/mol for the reaction
at 0°C and constant pressure:

H O(s) → H O(l)
2 2

How much energy would be required to melt a moderately large iceberg with a mass of 1.00 million metric tons (1.00 × 106
metric tons)? (A metric ton is 1000 kg.)
Given: energy per mole of ice and mass of iceberg
Asked for: energy required to melt iceberg
Strategy:
A. Calculate the number of moles of ice contained in 1 million metric tons (1.00 × 106 metric tons) of ice.
B. Calculate the energy needed to melt the ice by multiplying the number of moles of ice in the iceberg by the amount of energy
required to melt 1 mol of ice.
Solution:
A Because enthalpy is an extensive property, the amount of energy required to melt ice depends on the amount of ice present.
We are given ΔH for the process—that is, the amount of energy needed to melt 1 mol (or 18.015 g) of ice—so we need to
calculate the number of moles of ice in the iceberg and multiply that number by ΔH (+6.01 kJ/mol):

7.7.3 [Link]
 ⎛ 1000 kg ⎞ ⎛ 1000 g ⎞⎛ 1 mol H2 O ⎞
6
moles H2 O = 1.00 × 10 metric ton H O
2
⎝1 metric ton ⎠ ⎝ 1 kg ⎠ ⎝ 18.015 g H2 O ⎠

10
= 5.55 × 10 mol H O
2

B The energy needed to melt the iceberg is thus

6.01 kJ 10 11
( ) (5.55 × 10 mol H2 O ) = 3.34 × 10 kJ
mol H2 O

Because so much energy is needed to melt the iceberg, this plan would require a relatively inexpensive source of energy to be
practical. To give you some idea of the scale of such an operation, the amounts of different energy sources equivalent to the
amount of energy needed to melt the iceberg are shown below.
Possible sources of the approximately 3.34 × 10 11
kJ needed to melt a 1.00 × 10 metric ton iceberg
6

Combustion of 3.8 × 103 ft3 of natural gas

Combustion of 68,000 barrels of oil
Combustion of 15,000 tons of coal
1.1 × 10 kilowatt-hours of electricity
8

Alternatively, we can rely on ambient temperatures to slowly melt the iceberg. The main issue with this idea is the cost of
dragging the iceberg to the desired place.

Exercise 7.7.1 : Thermite Reaction

If 17.3 g of powdered aluminum are allowed to react with excess Fe 2
O
3
, how much heat is produced?

Answer
273 kJ

Enthalpies of Reaction
One way to report the heat absorbed or released would be to compile a massive set of reference tables that list the enthalpy changes
for all possible chemical reactions, which would require an incredible amount of effort. Fortunately, since enthalpy is a state
function, all we have to know is the initial and final states of the reaction. This allows us to calculate the enthalpy change for
virtually any conceivable chemical reaction using a relatively small set of tabulated data, such as the following:
Enthalpy of combustion (ΔHcomb) The change in enthalpy that occurs during a combustion reaction. Enthalpy changes have
been measured for the combustion of virtually any substance that will burn in oxygen; these values are usually reported as the
enthalpy of combustion per mole of substance.
Enthalpy of fusion (ΔHfus) The enthalpy change that acompanies the melting (fusion) of 1 mol of a substance. The enthalpy
change that accompanies the melting, or fusion, of 1 mol of a substance; these values have been measured for almost all the
elements and for most simple compounds.
Enthalpy of vaporization (ΔHvap) The enthalpy change that accompanies the vaporization of 1 mol of a substance. The enthalpy
change that accompanies the vaporization of 1 mol of a substance; these values have also been measured for nearly all the
elements and for most volatile compounds.
Enthalpy of solution (ΔHsoln) The change in enthalpy that occurs when a specified amount of solute dissolves in a given
quantity of solvent. The enthalpy change when a specified amount of solute dissolves in a given quantity of solvent.
Table 7.7.1: Enthalpies of Vaporization and Fusion for Selected Substances at Their Boiling Points and Melting Points
Substance ΔHvap (kJ/mol) ΔHfus (kJ/mol)

argon (Ar) 6.3 1.3

methane (CH4) 9.2 0.84

ethanol (CH3CH2OH) 39.3 7.6

7.7.4 [Link]
 Substance ΔHvap (kJ/mol) ΔHfus (kJ/mol)

benzene (C6H6) 31.0 10.9

water (H2O) 40.7 6.0

mercury (Hg) 59.0 2.29

iron (Fe) 340 14

The sign convention is the same for all enthalpy changes: negative if heat is released by the system and positive if heat is
absorbed by the system.

Summary
For a chemical reaction, the enthalpy of reaction (ΔH ) is the difference in enthalpy between products and reactants; the units
rxn

of ΔH rxnare kilojoules per mole. Reversing a chemical reaction reverses the sign of ΔH . rxn

Contributors
Modified by Joshua Halpern (Howard University)
Modified by Tom Neils (Grand Rapids Community College)

7.7: Enthalpy: The Heat Evolved in a Chemical Reaction at Constant Pressure is shared under a CC BY-NC-SA 4.0 license and was authored,
remixed, and/or curated by LibreTexts.

7.7.5 [Link]
7.8 Quantifying Heat
Skills to Develop
Distinguish the related properties of heat, thermal energy, and temperature

Thermal energy is kinetic energy associated with the random motion of atoms and molecules. Temperature is a quantitative
measure of “hot” or “cold.” Temperature can also be thought of as a relative scale that allows us to determine the likely direction
that heat will flow. When the atoms and molecules in an object are moving or vibrating quickly, they have a higher average kinetic
energy (KE), and we say that the object is “hot.” When the atoms and molecules are moving slowly, they have lower KE, and we
say that the object is “cold” (Figure 1). Assuming that no chemical reaction or phase change (such as melting or vaporizing)
occurs, increasing the amount of thermal energy in a sample of matter will cause its temperature to increase. And, assuming that no
chemical reaction or phase change (such as condensation or freezing) occurs, decreasing the amount of thermal energy in a sample
of matter will cause its temperature to decrease.

Figure 1 : (a) The molecules in a sample of hot water move more rapidly than (b) those in a sample of cold water.
Heat (q) is the transfer of thermal energy between two bodies at different temperatures. Heat flow (a redundant term, but one
commonly used) increases the thermal energy of one body and decreases the thermal energy of the other. Suppose we initially have
a high temperature (and high thermal energy) substance (H) and a low temperature (and low thermal energy) substance (L). The
atoms and molecules in H have a higher average KE than those in L. If we place substance H in contact with substance L, the
thermal energy is very likely to flow from substance H to substance L. The temperature of substance H will decrease, as will the
average KE of its molecules; the temperature of substance L will increase, along with the average KE of its molecules. Heat flow
will continue until the two substances are at the same temperature (thermal equilibrium) (Figure 2).

Figure 2 : (a) Substances H and L are initially at different temperatures, and their atoms have different average kinetic energies.
(b) When they are put into contact with each other, collisions between the molecules result in the transfer of kinetic (thermal)
energy from the hotter to the cooler matter. (c) The two objects reach “thermal equilibrium” when both substances are at the same
temperature, and their molecules have the same average kinetic energy.
Matter undergoing chemical reactions and physical changes can release or absorb heat. A change that releases heat is called an
exothermic process. For example, the combustion reaction that occurs when using an oxyacetylene torch is an exothermic process
—this process also releases energy in the form of light as evidenced by the torch’s flame (Figure 3a). A reaction or change that
absorbs heat is an endothermic process. A cold pack used to treat muscle strains provides an example of an endothermic process.
When the substances in the cold pack (water and a salt like ammonium nitrate) are brought together, the resulting process absorbs
heat, leading to the sensation of cold.

1 [Link]
 Figure 3 : (a) An oxyacetylene torch produces heat by the combustion of acetylene in oxygen. The energy released by this
exothermic reaction heats and then melts the metal being cut. The sparks are tiny bits of the molten metal flying away. (b) A cold
pack uses an endothermic process to create the sensation of cold. (credit a: modification of work by “Skatebiker”/Wikimedia
commons).
Historically, energy was measured in units of calories (cal). A calorie is the amount of energy required to raise one gram of water
by 1 degree C (also 1 kelvin). However, this quantity depends on the atmospheric pressure and the starting temperature of the
water. The ease of measurement of energy changes in calories has meant that the calorie is still frequently used. The Calorie (with a
capital C), or large calorie, commonly used in quantifying food energy content, is a kilocalorie. The SI unit of heat, work, and
energy is the joule. A joule (J) is defined as the amount of energy used when a force of 1 newton moves an object 1 meter. It is
named in honor of the English physicist James Prescott Joule. One joule is equivalent to 1 kg m2/s2, which is also called 1 newton–
meter. A kilojoule (kJ) is 1000 joules. To standardize its definition, 1 calorie has been set to equal 4.184 joules.

1 cal ≡ 4.184 J (1)

Application: Heat can do more than increase temperature

Most substances expand as their temperature increases and contract as their temperature decreases. This property can be used to
measure temperature changes, as shown in Figure 4. The operation of many thermometers depends on the expansion and
contraction of substances in response to temperature changes.

Figure 4 : (a) In an alcohol or mercury thermometer, the liquid (dyed red for visibility) expands when heated and contracts
when cooled, much more so than the glass tube that contains the liquid. (b) In a bimetallic thermometer, two different metals
(such as brass and steel) form a two-layered strip. When heated or cooled, one of the metals (brass) expands or contracts more
than the other metal (steel), causing the strip to coil or uncoil. Both types of thermometers have a calibrated scale that indicates
the temperature. (credit a: modification of work by “dwstucke”/Flickr). (c) The demonstration allows one to view the effects of
heating and cooling a coiled bimetallic strip.A bimetallic coil from a thermometer reacts to the heat from a lighter, by uncoiling
and then coiling back up when the lighter is removed. Animation used with permission from Hustvedt (via Wikipedia)

Direction of Heat Flow: Endothermic vs. Exothermic Processes

The reaction of powdered aluminum with iron(III) oxide, known as the thermite reaction, generates an enormous amount of heat—
enough, in fact, to melt steel. The balanced chemical equation for the reaction is as follows:
2 Al(s) + Fe O (s) → 2 Fe(s) + Al O (s) (2)
2 3 2 3

2 [Link]
We can also write this chemical equation as
2 Al(s) + Fe O (s) → 2 Fe(s) + Al O (s) + heat (3)
2 3 2 3

to indicate that heat is one of the products. Chemical equations in which heat is shown as either a reactant or a product are called
thermochemical equations. In this reaction, the system consists of aluminum, iron, and oxygen atoms; everything else, including
the container, makes up the surroundings. During the reaction, so much heat is produced that the iron liquefies. Eventually, the
system cools; the iron solidifies as heat is transferred to the surroundings. A process in which heat (q) is transferred from a system
to its surroundings is described as exothermic. By convention, q < 0 for an exothermic reaction.

Thermite Reactions - Compilation

When you hold an ice cube in your hand, heat from the surroundings (including your hand) is transferred to the system (the ice),
causing the ice to melt and your hand to become cold. We can describe this process by the following thermochemical equation:
heat + H O → H O (4)
2 (s) 2 (l)

When heat is transferred to a system from its surroundings, the process is endothermic. By convention, q >0 for an endothermic
reaction.

By convention, q < 0 for an exothermic reaction and q > 0 for an endothermic reaction.
Exercise 1
Decide whether the following are endothermic or exothermic processes
a. water evaporates off a shower door
b. an acid tablet being added to a pool and the surrounding water heats up
c. NH Cl is dissolved in water and the solution cools
4

d. the burning of a log in a campfire

Hint
During an endothermic process heat is absorbed from surroundings, causing them to cool, so in every case where there is
cooling there is most likely an endothermic process taking place. For exothermic reactions energy is being released to the
surroundings and so the surroundings feel like they have been heated by the process.
Answer a
endothermic
Answer b
exothermic
Answer c
endothermic
Answer d

3 [Link]
 exothermic

Heat is technically not a component in Chemical Reactions

Technically, it is poor form to have a heat term in the chemical reaction like in Equations 3 and 4 since is it not a true species
in the reaction. However, this is a convenient approach to represent exothermic and endothermic behavior and is commonly
used by chemists.

Measuring Heat
Because ΔH is defined as the gain or loss of heat at constant pressure, measurements made using a constant-pressure calorimeter (a
device used to measure enthalpy changes in processes at constant pressure) give ΔH values directly. This device is particularly well
suited to studying reactions carried out in solution at a constant atmospheric pressure. A “student” version, called a coffee-cup
calorimeter (Figure 5), is often encountered in general chemistry laboratories. Commercial calorimeters operate on the same
principle, but they can be used with smaller volumes of solution, have better thermal insulation, and can detect a change in
temperature as small as several millionths of a degree (10−6 °C). Because the heat released or absorbed at constant pressure is equal
to ΔH, the relationship between heat and ΔH rxn is

ΔHrxn = qsystem = −qcalorimeter = −mC ΔT (5)

The use of a constant-pressure calorimeter is illustrated in Example 1.

Figure 5 : A Coffee-Cup Calorimeter. This simplified version of a constant-pressure calorimeter consists of two Styrofoam cups
nested and sealed with an insulated stopper to thermally isolate the system (the solution being studied) from the surroundings (the
air and the laboratory bench). Two holes in the stopper allow the use of a thermometer to measure the temperature and a stirrer to
mix the reactants.

Example 1
J
If 2500. Joules of heat are transferred to a 25.5 gram solid with a specific heat capacity of 1.437 , by how many degrees
g ⋅o C

Celsius will the temperature of the solid increase?

Given: mass of a solid, specific heat of solid, heat added.
Asked for: Temperature increase of solid, ΔT
Strategy:
Calculate change in temperature of water using Equation 7.3.1
Solution:

4 [Link]
 q 2500.J
o
ΔT = = = 68.2 C
mass × C J
(25.5g) (1.437 )
o
g⋅ C

Exercise 2
If 1507. Joules of heat are transferred to a 26.50 gram solid, and the temperature of the solid increases by 27.85oC, what is the
J
specific heat capacity of the solid, in o
?
g⋅ C

Answer
J
2.042
o
g⋅ C

Example 2 :
A 25.7 gram piece of solid is heated to 98.7 oC and then placed in 150.2 grams of water in a calorimeter at 20.2oC. After sitting
J
for several minutes, the temperature of the water stabilizes at 22.3oC. The specific heat of water is 4.184 o
. Calculate the
g⋅ C

specific heat of the piece of solid.

Given: mass of a solid, mass of water, specific heat of water, initial and final temperatures.
Asked for: C of solid
Strategy:
A. Calculate change in heat of water using Equation 7.3.1
B. Calculate C of solid, given that qwater = -qsolid
Solution:
J
A. qwater = 150.2g × 4.184 o
o o
× (22.3 C − 20.2 C ) = 1320J
g⋅ C

B. qsolid = -qwater = −1320J = 25.7g × C solid

o
× (22.3 C − 98.7 C )
o

−1320J J
Csolid = = 0.672
o o
(25.7g)(−76.4 C ) g⋅ C

Exercise 3
A 14.8 gram piece of solid is heated to 100.2 oC and then placed in 102 grams of water in a calorimeter at 21.3oC. After sitting
J
for several minutes, the temperature of the water stabilizes at 22.9oC. The specific heat of water is 4.184 . Calculate the
g ⋅o C

specific heat of the piece of solid.

Answer
J
0.597
g ⋅o C

Heating and Cooling Curves for Water

Freezing, condensation, and deposition, which are the reverse of fusion, sublimation, and vaporization—are exothermic. Thus heat
pumps that use refrigerants are essentially air-conditioners running in reverse. Heat from the environment is used to vaporize the

5 [Link]
refrigerant, which is then condensed to a liquid in coils within a house to provide heat. The energy changes that occur during phase
changes can be quantified by using a heating or cooling curve.
Heating Curves

Figure 6 shows a heating curve, a plot of temperature versus heating time, for a 75 g sample of water. The sample is initially ice at
1 atm and −23°C; as heat is added, the temperature of the ice increases linearly with time. The slope of the line depends on both the
mass of the ice and the specific heat (Cs) of ice, which is the number of joules required to raise the temperature of 1 g of ice by
1°C. As the temperature of the ice increases, the water molecules in the ice crystal absorb more and more energy and vibrate more
vigorously. At the melting point, they have enough kinetic energy to overcome attractive forces and move with respect to one
another. As more heat is added, the temperature of the system does not increase further but remains constant at 0°C until all the ice
has melted. Once all the ice has been converted to liquid water, the temperature of the water again begins to increase. Now,
however, the temperature increases more slowly than before because the specific heat capacity of water is greater than that of ice.
When the temperature of the water reaches 100°C, the water begins to boil. Here, too, the temperature remains constant at 100°C
until all the water has been converted to steam. At this point, the temperature again begins to rise, but at a faster rate than seen in
the other phases because the heat capacity of steam is less than that of ice or water.

Figure 6 : A Heating Curve for Water. This plot of temperature shows what happens to a 75 g sample of ice initially at 1 atm and
−23°C as heat is added at a constant rate: A–B: heating solid ice; B–C: melting ice; C–D: heating liquid water; D–E: vaporizing
water; E–F: heating steam.
Thus the temperature of a system does not change during a phase change. In this example, as long as even a tiny amount of ice is
present, the temperature of the system remains at 0°C during the melting process, and as long as even a small amount of liquid
water is present, the temperature of the system remains at 100°C during the boiling process. The rate at which heat is added does
not affect the temperature of the ice/water or water/steam mixture because the added heat is being used exclusively to overcome the
attractive forces that hold the more condensed phase together. Many cooks think that food will cook faster if the heat is turned up
higher so that the water boils more rapidly. Instead, the pot of water will boil to dryness sooner, but the temperature of the water
does not depend on how vigorously it boils.

The temperature of a sample does not change during a phase change.

If heat is added at a constant rate, as in Figure 6, then the length of the horizontal lines, which represents the time during which the
temperature does not change, is directly proportional to the magnitude of the enthalpies associated with the phase changes. In
Figure 6, the horizontal line at 100°C is much longer than the line at 0°C because the enthalpy of vaporization of water is several
times greater than the enthalpy of fusion.
A superheated liquid is a sample of a liquid at the temperature and pressure at which it should be a gas. Superheated liquids are not
stable; the liquid will eventually boil, sometimes violently. The phenomenon of superheating causes “bumping” when a liquid is
heated in the laboratory. When a test tube containing water is heated over a Bunsen burner, for example, one portion of the liquid
can easily become too hot. When the superheated liquid converts to a gas, it can push or “bump” the rest of the liquid out of the test
tube. Placing a stirring rod or a small piece of ceramic (a “boiling chip”) in the test tube allows bubbles of vapor to form on the
surface of the object so the liquid boils instead of becoming superheated. Superheating is the reason a liquid heated in a smooth cup
in a microwave oven may not boil until the cup is moved, when the motion of the cup allows bubbles to form.

6 [Link]
Cooling Curves
The cooling curve, a plot of temperature versus cooling time, in Figure 7 plots temperature versus time as a 75 g sample of steam,
initially at 1 atm and 200°C, is cooled. Although we might expect the cooling curve to be the mirror image of the heating curve in
Figure 6, the cooling curve is not an identical mirror image. As heat is removed from the steam, the temperature falls until it
reaches 100°C. At this temperature, the steam begins to condense to liquid water. No further temperature change occurs until all the
steam is converted to the liquid; then the temperature again decreases as the water is cooled. We might expect to reach another
plateau at 0°C, where the water is converted to ice; in reality, however, this does not always occur. Instead, the temperature often
drops below the freezing point for some time, as shown by the little dip in the cooling curve below 0°C. This region corresponds to
an unstable form of the liquid, a supercooled liquid. If the liquid is allowed to stand, if cooling is continued, or if a small crystal of
the solid phase is added (a seed crystal), the supercooled liquid will convert to a solid, sometimes quite suddenly. As the water
freezes, the temperature increases slightly due to the heat evolved during the freezing process and then holds constant at the
melting point as the rest of the water freezes. Subsequently, the temperature of the ice decreases again as more heat is removed
from the system.

Figure 7 : A Cooling Curve for Water. This plot of temperature shows what happens to a 75 g sample of steam initially at 1 atm and
200°C as heat is removed at a constant rate: A–B: cooling steam; B–C: condensing steam; C–D: cooling liquid water to give a
supercooled liquid; D–E: warming the liquid as it begins to freeze; E–F: freezing liquid water; F–G: cooling ice.
Supercooling effects have a huge impact on Earth’s climate. For example, supercooling of water droplets in clouds can prevent the
clouds from releasing precipitation over regions that are persistently arid as a result. Clouds consist of tiny droplets of water, which
in principle should be dense enough to fall as rain. In fact, however, the droplets must aggregate to reach a certain size before they
can fall to the ground. Usually a small particle (a nucleus) is required for the droplets to aggregate; the nucleus can be a dust
particle, an ice crystal, or a particle of silver iodide dispersed in a cloud during seeding (a method of inducing rain). Unfortunately,
the small droplets of water generally remain as a supercooled liquid down to about −10°C, rather than freezing into ice crystals that
are more suitable nuclei for raindrop formation. One approach to producing rainfall from an existing cloud is to cool the water
droplets so that they crystallize to provide nuclei around which raindrops can grow. This is best done by dispersing small granules
of solid CO2 (dry ice) into the cloud from an airplane. Solid CO2 sublimes directly to the gas at pressures of 1 atm or lower, and the
enthalpy of sublimation is substantial (25.3 kJ/mol). As the CO2 sublimes, it absorbs heat from the cloud, often with the desired
results.

Example 3 : Cooling Hot Tea

If a 50.0 g ice cube at 0.0°C is added to 500 mL of tea at 20.0°C, what is the temperature of the tea when the ice cube has just
melted? Assume that no heat is transferred to or from the surroundings. The density of water (and iced tea) is 1.00 g/mL over
the range 0°C–20°C, the specific heats of liquid water and ice are 4.184 J/(g•°C) and 2.062 J/(g•°C), respectively, and the
enthalpy of fusion of ice is 6.01 kJ/mol.
Given: mass, volume, initial temperature, density, specific heats, and ΔH f us

Asked for: final temperature

Strategy:

7 [Link]
 Substitute the values given into the general equation relating heat gained to heat lost (Equation 5.39) to obtain the final
temperature of the mixture.
Solution:
When two substances or objects at different temperatures are brought into contact, heat will flow from the warmer one to the
cooler. The amount of heat that flows is given by
q = m Cs ΔT (6)

where q is heat, m is mass, Cs is the specific heat, and ΔT is the temperature change. Eventually, the temperatures of the two
substances will become equal at a value somewhere between their initial temperatures. Calculating the temperature of iced tea
after adding an ice cube is slightly more complicated. The general equation relating heat gained and heat lost is still valid, but in
this case we also have to take into account the amount of heat required to melt the ice cube from ice at 0.0°C to liquid water at
0.0°C.

Exercise 4 : Death by Freezing

Suppose you are overtaken by a blizzard while ski touring and you take refuge in a tent. You are thirsty, but you forgot to bring
liquid water. You have a choice of eating a few handfuls of snow (say 400 g) at −5.0°C immediately to quench your thirst or
setting up your propane stove, melting the snow, and heating the water to body temperature before drinking it. You recall that
the survival guide you leafed through at the hotel said something about not eating snow, but you cannot remember why—after
all, it’s just frozen water. To understand the guide’s recommendation, calculate the amount of heat that your body will have to
supply to bring 400 g of snow at −5.0°C to your body’s internal temperature of 37°C. Use the data in Example 3
Answer
200 kJ (4.1 kJ to bring the ice from −5.0°C to 0.0°C, 133.6 kJ to melt the ice at 0.0°C, and 61.9 kJ to bring the water from 0.0°C
to 37°C), which is energy that would not have been expended had you first melted the snow.

Contributors
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).
Modified by Tom Neils (Grand Rapids Community College)

7.8 Quantifying Heat is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

8 [Link]
7.9: Entropy and the Second Law of Thermodynamics
Skills to Develop
To understand the relationship between internal energy and entropy.

The first law of thermodynamics governs changes in the state function we have called internal energy (U ). Changes in the internal
energy (ΔU) are closely related to changes in the enthalpy (ΔH), which is a measure of the heat flow between a system and its
surroundings at constant pressure. This information, however, does not tell us whether a particular process or reaction will occur
spontaneously. (In chemistry, the word spontaneous means "very likely to proceed in the forward direction, as written, in order to
reach equilibrium.")
Let’s consider a familiar example of spontaneous change. If a hot frying pan that has just been removed from the stove is allowed
to come into contact with a cooler object, such as cold water in a sink, heat will flow from the hotter object to the cooler one, in this
case usually releasing steam. Eventually both objects will reach the same temperature, at a value between the initial temperatures of
the two objects. This transfer of heat from a hot object to a cooler one obeys the first law of thermodynamics: energy is conserved.
Now consider the same process in reverse. Suppose that a hot frying pan in a sink of cold water were to become hotter while the
water became cooler. As long as the same amount of thermal energy was gained by the frying pan and lost by the water, the first
law of thermodynamics would be satisfied. Yet we all know that such a process is very unlikely to occur: heat is always likely to
flow from a hot object to a cold one, but never likely to flow in the reverse direction. That is, by itself the magnitude of the heat
flow associated with a process does not predict whether the process will occur spontaneously.
For many years, chemists and physicists tried to identify a single measurable quantity that would enable them to predict whether a
particular process or reaction would occur spontaneously. Initially, many of them focused on enthalpy changes and hypothesized
that an exothermic process would always be spontaneous. But although it is true that many, if not most, spontaneous processes are
exothermic, there are also many spontaneous processes that are not exothermic. For example, at a pressure of 1 atm, ice melts
spontaneously at temperatures greater than 0°C, yet this is an endothermic process because heat is absorbed. Similarly, many salts
(such as NH4NO3, NaCl, and KBr) dissolve spontaneously in water even though they absorb heat from the surroundings as they
dissolve (i.e., ΔHsoln > 0). Reactions can also be both spontaneous and highly endothermic, like the reaction of barium hydroxide
with ammonium thiocyanate shown in Figure 7.9.1.

Figure 7.9.1 : An Endothermic Reaction. The reaction of barium hydroxide with ammonium thiocyanate is spontaneous but highly
endothermic, so water, one product of the reaction, quickly freezes into slush. When water is placed on a block of wood under the
flask, the highly endothermic reaction that takes place in the flask freezes water that has been placed under the beaker, so the flask
becomes frozen to the wood. For a full video: see [Link]
Thus enthalpy is not the only factor that determines whether a process is spontaneous. For example, after a cube of sugar has
dissolved in a glass of water so that the sucrose molecules are uniformly dispersed in a dilute solution, they never spontaneously
come back together in solution to form a sugar cube. Moreover, the molecules of a gas remain evenly distributed throughout the
entire volume of a glass bulb and never spontaneously assemble in only one portion of the available volume. To help explain why
these phenomena proceed spontaneously in only one direction requires an additional state function called entropy (S), a
thermodynamic property of all substances that is proportional to their degree of "possibilities".

Entropy
Chemical and physical changes in a system may be accompanied by either an increase or a decrease in the possible arrangements
(sometimes called disorder, randomness, or freedom) of the system, corresponding to an increase in entropy (ΔS > 0) or a decrease

7.9.1 [Link]
in entropy (ΔS < 0), respectively. As with any other state function, the change in entropy is defined as the difference between the
entropies of the final and initial states: ΔS = Sf − Si.
When a gas expands into a vacuum, its entropy increases because the increased volume allows for greater atomic or molecular
possibilities. The greater the number of atoms or molecules in the gas, the greater the possible arrangements. The magnitude of the
entropy of a system depends on the number of microscopic states, or microstates, associated with it (in this case, the number of
atoms or molecules); that is, the greater the number of microstates, the greater the entropy.
We can illustrate the concepts of microstates and entropy using a deck of playing cards, as shown in Figure 7.9.2. There are
approximately 1068 (52!) different ways they might be arranged, which corresponds to 1068 different microscopic states. Card
games assign a higher value to a hand that has a low degree of probability. In games such as five-card poker, only 4 of the
2,598,960 different possible hands, or microstates, contain the valued arrangement of cards called a royal flush, almost 1.1 million
hands contain one pair, and more than 1.3 million hands are completely disordered (according to the rules of poker) and therefore
have no value. Because the last two arrangements are far more probable than the first, the value of a poker hand is inversely
proportional to its entropy.

Figure 7.9.2 : Illustrating High- and Low-Entropy States with a Deck of Playing Cards. A randomly shuffled deck of 52 cards can
have any one of approximately 1068 different arrangements, which correspond to 1068 different microstates. The deck above shows
a single arrangement, and thus represents one of these microstates. If this is the sole, desired arrangement of cards, the
arrangement has a very low entropy because there is only one possible way to obtain this arrangement (1 out of 52!). The card
game of canasta uses 108 cards, and so a canasta deck has a higher number of possible microstates (108!), and could be said to
have a higher entropy than a standard deck.
Image used with permission (CC BY-3.0 ; Trainler).
We can see how to calculate these kinds of probabilities for a chemical system by considering the possible arrangements of a
sample of four gas molecules in a two-bulb container (Figure 7.9.3). There are five possible arrangements: all four molecules in the
left bulb (I); three molecules in the left bulb and one in the right bulb (II); two molecules in each bulb (III); one molecule in the left
bulb and three molecules in the right bulb (IV); and four molecules in the right bulb (V). If we assign a different color to each
molecule to keep track of it for this discussion (remember, however, that in reality the molecules are indistinguishable from one
another), we can see that there are 16 different ways the four molecules can be distributed in the bulbs, each corresponding to a
particular microstate. As shown in Figure 7.9.3, arrangement I is associated with a single microstate, as is arrangement V, so each
arrangement has a probability of 1/16. Arrangements II and IV each have a probability of 4/16 because each can exist in four
microstates. Similarly, six different microstates can occur as arrangement III, making the probability of this arrangement 6/16. Thus
the arrangement that we would expect to encounter most often, with half the gas molecules in each bulb, is the most probable
arrangement. The other states are not impossible but simply less likely.

7.9.2 [Link]
 Figure 7.9.3 : The Possible Microstates for a Sample of Four Gas Molecules in Two Bulbs of Equal Volume
There are 16 different ways to distribute four gas molecules between the bulbs, with each distribution corresponding to a particular
microstate. Arrangements I and V each produce a single microstate with a probability of 1/16. This particular arrangement is least
likely to be observed. Arrangements II and IV each produce four microstates, with a probability of 4/16. Arrangement III, with half
the gas molecules in each bulb, has a probability of 6/16. It is the one encompassing the most microstates, so it is the most
probable.
Instead of four molecules of gas, let’s now consider 1 L of an ideal gas which contains 2.69 × 1022 molecules. If we allow the
sample of gas to expand into a second 1 L container, the probability of finding all 2.69 × 1022 molecules in one container and none
in the other at any given time is extremely small, approximately 2
. The probability of such an occurrence is effectively
22
2.69×10

zero. Although nothing prevents the molecules in the gas sample from occupying only one of the two bulbs, that particular
arrangement is so improbable that it is never actually observed. The probability of arrangements with essentially equal numbers of
molecules in each bulb is quite high, however, because there are many equivalent microstates in which the molecules are
distributed equally. Hence a macroscopic sample of a gas occupies all of the space available to it, simply because this is the most
probable arrangement.
A system that has a large number of possible microstates because the particles are free to move has a high entropy. This is most
clearly seen in the entropy changes that accompany phase transitions, such as solid to liquid or liquid to gas. As you know, a
crystalline solid is composed of an ordered array of molecules, ions, or atoms that occupy fixed positions in a lattice, whereas the
molecules in a liquid are free to move and tumble within the volume of the liquid; molecules in a gas have even more freedom to
move than those in a liquid. Each degree of motion increases the number of available microstates, resulting in a higher entropy.
Thus the entropy of a system must increase during melting (ΔSfus > 0). Similarly, when a liquid is converted to a vapor, the greater
freedom of motion of the molecules in the gas phase means that ΔSvap > 0. Conversely, the reverse processes (condensing a vapor
to form a liquid or freezing a liquid to form a solid) must be accompanied by a decrease in the entropy of the system: ΔS < 0.

Entropy (S) is a thermodynamic property of all substances that is proportional to their degree of possibilities. The greater the
number of possible microstates for a system, the greater the disorder and the higher the entropy.

Experiments show that the magnitude of ΔSvap is 80–90 J/(mol•K) for a wide variety of liquids with different boiling points.
However, liquids that have highly ordered structures due to hydrogen bonding or other intermolecular interactions tend to have
significantly higher values of ΔSvap. For instance, ΔSvap for water is 102 J/(mol•K). Another process that is accompanied by
entropy changes is the formation of a solution. As illustrated in Figure 7.9.4, the formation of a liquid solution from a crystalline
solid (the solute) and a liquid solvent is expected to result in an increase in the number of available microstates of the system and
hence its entropy. Indeed, dissolving a substance such as NaCl in water disrupts both the ordered crystal lattice of NaCl and the
ordered hydrogen-bonded structure of water, leading to an increase in the entropy of the system. At the same time, however, each
dissolved Na+ ion becomes hydrated by an ordered arrangement of at least six water molecules, and the Cl− ions also cause the
water to adopt a particular local structure. Both of these effects increase the order of the system, leading to a decrease in entropy.
The overall entropy change for the formation of a solution therefore depends on the relative magnitudes of these opposing factors.
In the case of an NaCl solution, disruption of the crystalline NaCl structure and the hydrogen-bonded interactions in water is
quantitatively more important, so ΔSsoln > 0.

7.9.3 [Link]
 Figure 7.9.4 : The Effect of Solution Formation on Entropy
Dissolving NaCl in water results in an increase in the entropy of the system. Each hydrated ion, however, forms an ordered
arrangement with water molecules, which decreases the entropy of the system. The magnitude of the increase is greater than the
magnitude of the decrease, so the overall entropy change for the formation of an NaCl solution is positive.

Example 7.9.1
Predict which substance in each pair has the higher entropy and justify your answer.
a. 1 mol of NH3(g) or 1 mol of He(g), both at 25°C
b. 1 mol of Pb(s) at 25°C or 1 mol of Pb(l) at 800°C
Given: amounts of substances and temperature
Asked for: higher entropy
Strategy:
From the number of atoms present and the phase of each substance, predict which has the greater number of available
microstates and hence the higher entropy.
Solution:
a. Both substances are gases at 25°C, but one consists of He atoms and the other consists of NH3 molecules. With four atoms
instead of one, the NH3 molecules have more motions available, leading to a greater number of microstates. Hence we
predict that the NH3 sample will have the higher entropy.
b. The nature of the atomic species is the same in both cases, but the phase is different: one sample is a solid, and one is a
liquid. Based on the greater freedom of motion available to atoms in a liquid, we predict that the liquid sample will have the
higher entropy.

Exercise 7.9.1
Predict which substance in each pair has the higher entropy and justify your answer.
a. 1 mol of He(g) at 10 K and 1 atm pressure or 1 mol of He(g) at 250°C and 0.2 atm
b. a mixture of 3 mol of H2(g) and 1 mol of N2(g) at 25°C and 1 atm or a sample of 2 mol of NH3(g) at 25°C and 1 atm

Answer a
1 mol of He(g) at 250°C and 0.2 atm (higher temperature and lower pressure indicate greater volume and more microstates)
Answer a
a mixture of 3 mol of H2(g) and 1 mol of N2(g) at 25°C and 1 atm (more molecules of gas are present)

Video Solution

The Second Law of Thermodynamics

The entropy of the universe increases during a spontaneous process. It also increases during an non-spontaneous process that is
driven to occur by the addition of work to the system. The entropy of the universe will continue to increase until equilibrium is
reached. Although we do not know what it means for the universe to be at equilibrium, we do know that there is no change in
entropy for any chemical or physical process that is at equilibrium. Thus, equilibrium must be the most likely situation for any
system. A system at equilibrium is likely to stay at equilibrium, and a system that is not at equilibrium is likely to change so that

7.9.4 [Link]
 it can reach equilibrium. The most likely thing to happen does not have to happen, nor is it guaranteed to happen. Simply put,
the most likely thing to happen is the most likely thing to happen.

As an example, consider the entropy changes that accompany the transfer of heat from a hot object to a cold one, as occurs when
lava spewed from a volcano flows into cold ocean water. The cold substance, the water, gains heat (q > 0), so the change in the
entropy of the water can be written as ΔScold = q/Tcold. Similarly, the hot substance, the lava, loses heat (q < 0), so its entropy
change can be written as ΔShot = −q/Thot, where Tcold and Thot are the temperatures of the cold and hot substances, respectively.
The total entropy change of the universe accompanying this process is therefore
q q
ΔSuniv = ΔScold + ΔShot = + (− ) (7.9.1)
Tcold Thot

The numerators on the right side of Equation 7.9.1 are the same in magnitude but opposite in sign. Whether ΔSuniv is positive or
negative depends on the relative magnitudes of the denominators. By definition, Thot > Tcold, so −q/Thot must be less than q/Tcold,
and ΔSuniv must be positive. As predicted by the second law of thermodynamics, the entropy of the universe increases during this
process. Any process for which ΔSuniv is positive is, by definition, a spontaneous one that will (very likely) occur as written.
Conversely, any process for which ΔSuniv is negative will not occur as written but will (very likely) occur spontaneously in the
reverse direction. We see, therefore, that heat is spontaneously transferred from a hot substance, the lava, to a cold substance, the
ocean water. In fact, if the lava is hot enough (e.g., if it is molten), so much heat can be transferred that the water is converted to
steam (Figure 7.9.7).

Figure 7.9.7 : Spontaneous Transfer of Heat from a Hot Substance to a Cold Substance

Summary
A measure of the possible arrangements of a system is its entropy (S), a state function whose value increases with an increase in the
number of available microstates. For a given system, the greater the number of microstates, the higher the entropy. The change in
entropy of the system or the surroundings is the quantity of heat transferred divided by the temperature. The second law of
thermodynamics states that the entropy of a system at equilibrium is constant and does not have an effect on the entropy of the
universe, whereas in a system that is not at equilibrium, such as the transfer of heat from a hot object to a cold object, the entropy
of the universe increases.

Contributors
Modified by Tom Neils (Grand Rapids Community College)

7.9: Entropy and the Second Law of Thermodynamics is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

7.9.5 [Link]
7.10: Gibbs Free Energy
Skills to Develop
To understand the relationship between the standard Gibbs free energy change, the extent of reaction, and equilibrium
To understand the relationship between Gibbs free energy change and the direction in which a reaction will proceed to reach
equilibrium
To understand the relationship between Gibbs free energy and work.

Gibbs Free-Energy
The Gibbs free energy (G), often called simply free energy, was named in honor of J. Willard Gibbs (1838–1903), an American
physicist who first developed the concept. It is defined in terms of three other state functions with which you are already familiar:
enthalpy, temperature, and entropy:

G = H −TS (7.10.1)

Because it is a combination of state functions, G is also a state function.

The relationship between the entropy change of the surroundings and the heat gained or lost by the system provides the key
connection between the thermodynamic properties of the system and the change in entropy of the universe.

Standard Gibbs Free-Energy Change

We have seen that there is no way to measure absolute enthalpies, although we can measure changes in enthalpy (ΔH) during a
chemical reaction. Because enthalpy is one of the components of Gibbs free energy, we are consequently unable to measure
absolute free energies; we can measure only changes in free energy. The standard free-energy change (ΔG°) is the change in free
energy when one substance or a set of substances in their standard states is converted to one or more other substances, also in their
standard states. This set of conditions required for determining ΔG° is rarely, if ever, encountered when carrying out chemical
reactions, so the literal meaning of ΔG° is of questionable value. However, the sign and magnitude of ΔG° are extremely helpful
in describing whether the reaction is product-favored or reactant-favored when it has reached equilibrium, which is sometimes
known as the extent of a chemical reaction.
The standard free-energy change can be calculated from the definition of free energy, if the standard enthalpy and entropy changes
are known, using Equation 7.10.2:
ΔG° = ΔH ° − T ΔS° (7.10.2)

ΔG° < 0 means that the reaction is product-favored at equilibrium; the odds are in favor of making a significant amount of
product at equilibrium.

ΔG° > 0 means that the reaction is reactant-favored at equilibrium; the odds are against making a significant amount of
product at equilibrium.
It is important to recognize that a positive value of ΔG° for a reaction does not mean that no products will form if the
reactants in their standard states are mixed; it means only that, at equilibrium, the concentrations of the products will be less
than the concentrations of the reactants.
ΔG° = 0 means that the reaction is neither product-favored nor reactant-favored at equilibrium; there are 50:50 odds that a
significant amount of product will be made at equilibrium.
This situation is rare for chemical reactions, although it can happen. This situation describes all phase changes when they
occur at the exact phase change temperature.

Exercise 7.10.1
Calculate the standard free-energy change (ΔG ) at 25°C for the reaction
o

2 H2 (g) + N2 (g) ⇌ N2 H4 (l).

7.10.1 [Link]
 Is the reaction product-favored at equilibrium as written at 25°C?

Hint
At 25°C, the standard enthalpy change (ΔH ) is 50.6 kJ/mol, and the standard entropy change (ΔS ) is -0.332 kJ/(mol•K)
o o

Answer
149.5 kJ/mol
no, not product-favored, but reactant-favored, at equilibrium
Video Solution

Calculated values of ΔG° are used to predict whether a reaction will be product-favored at equilibrium when the reactants and
products are mixed under standard conditions. Very few reactions are actually carried out under standard conditions, and calculated
values of ΔG° may not tell us whether a given reaction will occur spontaneously under nonstandard conditions. What determines
whether a reaction will occur spontaneously is the free-energy change (ΔG, notice the missing nought!) under the actual
experimental conditions, which are usually quite different from ΔG°. Because ΔH and ΔS usually do not vary greatly with
temperature in the absence of a phase change, we can use tabulated values of ΔH° and ΔS° to calculate ΔG° at various
temperatures, as long as no phase change occurs over the temperature range being considered.
We can also use the signs of ΔH° and ΔS° to determine the sign of ΔG° for a given reaction at various temperatures. Using
Equation 7.10.2, the sign of ΔG° can be predicted for a reaction, using the signs of ΔH° and ΔS°:
ΔG° = ΔH ° − T ΔS° (7.10.3)

sign of ΔH° sign of ΔS° sign of ΔG° Meaning

The reaction is product-favored at

equilibrium at all temperatures;
_ + _
always likely; odds always favor
it
The reaction is reactant-favored at
equilibrium at all temperatures;
+ _ +
never likely; odds are always
against it
The sign of ΔG° is temperature
dependent. The reaction will be
+ + -/+
product-favored at relatively high
temperatures.
The sign of ΔG° is temperature
dependent. The reaction will be
_ _ -/+
product-favored at relatively low
temperatures.

NOTE: If ΔS° and ΔH° for a reaction have the same sign, then the sign of ΔG° depends on the temperature and thus the relative
magnitudes of the ΔH° and TΔS° terms.

If ΔS° and ΔH° for a reaction have the same sign, then there is a specific temperature at which the sign of ΔG° must equal 0 as the
reaction shifts from being reactant-favored at equilibrium to being product-favored at equilibrium, and vice versa. The temperature
at which this flip over occurs, at which a given reaction is neither product-favored nor reactant-favored, can be calculated by setting
ΔG° = 0 in Equation 7.10.2, as illustrated in Example 7.10.2.

Example 7.10.2

7.10.2 [Link]
 The reaction of nitrogen and hydrogen gas to produce ammonia

3 H2 (g) + N2 (g) ⇌ 2N H3 (l).

is one in which ΔH° is −91.8 kJ and ΔS° is −198.1 J/K (both are negative). Such reactions are predicted to be product-favored at
low temperatures but reactant-favored at high temperatures.
Calculate the temperature at which this reaction changes from product-favored to reactant-favored, assuming that ΔH° and ΔS°
are independent of temperature.
Given: ΔH° and ΔS°
Asked for: temperature at which reaction changes from product-favored to reactant-favored
Strategy:
Set ΔG° equal to zero in Equation 7.10.2 and solve for T, the temperature at which the reaction becomes reactant-favored.
SOLUTION
The temperature at which the reaction becomes reactant-favored at equilibrium is found by setting ΔG° equal to zero and
rearranging Equation 7.10.2 to solve for T:
∘ ∘ ∘
ΔG = ΔH − T ΔS =0

∘ ∘
ΔH = T ΔS

∘
ΔH (−91.8 kJ)(1000 J/kJ)
T = = = 463 K
∘
ΔS −198.1 J/K

This is a case in which a chemical engineer is severely limited by thermodynamics. Any attempt to increase the rate of reaction
of nitrogen with hydrogen by increasing the temperature will cause reactants to be favored over products above 463 K.

Exercise 7.10.2
ΔH°= -116.2 kJ and ΔS° = - 146.6 J/K for the reaction of nitric oxide and oxygen to form nitrogen dioxide.

2N O(g) + O2 (g) ⇌ 2N O2 (l).

Use those data to calculate the temperature at which this reaction changes from product-favored to reactant-favored.

Answer
792.6 K
Video Solution

Gibbs Free Energy and the Direction of Spontaneous Reactions

A second major goal of chemical thermodynamics is to establish criteria for predicting whether a particular reaction or process will
occur spontaneously, that is, if it will proceed in the forward direction, as written, to reach equilibrium. We have developed one
such criterion, the change in entropy of the universe: if ΔSuniv > 0 for a process or a reaction, then the process will go in the
forward direction as written to reach equilibrium. Conversely, if ΔSuniv < 0, a process will go in the reverse direction as written to
reach equilibrium; if ΔSuniv = 0, the system is already at equilibrium. The sign of ΔSuniv is a universally applicable and infallible
indicator of the direction of a reaction as it proceeds towards equilibrium. Unfortunately, using ΔSuniv requires that we calculate ΔS
for both a system and its surroundings. This calculation is not particularly useful for two reasons: we are normally much more
interested in the system than in the surroundings, and it is difficult to make quantitative measurements of the surroundings (i.e., the
rest of the universe). A criterion of spontaneity that is based solely on the state functions of a system would be much more
convenient, and is provided by the Gibbs free energy.

7.10.3 [Link]
The criterion for predicting the likely direction for the reaction to occur to reach equilibrium is based on (ΔG), the change in G, at
constant temperature and pressure. Although very few chemical reactions actually occur under conditions of constant temperature
and pressure, most systems can be brought back to the initial temperature and pressure without significantly affecting the value of
thermodynamic state functions such as G. At constant temperature and pressure,
ΔG = ΔH − T ΔS (7.10.4)

where all thermodynamic quantities are those of the system.

The relationship between the entropy change of the surroundings and the heat gained or lost by the system provides the key
connection between the thermodynamic properties of the system and the change in entropy of the universe. The relationship shown
in Equation 7.10.4 allows us to predict spontaneity by focusing exclusively on the thermodynamic properties and temperature of
the system. We predict that highly exothermic processes (ΔH ≪ 0 ) that increase the disorder of a system (ΔS ≫ 0 ) would
sys

therefore occur spontaneously. An example of such a process is the decomposition of ammonium nitrate fertilizer. Ammonium
nitrate was also used to destroy the Murrah Federal Building in Oklahoma City, Oklahoma, in 1995.
For a system at constant temperature and pressure, we can summarize the following results:
If ΔG < 0 , the process occurs spontaneously, that is, it proceeds in the forward direction, as written, until it reaches
equilibrium.
If ΔG = 0 , the system is at equilibrium.
If ΔG > 0 , the process is not spontaneous as written but occurs spontaneously in the reverse direction, until it reaches
equilibrium.
To further understand how the various components of ΔG dictate whether a process occurs spontaneously, we now look at a simple
and familiar physical change: the conversion of liquid water to water vapor. If this process is carried out at 1 atm and the normal
boiling point of 100.00°C (373.15 K), we can calculate ΔG from the experimentally measured value of ΔHvap (40.657 kJ/mol). For
vaporizing 1 mol of water, ΔH = 40, 657; J, so the process is highly endothermic. The value of ΔS is 108.96 J/K
Hence there is an increase in the disorder of the system. At the normal boiling point of water,
ΔG100∘ C = ΔH100∘ C − T ΔS100∘ C

= 40,657 J − [(373.15 K)(108.96 J/K)]

=0 J

The energy required for vaporization offsets the increase in disorder of the system. Thus ΔG = 0, and the liquid and vapor are in
equilibrium, as is true of any liquid at its boiling point under standard conditions.
Now suppose we were to superheat 1 mol of liquid water to 110°C. The value of ΔG for the vaporization of 1 mol of water at
110°C, assuming that ΔH and ΔS do not change significantly with temperature, becomes
ΔG110∘ C = ΔH − T ΔS

= 40,657 J − [(383.15 K)(108.96 J/K)]

= −1091 J

At 110°C, ΔG < 0 , and vaporization is predicted to occur spontaneously and irreversibly.

We can also calculate ΔG for the vaporization of 1 mol of water at a temperature below its normal boiling point—for example,
90°C—making the same assumptions:

ΔG90∘ C = ΔH − T ΔS

= 40,657 J − [(363.15 K)(108.96 J/K)]

= 1088 J

At 90°C, ΔG > 0, and water does not spontaneously convert to water vapor. When using all the digits in the calculator display in
carrying out our calculations, ΔG110°C = 1090 J = −ΔG90°C, as we would predict.
Relating Enthalpy and Entropy changes under Equilibrium Conditions
ΔG = 0 only if ΔH = T ΔS .

7.10.4 [Link]
We can also calculate the temperature at which liquid water is in equilibrium with water vapor. Inserting the values of ΔH and ΔS
into the definition of ΔG (Equation 7.10.2), setting ΔG = 0 , and solving for T ,
0 J=40,657 J−T(108.96 J/K)
T=373.15 K
Thus ΔG = 0 at T = 373.15 K and 1 atm, which indicates that liquid water and water vapor are in equilibrium; this temperature is
called the normal boiling point of water. At temperatures greater than 373.15 K, ΔG is negative, and water evaporates
spontaneously and irreversibly. Below 373.15 K, ΔG is positive, and water does not evaporate spontaneously. Instead, water vapor
at a temperature less than 373.15 K and 1 atm will spontaneously and irreversibly condense to liquid water. Figure 7.10.1 shows
how the ΔH and T ΔS terms vary with temperature for the vaporization of water. When the two lines cross, ΔG = 0 , and
ΔH = T ΔS .

Figure 7.10.1 : Temperature Dependence of ΔH and TΔS for the Vaporization of Water. Both ΔH and TΔS are temperature
dependent, but the lines have opposite slopes and cross at 373.15 K at 1 atm, where ΔH = TΔS. Because ΔG = ΔH − TΔS, at this
temperature ΔG = 0, indicating that the liquid and vapor phases are in equilibrium. The normal boiling point of water is therefore
373.15 K. Above the normal boiling point, the TΔS term is greater than ΔH, making ΔG < 0; hence, liquid water evaporates
spontaneously. Below the normal boiling point, the ΔH term is greater than TΔS, making ΔG > 0. Thus liquid water does not
evaporate spontaneously, but water vapor spontaneously condenses to liquid.

The Relationship between ΔG and Work

In the previous subsection, we learned that the value of ΔG allows us to predict the spontaneity of a physical or a chemical change.
In addition, the magnitude of ΔG for a process provides other important information. The change in free energy (ΔG) is equal to
the maximum amount of work that a system can perform on the surroundings while undergoing a spontaneous change (at constant
temperature and pressure): ΔG = wmax. To see why this is true, let’s look again at the relationships among free energy, enthalpy, and
entropy expressed in Equation 7.10.2. We can rearrange this equation as follows:

ΔH = ΔG + T ΔS (7.10.5)

This equation tells us that when energy is released during an exothermic process (ΔH < 0), such as during the combustion of a fuel,
some of that energy can be used to do work (ΔG < 0), while some is used to increase the entropy of the universe (TΔS > 0). Only if
the process occurs infinitely slowly in a perfectly reversible manner will the entropy of the universe be unchanged. (For more
information on entropy and reversibility, see the previous section). Because no real system is perfectly reversible, the entropy of the
universe increases during all processes that produce energy. As a result, no process that uses stored energy can ever be 100%
efficient; that is, ΔH will never equal ΔG because ΔS has a positive value.
One of the major challenges facing engineers is to maximize the efficiency of converting stored energy to useful work or
converting one form of energy to another. As indicated in Table 7.10.1, the efficiencies of various energy-converting devices vary

7.10.5 [Link]
widely. For example, an internal combustion engine typically uses only 25%–30% of the energy stored in the hydrocarbon fuel to
perform work; the rest of the stored energy is released in an unusable form as heat. In contrast, gas–electric hybrid engines, now
used in several models of automobiles, deliver approximately 50% greater fuel efficiency. A large electrical generator is highly
efficient (approximately 99%) in converting mechanical to electrical energy, but a typical incandescent light bulb is one of the least
efficient devices known (only approximately 5% of the electrical energy is converted to light). In contrast, a mammalian liver cell
is a relatively efficient machine and can use fuels such as glucose with an efficiency of 30%–50%.
Table 7.10.1: Approximate Thermodynamic Efficiencies of Various Devices
Device Energy Conversion Approximate Efficiency (%)

large electrical generator mechanical → electrical 99

chemical battery chemical → electrical 90

home furnace chemical → heat 65

small electric tool electrical → mechanical 60

space shuttle engine chemical → mechanical 50

mammalian liver cell chemical → chemical 30–50

spinach leaf cell light → chemical 30

internal combustion engine chemical → mechanical 25–30

fluorescent light electrical → light 20

solar cell light → electricity 10-20

incandescent light bulb electricity → light 5

yeast cell chemical → chemical 2–4

Summary
The change in Gibbs free energy, which is based solely on changes in state functions, is the criterion for describing two aspects
of a reaction.
Standard free-energy change:

ΔG° = ΔH ° − T ΔS°

The standard free-energy change (ΔG°) is the change in free energy when one substance or a set of substances in their standard
states is converted to one or more other substances, also in their standard states. The sign of ΔG° tells us if a reaction will be
reactant-favored (+ ΔG°) or product-favored ( - ΔG°) at equilibrium. The magnitude of ΔG° tells us the extent of the reaction. A
large +ΔG° tells us the reaction makes very little product at equilibrium. A large - ΔG° tells us the reaction makes a great deal of
product at equilibrium.
Free-energy change:

ΔG = ΔH − T ΔS

The change in free energy (ΔG) is the difference between the heat released during a process and the heat released for the same
process occurring in a reversible manner. If a system is at equilibrium, ΔG = 0. If the process is spontaneous, ΔG < 0. If the process
is not spontaneous as written, but is spontaneous in the reverse direction, ΔG > 0. At constant temperature and pressure, ΔG is
equal to the maximum amount of work a system can perform on its surroundings while undergoing a spontaneous change.

Contributors
Modified by Tom Neils (Grand Rapids Community College)

7.10: Gibbs Free Energy is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

7.10.6 [Link]
7.11 Gibbs Free Energy and Equilibrium
Skills to Develop
To know the relationship between free energy and the equilibrium constant.

We have identified three criteria for whether a given reaction will occur spontaneously (that is, proceed in the forward direction, as
written, to reach equilibrium): ΔSuniv > 0, ΔGsys < 0, and the relative magnitude of the reaction quotient Q versus the equilibrium
constant K. Recall that if K > Q, then the reaction proceeds spontaneously to the right as written, resulting in the net conversion of
reactants to products. Conversely, if K < Q, then the reaction proceeds spontaneously to the left as written, resulting in the net
conversion of products to reactants. If K = Q, then the system is at equilibrium, and no net reaction occurs. Table 1 summarizes
these criteria and their relative values for spontaneous, nonspontaneous, and equilibrium processes.
Table 1 : Criteria for the Spontaneity of a Process as Written
Spontaneous Equilibrium Nonspontaneous*

ΔSuniv > 0 ΔSuniv = 0 ΔSuniv < 0

ΔGsys < 0 ΔGsys = 0 ΔGsys > 0

K>Q K=Q K<Q

*Spontaneous in the reverse direction.

Because all three criteria are assessing the same thing—the spontaneity of the process—it would be most surprising indeed if they
were not related. In this section, we explore the relationship between the free energy change of reaction (ΔG) and the instantaneous
reaction quotient (Q). To do so, we will first reveal the relationship between the standard free energy change of a reaction (ΔG°)
and the equilibrium constant (K).

Free Energy and the Equilibrium Constant

Because ΔH° and ΔS° determine the magnitude of ΔG° and because K is a measure of the ratio of the concentrations of products to
the concentrations of reactants, we should be able to express K in terms of ΔG° and vice versa.
Combining terms gives the following relationship between ΔG and the reaction quotient Q:
∘ ∘
ΔG = ΔG + RT lnQ = ΔG + RT ln Q (1)

where ΔG° indicates that all reactants and products are in their standard states. For a system at equilibrium (K = Q ,), and as
you’ve learned in this chapter, ΔG = 0 for a system at equilibrium. Therefore, we can describe the relationship between ΔG° and K
as follows:
0 = ΔG° + RT ln K (2)

ΔG° = −RT ln K (3)

If you combine equations 1 and 3, you get the equation

Q
ΔG = RT ln (4)
K

If the products and reactants are in their standard states and ΔG° < 0, then K > 1, and products are favored over reactants at
equilibrium. Conversely, if ΔG° > 0, then K < 1, and reactants are favored over products at equilibrium. If ΔG° = 0, then K = 1 ,
and neither reactants nor products are favored at equilibrium.

For a product-favored process under standard conditions, K is greater than 1.

Example 1
Calculate K for the reaction of O2 with N2 to give NO at 423 K:
N2(g) + O2(g) ⇌ 2N O(g)

1 [Link]
ΔG° for this reaction is +22.7 kJ/mol of N2.
Given: ΔG°, and temperature
Asked for: K
Strategy:
Substitute values for ΔG° and T (in kelvin) into Equation 3 to calculate K, the equilibrium constant for the formation of nitrogen
monoxide.
SOLUTION
For equilibrium conditions, rearranging Equation 3,
∘
ΔG = −RT ln Kp (5)
∘
−ΔG
= ln Kp (6)
RT

Inserting the value of ΔG° and the temperature (423 K) into this equation,
(−22.7 kJ)(1000 J/kJ)
ln K = − = −6.45 (7)
(8.314 J/K)(423 K)
−3
K = 1.6 × 10 (8)

Thus the equilibrium constant for the formation of nitrogen monoxide at room temperature is less than 1. The reaction is
reactant-favored at equilibrium.

Exercise 1
Calculate K for the reaction of NO with O2 to give NO2 at 25°C. ΔG° for this reaction is −70.5 kJ/mol of O2.

Answer
2.2 × 1012

Example 2
ΔG° is −32.7 kJ/mol of N2 for the reaction at 100oC

N2(g) + 3 H2(g) ⇌ 2N H3(g)

Calculate ΔG for the same reaction under the following nonstandard conditions:
= 2.00 M,
[ N2 ]

= 7.00 M,
[ H2 ]

[ NH ] = 0.021 M,
3

and T = 100°C.
In which direction must the reaction proceed to reach equilibrium?
Given: balanced chemical equation, molarity of each species, temperature, and ΔG°
Asked for: the direction in which the reaction will proceed to reach equilibrium
Strategy:
A. Using the concentration values given, calculate Q.
B. Using the value of ΔG°, calculate the value of K using Equation 3
C. Substitute the values of K and Q into Equation 4 to obtain ΔG for the reaction under nonstandard conditions.
Solution:
A Using the equilibrium constant expression for the given reaction, we can calculate Q:
2 2
[NH3 ] (0.021)
−7
Q = = = 6.4 × 10
3 3
[ N2 ][ H2 ] (2.00)(7.00)

2 [Link]
 B Using the value of ΔG°, calculate the value of K

o
J
ΔG = −32, 700J = −(8.314 )(373K)lnK (9)
g⋅ K

−32, 700J
= lnK (10)
J
−8.314 ⋅ 373K
g⋅ K

10.54
e = 38, 000J = K (11)

C Substituting the values of K and Q into Equation 1,

−7
Q 1kJ 6.4 × 10
ΔG = RT ln = (8.314J/K)(373K) ( ) ln
4
K 1000J 3.8 × 10

= −77 kJ 2

Because ΔG < 0 and K > Q, the reaction is spontaneous in the forward direction, as written. In other words, the reaction must
proceed to the right to reach equilibrium.

Exercise 2
Calculate ΔG for the reaction N + O
2g ⇌ 2N O
2(g)
under the conditions: T = 423 K, [N O ] = 0.0100 M, [O ] = 0.200 M, and
g 2

[N ] = 1.00 × 10−4 M. The value of ΔG° for this reaction is +22.7 kJ. In which direction will the reaction proceed to reach
2

equilibrium?

Answer
ΔG = +28.3 kJ; the reaction is nonspontaneous to the right as written, so the reaction will go to the left to reach equilibrium.
This can be verified by the fact that K < Q.

Temperature Dependence of the Equilibrium Constant

The fact that ΔG° and K are related provides us with another explanation of why equilibrium constants are temperature dependent.
This relationship is shown explicitly in Equation 3, which can be rearranged as follows:
∘ ∘
ΔH ΔS
ln K = − + (12)
RT R

Assuming ΔH° and ΔS° are temperature independent, for an exothermic reaction (ΔH° < 0), the magnitude of K decreases with
increasing temperature, whereas for an endothermic reaction (ΔH° > 0), the magnitude of K increases with increasing temperature.
The quantitative relationship expressed in Equation 12 agrees with the qualitative predictions made by applying Le Chatelier’s
principle. Because heat is produced in an exothermic reaction, adding heat (by increasing the temperature) will shift the equilibrium
to the left, favoring the reactants and decreasing the magnitude of K. Conversely, because heat is consumed in an endothermic
reaction, adding heat will shift the equilibrium to the right, favoring the products and increasing the magnitude of K. Equation 12
also shows that the magnitude of ΔH° dictates how rapidly K changes as a function of temperature. In contrast, the magnitude and
sign of ΔS° affect the magnitude of K but not its temperature dependence.
If we know the value of K at a given temperature and the value of ΔH° for a reaction, we can estimate the value of K at any other
temperature, even in the absence of information on ΔS°. Suppose, for example, that K1 and K2 are the equilibrium constants for a
reaction at temperatures T1 and T2, respectively. Applying Equation 12 gives the following relationship at each temperature:
∘ ∘
−ΔH ΔS
ln K1 = + (13)
RT1 R
∘ ∘
−ΔH ΔS
ln K2 = + (14)
RT2 R

Subtracting ln K from ln K ,
1 2

3 [Link]
 ∘
K2 ΔH 1 1
ln K2 − ln K1 = ln = ( − ) (15)
K1 R T1 T2

Thus calculating ΔH° from tabulated enthalpies of formation and measuring the equilibrium constant at one temperature (K1) allow
us to calculate the value of the equilibrium constant at any other temperature (K2), assuming that ΔH° and ΔS° are independent of
temperature.

Summary
Both K and ΔG° can be used to predict the ratio of products to reactants at equilibrium for a given reaction. ΔG° is related to K by
the equation ΔG° = −RT ln K .
If ΔG° < 0, then K > 1, and products are favored over reactants at equilibrium.
If ΔG° > 0, then K < 1, and reactants are favored over products at equilibrium.
If ΔG° = 0, then K = 1, and the amount of products will be roughly equal to the amount of reactants at equilibrium. This is a
rare occurrence for chemical reactions.
If a system is not at equilibrium, ΔG and Q can be used to tell us in which direction the reaction must proceed to reach equilibrium.
Q
ΔG is related to Q by the equation ΔG = RT ln .
K

If ΔG < 0, then K > Q, and the reaction must proceed to the right to reach equilibrium.
If ΔG > 0, then K < Q, and the reaction must proceed to the left to reach equilibrium.
If ΔG = 0, then K = Q, and the reaction is at equilibrium.
We can use the measured equilibrium constant K at one temperature, along with ΔH° to estimate the equilibrium constant for a
reaction at any other temperature.

Contributors
Mike Blaber (Florida State University)
Modified by Tom Neils (Grand Rapids Community College)

7.11 Gibbs Free Energy and Equilibrium is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

4 [Link]
What we are studying
What we are studying is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1 [Link]
 CHAPTER OVERVIEW

8: Acids and Bases

8.1: An Introduction to Acids and Bases
8.2: Brønsted-Lowry Acids and Bases
8.3 Lewis Acids and Bases
8.4: Acid Strength and the Acid Dissociation Constant (Ka)
8.5: Autoionization of Water and pH
8.6 - Finding the Hydronium Ion Concentration and pH of Strong and Weak Acid Solutions
8.7: The Acid-Base Properties of Ions and Salts
8.8: Buffers: Solutions That Resist pH Change
8.9 Buffer Capacity and Buffer Range
8.10: Lewis Acids and Bases
8.11: Acid/Base (Exercises)

8: Acids and Bases is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
8.1: An Introduction to Acids and Bases
Why Do We Care about Acids and Bases?

Heartburn is caused by a buildup of excessive amounts of stomach acid, particularly HCl. This acid is used to digest the food we
eat, but it can often back up into the esophagus causing that burning sensation many of us are familiar with. The symptoms of
heartburn can be treated with a mild base, which acts to neutralize the excess HCl. For example, Tums is a very commonly used
antacid that can be bought over the counter. Other antacids, such as Alka Seltzer, work in similar ways. Below is shown the
reaction in which calcium carbonate (the active ingredient in Tums) neutralizes HCl in a simple proton transfer reaction. Following
this acid-base reaction, carbonic acid quickly degrades into CO2 and H2O.

A comparison of a healthy condition to GERD. Image used with permission (Cc BY-SA 4.0; BruceBlaus .

C aC O3(s) + 2H C l(aq) → H2 C O3(aq) + C aC l2(aq)

H2 C O3(aq) → H2 O(aq) + C O2(g)

General Descriptions of Acids and Bases

Acids and bases are common in many solutions that exist everywhere, and can be defined by their physical and chemical
observations (Table 8.1.1).
Table 8.1.1: General Properties of Acids and Bases
ACIDS BASES

produce a piercing pain in a wound. give a slippery feel.

taste sour. taste bitter.

are colorless when placed in phenolphthalein (an indicator). are pink when placed in phenolphthalein (an indicator).

are red on blue litmus paper (a pH indicator). are blue on red litmus paper (a pH indicator).

8.1.1 [Link]
 ACIDS BASES

have a pH<7 at 25oC. have a pH>7 at 25oC.

produce carbon dioxide when reacted with carbonates.

Common examples: Lemons, oranges, vinegar, urine, sulfuric acid, Common Examples: Soap, toothpaste, bleach, cleaning agents,
hydrochloric acid limewater, ammonia water, sodium hydroxide.

Acids and bases in aqueous solutions will conduct electricity because they contain dissolved ions. Therefore, acids and bases are
electrolytes. Strong acids and bases will be strong electrolytes. Weak acids and bases will be weak electrolytes.

The Arrhenius Definition of Acids and Bases

In 1884, the Swedish chemist Svante Arrhenius proposed two specific classifications of compounds, termed acids and bases. When
dissolved in an aqueous solution, certain ions were released into the solution. The Arrhenius definition of acid-base reactions is a
development of the "hydrogen theory of acids". It was used to provide a modern definition of acids and bases, and followed from
Arrhenius's work with Friedrich Wilhelm Ostwald in establishing the presence of ions in aqueous solution in 1884. This led to
Arrhenius receiving the Nobel Prize in Chemistry in 1903.
An Arrhenius acid is a compound that increases the concentration of H ions that are present when added to water. These H ions
+ +

form the hydronium ion (H O ) when they combine with water molecules. This process is represented in a chemical equation by
3
+

adding H2O to the reactants side.

+ −
H C l(aq) → H + Cl (8.1.1)
(aq) (aq)

In this reaction, hydrochloric acid (H C l) dissociates into hydrogen (H ) and chlorine (C l ) ions when dissolved in water, thereby
+ −

releasing H+ ions into solution. Formation of the hydronium ion equation:

+ −
H C l(aq) + H2 O(l) → H3 O + Cl (8.1.2)
(aq) (aq)

The Arrhenius definitions of acidity and alkalinity are restricted to aqueous solutions and refer to the concentration of the solvated
ions. Under this definition, pure H SO or H C l dissolved in acetone are not acidic, despite the fact that both of these acids will
2 4

donate a proton to acetone. In addition, under the Arrhenius definition, a solution of sodium amide (N aN H ) in liquid ammonia is
2

not alkaline, despite the fact that the amide ion (N H ) will readily deprotonate ammonia. Thus, the Arrhenius definition can only
2
−

describe acids and bases in an aqueous environment.

Limitation of the Arrhenius Definition of Acids and Bases
The Arrhenius definition can only describe acids and bases in an aqueous environment.

Contributors
Anonymous
Modified by Tom Neils (Grand Rapids Community College)

8.1: An Introduction to Acids and Bases is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

8.1.2 [Link]
8.2: Brønsted-Lowry Acids and Bases
For all of the acid/base reactions, remember that the activity of water, as the solvent, is defined as 1.00. Therefore, the activity of
water (sometimes mistakenly shown as the
[H2O]) will not appear explicitly in any law of mass action equations (equilibrium constant expressions). The activity is not left
out, it simply has a value of 1.00.

 Learning Objectives
Identify acids, bases, and conjugate acid-base pairs according to the Brønsted-Lowry definition
Write equations for acid and base ionization reactions
Use the ion-product constant for water to calculate hydronium and hydroxide ion concentrations
Describe the acid-base behavior of amphiprotic substances

Acids and bases have been known for a long time. When Robert Boyle characterized them in 1680, he noted that acids dissolve
many substances, change the color of certain natural dyes (for example, they change litmus from blue to red), and lose these
characteristic properties after coming into contact with alkalis (bases). In the eighteenth century, it was recognized that acids have a
sour taste, react with limestone to liberate a gaseous substance (now known to be CO2), and interact with alkalis to form neutral
substances. In 1815, Humphry Davy contributed greatly to the development of the modern acid-base concept by demonstrating that
hydrogen is the essential constituent of acids. Around that same time, Joseph Louis Gay-Lussac concluded that acids are substances
that can neutralize bases and that these two classes of substances can be defined only in terms of each other. The significance of
hydrogen was reemphasized in 1884 when Svante Arrhenius defined an acid as a compound that dissolves in water to yield
hydrogen cations (now recognized to be hydronium ions) and a base as a compound that dissolves in water to yield hydroxide
anions.
Previously, we defined acids and bases as Arrhenius did: An acid is a compound that dissolves in water to yield hydronium ions (
H O ) and a base as a compound that dissolves in water to yield hydroxide ions (OH ). This definition is not wrong; it is simply
+ −
3

limited. We extended the definition of an acid or a base using the more general definition proposed in 1923 by the Danish chemist
Johannes Brønsted and the English chemist Thomas Lowry. Their definition centers on the proton, H . A proton is what remains +

when a normal hydrogen atom, H , loses an electron. A compound that donates a proton to another compound is called a Brønsted-
1
1

Lowry acid, and a compound that accepts a proton is called a Brønsted-Lowry base. An acid-base reaction is the transfer of a
proton from a proton donor (acid) to a proton acceptor (base). In a subsequent chapter of this text we will introduce the most
general model of acid-base behavior introduced by the American chemist G. N. Lewis.
Acids may be compounds such as H C l or H SO , organic acids like acetic acid (CH COOH ) or ascorbic acid (vitamin C), or
2 4 3

H O . Anions (such as HSO , H PO , HS , and HCO ) and cations (such as H O , NH , and [Al (H O) ] ) may also act
− − − − + + 3 +
2 4 2 4 3 3 4 2 6

as acids. Bases fall into the same three categories. Bases may be neutral molecules (such as H O , NH , and CH NH ), anions 2 3 3 2
2 +
(such as OH , HS , HCO , CO , F , and PO ), or cations (such as [Al(H O) OH] ). The most familiar bases are ionic
− − −
3
2 −
3
− 3 −
4 2 5

compounds such as NaOH and Ca(OH) , which contain the hydroxide ion, OH . The hydroxide ion in these compounds accepts
2
−

a proton from acids to form water:

+ −
H + OH → H O (8.2.1)
2

We call the product that remains after an acid donates a proton the conjugate base of the acid. This species is a base because it can
accept a proton (to re-form the acid):

acid ⇌ proton + conjugate base (8.2.2)

+ −
HF ⇌ H +F (8.2.3)

+ −
H SO ⇌ H + HSO (8.2.4)
2 4 4

+ −
H O⇌ H + OH (8.2.5)
2

− + 2 −
HSO ⇌ H + SO (8.2.6)
4 4

+ +
NH ⇌ H + NH (8.2.7)
4 3

8.2.1 [Link]
We call the product that results when a base accepts a proton the base’s conjugate acid. This species is an acid because it can give
up a proton (and thus re-form the base):
base + proton ⇌ conjugate acid (8.2.8)

− +
OH +H ⇌ H O (8.2.9)
2

+ +
H O+H ⇌ H O (8.2.10)
2 3

+ +
NH +H ⇌ NH (8.2.11)
3 4

2 − + −
S +H ⇌ HS (8.2.12)

2 − + −
CO +H ⇌ HCO (8.2.13)
3 3

\[\ce{F^- +H^+ \rightleftharpoons HF} \label{16.2.3g} \]

In these two sets of equations, the behaviors of acids as proton donors and bases as proton acceptors are represented in isolation. In
reality, all acid-base reactions involve the transfer of protons between acids and bases. For example, consider the acid-base reaction
that takes place when ammonia is dissolved in water. A water molecule (functioning as an acid) transfers a proton to an ammonia
molecule (functioning as a base), yielding the conjugate base of water, OH , and the conjugate acid of ammonia, NH :
− +
4

A conjugate acid base pair if when we remove a H plus from the acid to get the conjugate base. Another conjugate acid base pair is
when we add H plus to a base to get a conjugate acid. In a reaction: the acid and base are the reactants and the products are the
conjugate base and conjugate acid.
The reaction between a Brønsted-Lowry acid and water is called acid ionization. For example, when hydrogen fluoride dissolves in
water and ionizes, protons are transferred from hydrogen fluoride molecules to water molecules, yielding hydronium ions and
fluoride ions:

In this reaction HF is treated as the acid and water is treated as the base. The products as H3O plus and F minus. H3O plus is the
acid and F minus is the base.
When we add a base to water, a base ionization reaction occurs in which protons are transferred from water molecules to base
molecules. For example, adding pyridine to water yields hydroxide ions and pyridinium ions:
<div data-mt-source="1" &quot;This " height="167" width="612" src="/@api/deki/files/56740/CNX_Chem_14_01_NH3_img.jpg">
Notice that both these ionization reactions are represented as equilibrium processes. The relative extent to which these acid and
base ionization reactions proceed is an important topic treated in a later section of this chapter. In the preceding paragraphs we saw
that water can function as either an acid or a base, depending on the nature of the solute dissolved in it. In fact, in pure water or in
any aqueous solution, water acts both as an acid and a base. A very small fraction of water molecules donate protons to other water
molecules to form hydronium ions and hydroxide ions:

8.2.2 [Link]
 Here we have 2 water molecules reacting together. One water molecule is an acid while the second water molecule acts as a base.
For the products, we get H3O plus and OH minus. H3O plus is the acid and OH minus is the base.
This type of reaction, in which a substance ionizes when one molecule of the substance reacts with another molecule of the same
substance, is referred to as autoionization. Pure water undergoes autoionization to a very slight extent. Only about two out of
every 10 molecules in a sample of pure water are ionized at 25 °C. The equilibrium constant for the ionization of water is called
9

the ion-product constant for water (Kw):

+ − + −
H O(l) + H O(l) ⇌ H O + HO Kw = [ H O ][ OH ] (8.2.14)
2 2 3 (aq) (aq) 3

The slight ionization of pure water is reflected in the small value of the equilibrium constant; at 25 °C, Kw has a value of
1.0 × 10
−14
. The process is endothermic, and so the extent of ionization and the resulting concentrations of hydronium ion and
hydroxide ion increase with temperature. For example, at 100 °C, the value for K is approximately 5.1 × 10 , roughly 100-
w
−13

times larger than the value at 25 °C.

Conjugate Acid-Base Pairs

A Video Discussing Conjugate Acid-Base Pairs: Conjugate Acid-Base Pairs [[Link]]

 Example 8.2.1: Ion Concentrations in Pure Water

What are the hydronium ion concentration and the hydroxide ion concentration in pure water at 25 °C?

Solution
The autoionization of water yields the same number of hydronium and hydroxide ions. Therefore, in pure water,
[ H O ] = [ OH ] . At 25 °C:
+ −

+ − + 2+ − 2+ −14
Kw = [ H O ][ OH ] = [H O ] = [ OH ] = 1.0 × 10
3 3

So:
− −−−−−−− −
+ − −14 −7
[H O ] = [ OH ] = √ 1.0 × 10 = 1.0 × 10 M
3

The hydronium ion concentration and the hydroxide ion concentration are the same, and we find that both equal
M .
−7
1.0 × 10

8.2.3 [Link]
  Exercise 8.2.1

The ion product of water at 80 °C is 2.4 × 10 −13

. What are the concentrations of hydronium and hydroxide ions in pure water
at 80 °C?

Answer
+ − −7
[H O ] = [ OH ] = 4.9 × 10 M
3

It is important to realize that the autoionization equilibrium for water is established in all aqueous solutions. Adding an acid or base
to water will not change the position of the equilibrium determined by the autoionization reaction but it does shift the relative
concentrations of [OH−] and [H O ]. Example 16.2.2 demonstrates the quantitative aspects of this relation between hydronium
3
+

and hydroxide ion concentrations.

Self-Ionization of Water (Kw)

A Video Describing the Self-Ionization of Water (Kw): Self-Ionization of Water (Kw) [[Link]]

 Example 8.2.2: The Inverse Proportionality of [H 3

O
+
] and [OH −
]

A solution of carbon dioxide in water has a hydronium ion concentration of 2.0 × 10

−6
M . What is the concentration of
hydroxide ion at 25 °C?

Solution
We know the value of the ion-product constant for water at 25 °C:
+ −
2 H O(l) ⇌ H O + OH
2 3 (aq) (aq)

+ − −14
Kw = [ H O ][ OH ] = 1.0 × 10
3

Thus, we can calculate the missing equilibrium concentration.

Rearrangement of the Kw expression yields that [OH −
] is directly proportional to the inverse of [H3O+]:
−14
−
Kw 1.0 × 10 −9
[ OH ] = = = 5.0 × 10
+ −6
[H O ] 2.0 × 10
3

The hydroxide ion concentration in water is reduced to 5.0 × 10 M as the hydrogen ion concentration increases to
−9

M . This is expected from Le Chatelier’s principle; the autoionization reaction shifts to the left to reduce the stress
−6
2.0 × 10

of the increased hydronium ion concentration and the [OH ] is reduced relative to that in pure water.
−

A check of these concentrations confirms that our arithmetic is correct:

+ − −6 −9 −14
Kw = [ H O ][ OH ] = (2.0 × 10 )(5.0 × 10 ) = 1.0 × 10
3

8.2.4 [Link]
  Exercise 8.2.2

What is the hydronium ion concentration in an aqueous solution with a hydroxide ion concentration of 0.001 M at 25 °C?

Answer
+ −11
[H O ] = 1 × 10 M
3

Amphiprotic Species
Like water, many molecules and ions may either gain or lose a proton under the appropriate conditions. Such species are said to be
amphiprotic. Another term used to describe such species is amphoteric, which is a more general term for a species that may act
either as an acid or a base by any definition (not just the Brønsted-Lowry one). Consider for example the bicarbonate ion, which
may either donate or accept a proton as shown here:
− 2 − +
HCO + H O(l) ⇌ CO +H O (8.2.15)
3(aq) 2 3(aq) 3 (aq)

− −
HCO + H O(l) ⇌ H CO3(aq) + OH (8.2.16)
3(aq) 2 2 (aq)

 Example 8.2.3: The Acid-Base Behavior of an Amphoteric Substance

Write separate equations representing the reaction of HSO −

a. as an acid with OH −

b. as a base with HI

Solution
a. H SO
−

3(aq)
+ OH
−

(aq)
⇌ SO
2−

3(aq)
+ H2 O(l)

b. H SO −

3(aq)
+ H I(aq) ⇌ H2 S O3(aq) + I
−

(aq)

 Example 8.2.4

Write separate equations representing the reaction of H 2

PO4
−

a. as a base with HBr

b. as an acid with OH −

Answer
a. H2 P O
−

4(aq)
+ H Br(aq) ⇌ H3 P O4(aq) + Br
−

(aq)

b. H 2P O
−

4(aq)
+ OH
−

(aq)
⇌ HP O
2−

4(aq)
+ H2 O(l)

Summary
A compound that can donate a proton (a hydrogen ion) to another compound is called a Brønsted-Lowry acid. The compound that
accepts the proton is called a Brønsted-Lowry base. The species remaining after a Brønsted-Lowry acid has lost a proton is the
conjugate base of the acid. The species formed when a Brønsted-Lowry base gains a proton is the conjugate acid of the base. Thus,
an acid-base reaction occurs when a proton is transferred from an acid to a base, with formation of the conjugate base of the
reactant acid and formation of the conjugate acid of the reactant base. Amphiprotic species can act as both proton donors and
proton acceptors. Water is the most important amphiprotic species. It can form both the hydronium ion, H3O+, and the hydroxide
ion, OH when it undergoes autoionization:
−

8.2.5 [Link]
 + −
2 H O(l) ⇌ H3 O + OH
2 (aq) (aq)

The ion product of water, Kw is the equilibrium constant for the autoionization reaction:
+ − −14
Kw = [ H2 O ][OH ] = 1.0 × 10 at 25°C

Key Equations
+ − −14
Kw = [ H O ][ OH ] = 1.0 × 10 (at 25 °C)
3

Glossary
acid ionization
reaction involving the transfer of a proton from an acid to water, yielding hydronium ions and the conjugate base of the acid

amphiprotic
species that may either gain or lose a proton in a reaction

amphoteric
species that can act as either an acid or a base

autoionization
reaction between identical species yielding ionic products; for water, this reaction involves transfer of protons to yield
hydronium and hydroxide ions

base ionization
reaction involving the transfer of a proton from water to a base, yielding hydroxide ions and the conjugate acid of the base

Brønsted-Lowry acid
proton donor

Brønsted-Lowry base
proton acceptor

conjugate acid
substance formed when a base gains a proton

conjugate base
substance formed when an acid loses a proton

ion-product constant for water (Kw)

equilibrium constant for the autoionization of water

Contributors and Attributions

Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold (University of Delaware) and Richard Langley
(Stephen F. Austin State University) with contributing authors. Textbook content produced by OpenStax College is licensed
under a Creative Commons Attribution License 4.0 license. Download for free at [Link]
2bd...a7ac8df6@9.110).
Modified by Tom Neils (Grand Rapids Community College)

8.2: Brønsted-Lowry Acids and Bases is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.
16.2: Brønsted–Lowry Acids and Bases is licensed CC BY-NC-SA 3.0.

8.2.6 [Link]
8.3 Lewis Acids and Bases
Skills to Develop
Understand that there is a more comprehensive theory of acid-base chemistry, called the Lewis concept, that describes acid-
base reactions as the sharing of electron pairs.

The Brønsted-Lowry proton donor-acceptor concept has been one of the most successful theories of Chemistry. But as with any
such theory, it is fair to ask if this is not just a special case of a more general theory that could encompass an even broader range of
chemical science. In 1916, G.N. Lewis of the University of California proposed that the electron pair is the dominant actor in acid-
base chemistry. The Lewis theory did not become very well known until about 1923 (the same year that Brønsted and Lowry
published their work), but since then it has been recognized as a very powerful tool for describing chemical reactions of widely
different kinds and is widely used in organic and inorganic chemistry. According to Lewis,
An acid is a substance that accepts a pair of electrons, and in doing so, forms a covalent bond with the entity that supplies the
electrons.
A base is a substance that donates an unshared pair of electrons to a recipient species with which the electrons can be shared.

In modern chemistry, electron donors are often referred to as nucleophiles, while

acceptors are electrophiles.
We will discuss Lewis acids and bases in more detail at the end of the chapter.

Contributors
Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook
Modified by Tom Neils (Grand Rapids Community College)

8.3 Lewis Acids and Bases is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1 [Link]
8.4: Acid Strength and the Acid Dissociation Constant (Ka)
Skills to Develop
To know the relationship between acid or base strength and the magnitude of K , K , pK , and pK . a b a b

To understand the leveling effect.

The magnitude of the equilibrium constant for an ionization reaction can be used to determine the relative strengths of acids and
bases. For example, the general equation for the ionization of a weak acid in water, where HA is the parent acid and A− is its
conjugate base, is as follows:
+ −
H A(aq) + H2 O(l) ⇌ H3 O +A (8.4.1)
(aq) (aq)

The equilibrium constant for this dissociation is as follows:

+ −
[ H3 O ][ A ]
K = (8.4.2)
[ H2 O][H A]

As we noted earlier, the equilibrium constant expression (Law of Mass Action) is really a ratio of activities. The activities of the
solutes can be replaced with their molar concentration without too much error if the solutions are dilute enough. However, the
activity of water is essentially constant for all reactions in dilute aqueous solutions, and is assigned the value of "1" by definition.
Thus, the [H O] in Equation 8.4.2 is actually a misapplication of the approximation carried out for solutes. The proper sequence of
2

approximations and substitutions is

+ − + −
(aH + )(aA− ) [ H3 O ][ A ] [ H3 O ][ A ]
3O

K = Ka = ≈ = (8.4.3)
(aH A )(aH2 O ) [H A][1] [H A]

Again, for simplicity, H O can be written as H in Equation 8.4.3. Keep in mind, though, that free H does not exist in
3
+ + +

aqueous solutions and that a proton is transferred to H O in all acid ionization reactions to form hydronium ions, H O . The
2 3
+

larger the K , the stronger the acid and the higher the H concentration at equilibrium. As with all equilibrium constants, acid–
a
+

base ionization constants are unitless because each of the activities is divided by the standard activity with the same units . The
values of K for a number of common acids are given in Table 8.4.1.
a

Table 8.4.1: Values of K , pK , K , and pK for Selected Acids (H A and Their Conjugate Bases (A )
a a b b
−

Acid HA Ka pKa A
−
Kb pKb

hydroiodic acid HI 2 × 10
9
−9.3 I
−
5.5 × 10
−24
23.26

sulfuric acid (1)* H2 S O4 1 × 10

2
−2.0 HSO
−
4
1 × 10
−16
16.0

nitric acid HN O3 2.3 × 10

1
−1.37 NO
−
3
4.3 × 10
−16
15.37

hydronium ion H3 O
+
1.0 0.00 H2 O 1.0 × 10
−14
14.00

sulfuric acid (2)* HSO

−
4
1.0 × 10
−2
1.99 SO
2−
4
9.8 × 10
−13
12.01

hydrofluoric acid HF 6.3 × 10

−4
3.20 F
−
1.6 × 10
−11
10.80

nitrous acid HN O2 5.6 × 10

−4
3.25 N O2
−
1.8 × 10
−11
10.75

formic acid HC O2 H 1.78 × 10

−4
3.750 HC O2 − 5.6 × 10
−11
10.25

benzoic acid C6 H5 C O2 H 6.3 × 10

−5
4.20 C6 H5 C O
−
2
1.6 × 10
−10
9.80

acetic acid C H3 C O2 H 1.7 × 10

−5
4.76 C H3 C O
−
2
5.8 × 10
−10
9.24

pyridinium ion C5 H5 N H
+
5.9 × 10
−6
5.23 C5 H5 N 1.7 × 10
−9
8.77

hypochlorous acid HOCl 4.0 × 10

−8
7.40 OCl
−
2.5 × 10
−7
6.60

hydrocyanic acid HCN 6.2 × 10

−10
9.21 CN
−
1.6 × 10
−5
4.79

ammonium ion NH
+
4
5.6 × 10
−10
9.25 N H3 1.8 × 10
−5
4.75

water H2 O 1.0 × 10
−14
14.00 OH
−
1.00 0.00

*The number in parentheses indicates the ionization step referred to for a polyprotic acid.

8.4.1 [Link]
 Acid HA Ka pKa A
−
Kb pKb

acetylene C2 H2 1 × 10
−26
26.0 HC
−
2
1 × 10
12
−12.0

ammonia N H3 1 × 10
−35
35.0 NH
−
2
1 × 10
21
−21.0

*The number in parentheses indicates the ionization step referred to for a polyprotic acid.

Weak bases react with water to produce the hydroxide ion, as shown in the following general equation, where B is the parent base
and BH+ is its conjugate acid:
+ −
B(aq) + H2 O(l) ⇌ BH + OH (8.4.4)
(aq) (aq)

The equilibrium constant for this reaction is the base ionization constant (Kb), also called the base dissociation constant:
+ −
[BH ][OH ]
K = Kb = (8.4.5)
[B]

Once again, the activity of water is defined as a value of "1" because it is the solvent. The larger the K , the stronger the base and b

the higher the OH concentration at equilibrium. The values of K for a number of common weak bases are given in Table 8.4.2.
−
b

Table 8.4.2: Values of K , pK , K , and pK for Selected Weak Bases (B) and Their Conjugate Acids (BH+)
b b a a

Base B Kb pKb BH
+
Ka pKa

hydroxide ion OH
−
1.0 0.00* H2 O 1.0 × 10
−14
14.00

phosphate ion PO
3−

4
2.1 × 10
−2
1.68 HP O
2−

4
4.8 × 10
−13
12.32

dimethylamine (C H3 )2 N H 5.4 × 10
−4
3.27 (C H3 )2 N H
+

2
1.9 × 10
−11
10.73

methylamine C H3 N H2 4.6 × 10
−4
3.34 C H3 N H
3
+
2.2 × 10
−11
10.66

trimethylamine (C H3 )3 N 6.3 × 10
−5
4.20 (C H3 )3 N H
+
1.6 × 10
−10
9.80

ammonia N H3 1.8 × 10
−5
4.75 NH
+

4
5.6 × 10
−10
9.25

pyridine C5 H5 N 1.7 × 10
−9
8.77 C5 H5 N H
+
5.9 × 10
−6
5.23

aniline C6 H5 N H2 7.4 × 10
−10
9.13 C6 H5 N H
+

3
1.3 × 10
−5
4.87

water H2 O 1.0 × 10
−14
14.00 H3 O
+
1.0
∗
0.00

*As in Table 8.4.1.

There is a simple relationship between the magnitude of K for an acid and K for its conjugate base. Consider, for example, the
a b

ionization of hydrocyanic acid (H C N ) in water to produce an acidic solution, and the reaction of C N with water to produce a −

basic solution:
+ −
H C N(aq) + H2 O(l) ⇌ H3 O + CN (8.4.6)
(aq) (aq)

− −
CN + H2 O(l) ⇌ OH + H C N(aq) (8.4.7)
(aq) (aq)

The equilibrium constant expression for the ionization of HCN is as follows:

+ −
[ H3 O ][C N ]
Ka = (8.4.8)
[H C N ]

The corresponding expression for the reaction of cyanide with water is as follows:
−
[OH ][H C N ]
Kb = (8.4.9)
−
[C N ]

8.4.2 [Link]
If we add Equations 8.4.6 and 8.4.7, we obtain the following:

Reaction Equilibrium Constants

+ − + −
H2 O + HCN ⇌ H3 O + CN Ka = [H3 O ] [C N ] / [HCN ]
(l) (aq ) (aq ) (aq )

− − − −
CN + H2 O ⇌ OH + HCN Kb = [O H ] [HCN ] / [C N ]
(aq ) (l) (aq ) (aq )

+ − + −
2 H2 O ⇌ H3 O + OH K = Ka × Kb = [H3 O ][O H ]
(l) (aq ) (aq )

In this case, the sum of the reactions described by K and K is the equation for the autoionization of water, and the product of the
a b

two equilibrium constants is K : w

Ka Kb = Kw (8.4.10)

Thus if we know either K for an acid or

a Kb for its conjugate base, we can calculate the other equilibrium constant for any
conjugate acid–base pair.
We can use negative logarithms to avoid exponential notation in writing acid and base ionization constants, by defining pKa as
follows:

pKa = − log10 Ka (8.4.11)

−pKa
Ka = 10 (8.4.12)

and pK as
b

p Kb = − log Kb (8.4.13)
10

−pKb
Kb = 10 (8.4.14)

Similarly, Equation 8.4.10, which expresses the relationship between K and K , can be written in logarithmic form as follows:
a b

p Ka + p Kb = p Kw (8.4.15)

At 25 °C, this becomes

p Ka + p Kb = 14.00 (8.4.16)

The values of pK and pK are given for several common acids and bases in Tables 8.4.1 and 8.4.2, respectively, and a more
a b

extensive set of data is provided in Tables E1 and E2. Because of the use of negative logarithms, smaller values of pK correspond a

to larger acid ionization constants and hence stronger acids. For example, nitrous acid (H N O ), with a pK of 3.25, is about a 2 a

million times stronger acid than hydrocyanic acid (HCN), with a pK of 9.21. Conversely, smaller values of pK correspond to
a b

larger base ionization constants and hence stronger bases.

8.4.3 [Link]
Figure 8.4.1 : The Relative Strengths of Some Common Conjugate Acid–Base Pairs. The strongest acids are at the bottom left, and
the strongest bases are at the top right. The conjugate base of a strong acid is a very weak base, and, conversely, the conjugate acid
of a strong base is a very weak acid.
The relative strengths of some common acids and their conjugate bases are shown graphically in Figure 8.4.1. The conjugate acid–
base pairs are listed in order (from top to bottom) of increasing acid strength, which corresponds to decreasing values of pK . This
a

order corresponds to decreasing strength of the conjugate base or increasing values of pK . At the bottom left of Figure 8.4.2 are
b

the common strong acids; at the top right are the most common strong bases. Notice the inverse relationship between the strength
of the parent acid and the strength of the conjugate base. Thus the conjugate base of a strong acid is a very weak base, and the
conjugate base of a very weak acid is a strong base.

The conjugate base of a strong acid is a weak base and vice versa.
We can use the relative strengths of acids and bases to predict the direction of an acid–base reaction by following a single rule: an
acid–base equilibrium always favors the side with the weaker acid and base, as indicated by these arrows:

stronger acid + stronger base−

↽⇀ weaker acid + weaker base (8.4.17)

In an acid–base reaction, the proton always reacts with the stronger base.
For example, hydrochloric acid is a strong acid that ionizes essentially completely in dilute aqueous solution to produce H O and
3
+

C l ; only negligible amounts of H C l molecules remain undissociated. Hence the ionization equilibrium lies virtually all the way
−

to the right, as represented by a single arrow:

+ −
H C l(aq) + H2 O(l) → H3 O + Cl (8.4.18)
(aq) (aq)

In contrast, acetic acid is a weak acid, and water is a weak base. Consequently, aqueous solutions of acetic acid contain mostly
acetic acid molecules in equilibrium with a small concentration of H O and acetate ions, and the ionization equilibrium lies far to
3
+

the left, as represented by these arrows:

8.4.4 [Link]
 ⇀ + −
CH CO H +H O ↽− H O + CH CO (8.4.19)
3 2 (aq) 2 (l) 3 (aq) 3 2 (aq)

Similarly, in the reaction of ammonia with water, the hydroxide ion is a strong base, and ammonia is a weak base, whereas the
ammonium ion is a stronger acid than water. Hence this equilibrium also lies to the left:
⇀ + −
H2 O(l) + N H3(aq) ↽− NH + OH (8.4.20)
4(aq) (aq)

All acid–base equilibria favor the side with the weaker acid and base. Thus the proton is
bound to the stronger base.
Example 8.4.1 : Butyrate and Dimethylammonium Ions
a. Calculate K and pK of the butyrate ion (C H C H C H C O ). The pK of butyric acid at 25°C is 4.83. Butyric acid is
b b 3 2 2
−

2 a

responsible for the foul smell of rancid butter.

b. Calculate K and pK of the dimethylammonium ion ((C H ) N H ). The base ionization constant K of dimethylamine (
a a 3 2 2
+
b

(C H ) N H) is 5.4 × 10 at 25°C. −4
3 2

Given: pK and K a b

Asked for: corresponding K and pK , K and pK b b a a

Strategy:
The constants K and K are related as shown in Equation 8.4.10. The pK and pK for an acid and its conjugate base are
a b a b

related as shown in Equations 8.4.15 and 8.4.16. Use the relationships pK = −log K and K = 10−pK (Equations 8.4.11 and
8.4.13) to convert between K and pK or K and pK . a a b b

Solution:
We are given the pK for butyric acid and asked to calculate the K and the pK for its conjugate base, the butyrate ion.
a b b

Because the pK value cited is for a temperature of 25°C, we can use Equation 8.4.16: pK + pK = pKw = 14.00. Substituting
a a b

the pK and solving for the pK ,

a b

4.83 + p Kb = 14.00 (8.4.21)

p Kb = 14.00 − 4.83 = 9.17 (8.4.22)

Because pK b = − log Kb , K is 10
b
−9.17
= 6.8 × 10
−10
.
In this case, we are given K for a base (dimethylamine) and asked to calculate K and pK for its conjugate acid, the
b a a

dimethylammonium ion. Because the initial quantity given is K rather than pK , we can use Equation 8.4.10: K K = K . b b a b w

Substituting the values of K and K at 25°C and solving for K ,

b w a

−4 −14
Ka (5.4 × 10 ) = 1.01 × 10 (8.4.23)

−11
Ka = 1.9 × 10 (8.4.24)

Because pK = −log K , we have pK

a a a = − log(1.9 × 10
−11
) = 10.72 . We could also have converted K to pK to obtain the
b b

same answer:
−4
p Kb = − log(5.4 × 10 ) = 3.27 (8.4.25)

pKa + p Kb = 14.00 (8.4.26)

p Ka = 10.73 (8.4.27)

−pKa −10.73 −11

Ka = 10 = 10 = 1.9 × 10 (8.4.28)

If we are given any one of these four quantities for an acid or a base (K , pK , K , or pK ), we can calculate the other three. a a b b

Exercise 8.4.1 : Lactic Acid

Lactic acid (C H C H (OH )C O H) is responsible for the pungent taste and smell of sour milk; it is also thought to produce
3 2

soreness in fatigued muscles. Its pK is 3.86 at 25°C. Calculate K for lactic acid and pK and K for the lactate ion.
a a b b

8.4.5 [Link]
 Answer:
Ka = 1.4 × 10
−4
for lactic acid;
pKb = 10.14 and
Kb = 7.2 × 10
−11
for the lactate ion

Solutions of Strong Acids and Bases: The Leveling Effect

You will notice in Table 8.4.1 that acids like H SO and H N O lie above the hydronium ion, meaning that they have pK values
2 4 3 a

less than zero and are stronger acids than the H O ion. Recall from Chapter 4 that the acidic proton in virtually all oxoacids is
3
+

bonded to one of the oxygen atoms of the oxoanion. Thus nitric acid should properly be written as H ON O . Unfortunately, 2

however, the formulas of oxoacids are almost always written with hydrogen on the left and oxygen on the right, giving H N O 3

instead. In fact, all six of the common strong acids that we first encountered in Chapter 4 have pK values less than zero, which a

means that they have a greater tendency to lose a proton than does the H O ion. Conversely, the conjugate bases of these strong
3
+

acids are weaker bases than water. Consequently, the proton-transfer equilibria for these strong acids lie far to the right, and adding
any of the common strong acids to water results in an essentially stoichiometric reaction of the acid with water to form a solution of
the H O ion and the conjugate base of the acid.
3
+

Although K for H I is about 108 greater than K for H N O , the reaction of either H I or H N O with water gives an essentially
a a 3 3

stoichiometric solution of H O and I− or N O . In fact, a 0.1 M aqueous solution of any strong acid actually contains 0.1 M
3
+ −
3

H O , regardless of the identity of the strong acid. This phenomenon is called the leveling effect: any species that is a stronger
+
3

acid than the conjugate acid of water (H O ) is leveled to the strength of H O in aqueous solution because H O is the
3
+
3
+
3
+

strongest acid that can exist in equilibrium with water. Consequently, it is impossible to distinguish between the strengths of acids
such as HI and HNO3 in aqueous solution, and an alternative approach must be used to determine their relative acid strengths.
One method is to use a solvent such as anhydrous acetic acid. Because acetic acid is a stronger acid than water, it must also be a
weaker base, with a lesser tendency to accept a proton than H O. Measurements of the conductivity of 0.1 M solutions of both HI
2

and H N O in acetic acid show that HI is completely dissociated, but H N O is only partially dissociated and behaves like a weak
3 3

acid in this solvent. This result clearly tells us that HI is a stronger acid than H N O . The relative order of acid strengths and 3

approximate K and pK values for the strong acids at the top of Table 8.4.1 were determined using measurements like this and
a a

different nonaqueous solvents.

In aqueous solutions, H O is the strongest acid and OH

3
+ −
is the strongest base that can
exist in equilibrium with H O. 2

The leveling effect applies to solutions of strong bases as well: In aqueous solution, any base stronger than OH− is leveled to the
strength of OH− because OH− is the strongest base that can exist in equilibrium with water. Salts such as K O, N aOC H 2 3

(sodium methoxide), and N aN H (sodamide, or sodium amide), whose anions are the conjugate bases of species that would lie
2

below water in Table 8.4.2, are all strong bases that react essentially completely (and often violently) with water, accepting a
proton to give a solution of OH and the corresponding cation:
−

− +
K2 O(s) + H2 O(l) → 2OH + 2K (8.4.29)
(aq) (aq)

− +
N aOC H3(s) + H2 O(l) → OH +Na + C H3 OH(aq) (8.4.30)
(aq) (aq)

− +
N aN H2(s) + H2 O(l) → OH +Na + N H3(aq) (8.4.31)
(aq) (aq)

Other examples that you may encounter are potassium hydride (KH ) and organometallic compounds such as methyl lithium (
C H Li).
3

Polyprotic Acids and Bases

As you learned, polyprotic acids such as H SO , H P O , and H C O contain more than one ionizable proton, and the protons
2 4 3 4 2 3

are lost in a stepwise manner. The fully protonated species is always the strongest acid because it is easier to remove a proton from
a neutral molecule than from a negatively charged ion. Thus acid strength decreases with the loss of subsequent protons, and,
correspondingly, the pK increases. Consider H SO , for example:
a 2 4

− −⇀ 2− +
H SO ↽ SO +H p Ka = −2 (8.4.32)
4(aq) 4(aq) (aq)

8.4.6 [Link]
The equilibrium in the first reaction lies far to the right, consistent with H SO being a strong acid. In contrast, in the second 2 4

reaction, appreciable quantities of both H SO and SO are present at equilibrium.

−

4
2−

For a polyprotic acid, acid strength decreases and the pK increases with the sequential a

loss of each proton.

The hydrogen sulfate ion (H SO ) is both the conjugate base of H SO and the conjugate acid of SO . Just like water, HSO4−
−
4 2 4
2−
4

can therefore act as either an acid or a base, depending on whether the other reactant is a stronger acid or a stronger base.
Conversely, the sulfate ion (SO ) is a polyprotic base that is capable of accepting two protons in a stepwise manner:
2−

2− − −
SO + H2 O(aq) −⇀
↽ H SO + OH (8.4.33)
4(aq) 4(aq) (aq)

− −
H SO + H2 O(aq) −⇀
↽ H2 S O4(aq) + OH (8.4.34)
4(aq) (aq)

Like any other conjugate acid–base pair, the strengths of the conjugate acids and bases are related by pK + pK = pKw. Consider, a b

for example, the H SO /SO conjugate acid–base pair. From Table 8.4.1, we see that the pK of H SO is 1.99. Hence the pK
−

4
2−

4 a
−

4 b

of SO is 14.00 − 1.99 = 12.01. Thus sulfate is a rather weak base, whereas OH is a strong base, so the equilibrium shown in
2−
4
−

Equation 8.4.34 lies to the left. The H SO ion is also a very weak base (pK of H SO = 2.0, pK of
−
4 a 2 4 b

= 14 − (−2.0) = 16 ), which is consistent with what we expect for the conjugate base of a strong acid.
−
H SO
4

Example 8.4.2
Predict whether the equilibrium for each reaction lies to the left or the right as written.
+ 3− 2−
NH +PO ⇌ N H3(aq) + H P O
4(aq) 4(aq) 4(aq)

− −
C H3 C H2 C O2 H(aq) + C N ⇌ C H3 C H2 C O + H C N(aq)
(aq) 2(aq)

Given: balanced chemical equation

Asked for: equilibrium position
Strategy:
Identify the conjugate acid–base pairs in each reaction. Then refer to Tables 8.4.1and8.4.2 and Figure 8.4.2 to determine which
is the stronger acid and base. Equilibrium always favors the formation of the weaker acid–base pair.
Solution:
The conjugate acid–base pairs are N H /N H and H P O /P O . According to Tables 8.4.1 and 8.4.2, N H
4
+
3
2−
4
3−
4
+
4
is a stronger
acid (pK = 9.25) than H P O (pKa = 12.32), and P O is a stronger base (pK = 1.68) than N H (pK
a
2−

4
3−

4
b 3 b = 4.75 ). The
equilibrium will therefore lie to the right, favoring the formation of the weaker acid–base pair:
+ 3− −⇀ NH 2−
NH + PO ↽ 3(aq) + H P O (8.4.35)
4(aq) 4(aq) 4(aq)
weaker base
stronger acid stronger base weaker acid

The conjugate acid–base pairs are C H C H C O H /C H C H C O and H C N /C N . According to Table 8.4.1, HCN is a
3 2 2 3 2
−
2
−

weak acid (pKa = 9.21) and C N is a moderately weak base (pKb = 4.79). Propionic acid (C H C H C O H) is not listed in
−
3 2 2

Table 8.4.1, however. In a situation like this, the best approach is to look for a similar compound whose acid–base properties are
listed. For example, propionic acid and acetic acid are identical except for the groups attached to the carbon atom of the
carboxylic acid (−CH CH versus −CH ), so we might expect the two compounds to have similar acid–base properties. In
2 3 3

particular, we would expect the pK of propionic acid to be similar in magnitude to the pK of acetic acid. (In fact, the pK of
a a a

propionic acid is 4.87, compared to 4.76 for acetic acid, which makes propionic acid a slightly weaker acid than acetic acid.)
Thus propionic acid should be a significantly stronger acid than H C N . Because the stronger acid forms the weaker conjugate
base, we predict that cyanide will be a stronger base than propionate. The equilibrium will therefore lie to the right, favoring the
formation of the weaker acid–base pair:
− −
C H3 C H2 C O2 H(aq) + CN −⇀
↽ C H3 C H2 C O + H C N(aq) (8.4.36)
(aq) 2(aq)
stronger acid weaker acid
stronger base weaker base

Exercise 8.4.1

8.4.7 [Link]
 Predict whether the equilibrium for each reaction lies to the left or the right as written.
a. H2 O(l) + H S
−

(aq)
⇌ OH
−

(aq)
+ H2 S(aq)

b. H C O −

2(aq)
+ H SO
−

4(aq)
⇌ H C O2 H(aq) + S O
2−

4(aq)

Answer a
left
Answer b
left

Summary
Acid–base reactions always contain two conjugate acid–base pairs. Each acid and each base has an associated ionization constant
that corresponds to its acid or base strength. Two species that differ by only a proton constitute a conjugate acid–base pair. The
magnitude of the equilibrium constant for an ionization reaction can be used to determine the relative strengths of acids and bases.
For an aqueous solution of a weak acid, the dissociation constant is called the acid ionization constant (K ). Similarly, the a

equilibrium constant for the reaction of a weak base with water is the base ionization constant (K ). For any conjugate acid–base
b

pair, K K = K . Smaller values of pK correspond to larger acid ionization constants and hence stronger acids. Conversely,
a b w a

smaller values of pK correspond to larger base ionization constants and hence stronger bases. At 25°C, pK + pK = 14.00 .
b a b

Acid–base reactions always proceed in the direction that produces the weaker acid–base pair. No acid stronger than H O and no 3
+

base stronger than OH can exist in aqueous solution, leading to the phenomenon known as the leveling effect. Polyprotic acids
−

(and bases) lose (and gain) protons in a stepwise manner, with the fully protonated species being the strongest acid and the fully
deprotonated species the strongest base.

Key Equations
Acid ionization constant:
+ −
[ H3 O ][ A ]
Ka = (8.4.37)
[H A]

Base ionization constant:

+ −
[BH ][OH ]
Kb = (8.4.38)
[B]

Relationship between K and K of a conjugate acid–base pair:

a b

Ka Kb = Kw (8.4.39)

Definition of pK : a

pKa = − log10 Ka (8.4.40)

−pKa
Ka = 10 (8.4.41)

Definition of pK : b

p Kb = − log10 Kb (8.4.42)

−pKb
Kb = 10 (8.4.43)

Relationship between pK and pK of a conjugate acid–base pair:

a b

p Ka + p Kb = p Kw (8.4.44)

p Ka + p Kb = 14.00 at 25°C (8.4.45)

8.4.8 [Link]
Contributors
Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook
Modified by Tom Neils (Grand Rapids Community College)

8.4: Acid Strength and the Acid Dissociation Constant (Ka) is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or
curated by LibreTexts.

8.4.9 [Link]
8.5: Autoionization of Water and pH
Skills to Develop
To understand the autoionization reaction of liquid water.
To know the relationship among pH, pOH, and pK . w

As you learned previously acids and bases can be defined in several different ways (Table 8.5.1). Recall that the Arrhenius
definition of an acid is a substance that dissociates in water to produce H ions (protons), and an Arrhenius base is a substance
+

that dissociates in water to produce OH (hydroxide) ions. According to this view, an acid–base reaction involves the reaction of a
−

proton with a hydroxide ion to form water. Although Brønsted and Lowry defined an acid similarly to Arrhenius by describing an
acid as any substance that can donate a proton, the Brønsted–Lowry definition of a base is much more general than the Arrhenius
definition. In Brønsted–Lowry terms, a base is any substance that can accept a proton, so a base is not limited to just a hydroxide
ion. This means that for every Brønsted–Lowry acid, there exists a corresponding conjugate base with one fewer proton.
Consequently, all Brønsted–Lowry acid–base reactions actually involve two conjugate acid–base pairs and the transfer of a proton
from one substance (the acid) to another (the base). In contrast, the Lewis definition of acids and bases, focuses on accepting or
donating pairs of electrons rather than protons. A Lewis base is an electron-pair donor, and a Lewis acid is an electron-pair
acceptor.
Table 8.5.1: Definitions of Acids and Bases
Definition Acids Bases

Arrhenius H
+
donor OH
−
donor

Brønsted–Lowry H
+
donor H
+
acceptor

Lewis electron-pair acceptor electron-pair donor

Because this chapter deals with acid–base equilibria in aqueous solution, our discussion will use primarily the Brønsted–Lowry
definitions and nomenclature. Remember, however, that all three definitions are just different ways of looking at the same kind of
reaction: a proton is an acid, and the hydroxide ion is a base—no matter which definition you use. In practice, chemists tend to use
whichever definition is most helpful to make a particular point or understand a given system. If, for example, we refer to a base as
having one or more lone pairs of electrons that can accept a proton, we are simply combining the Lewis and Brønsted–Lowry
definitions to emphasize the characteristic properties of a base.

Acid–Base Properties of Water

Recall that because of its highly polar structure, liquid water can act as either an acid (by donating a proton to a base) or a base (by
using a lone pair of electrons to accept a proton). For example, when a strong acid such as HCl dissolves in water, it dissociates into
chloride ions (C l ) and protons (H ). The proton, in turn, reacts with a water molecule to form the hydronium ion (H O ):
− +
3
+

+ −
H C l(aq) + H2 O(l) → H3 O + Cl (8.5.1)
(aq) (aq)
acid base acid base

In this reaction, H C l is the acid, and water acts as a base by accepting an H +

ion. The reaction in Equation 8.5.1 is often written
in a simpler form by removing H O from each side:
2

+ −
H C l(aq) → H + Cl (8.5.2)
(aq) (aq)

In Equation 8.5.2, the hydronium ion is represented by H

+
, although free H
+
ions do not exist in liquid water as this reaction
demonstrates:
+ +
H + H2 O(l) → H3 O (8.5.3)
(aq) (aq)

Water can also act as an acid, as shown in Equation 8.5.4. In this equilibrium reaction, H 2O donates a proton to N H , which acts
3

as a base:

8.5.1 [Link]
 + −
H2 O(aq) + N H3(aq) ⇌ N H + OH (8.5.4)
4(aq) (aq)
acid base
acid base

Water is thus termed amphiprotic, meaning that it can behave as either an acid or a base, depending on the nature of the other
reactant. Notice that Equation 8.5.4 is an equilibrium reaction as indicated by the double arrow and hence has an equilibrium
constant associated with it.

The Relationship among pH, pOH, and pK w

As mentioned on a previous page, water can undergo the self-ionization reaction called autoprotolysis:
+ −
H2 O(l) + H2 O(l) ⇌ H3 O + OH
(aq) (aq)

The equilibrium constant for this reaction is

+ − −14 o
Kw = [ H3 O ][OH ] = 1.0x 10 at 25 C (8.5.5)

Thus, at 25 oC, for pure water, the [H3O+] = [OH-] = 1.0 x 10-7M. If a substance is added to water so that the [H3O+] > [OH-], the
solution is considered acidic. If a substance is added to water so that the [H3O+] < [OH-], the solution is considered basic. This is a
perfectly reasonable set of relationships to use to decide if a solution is acidic or basic. However, scientists in the early 1900's
decided to add a second set of relationships to describe the acidity of a solution, using logarithms to convert the small [H3O+] and
[OH-] concentrations to a more 'manageable' number. This second set of relationships involves the calculation of pH and pOH
values, where pH and the H (H O ) concentration are related as follows:
+
3
+

+
pH = − log10 [ H ] (8.5.6)

+ −pH
[H ] = 10 (8.5.7)

Because the scale is logarithmic, a pH difference of 1 between two solutions corresponds to a difference of a factor of 10 in their
hydronium ion concentrations. Using the pH scale, the pH of a neutral solution is 7.00 ([H O ] = 1.0 × 10 M ), whereas acidic 3
+ −7

solutions have pH < 7.00 (corresponding to [H O ] > 1.0 × 10 ) and basic solutions have pH > 7.00 (corresponding to
3
+ −7

+
[ H O ] < 1.0 × 10
3
−7
).
Similar notation systems are used to describe many other chemical quantities that contain a large negative exponent. For example,
chemists use an analogous pOH scale to describe the hydroxide ion concentration of a solution. The pOH and [OH ] are related as −

follows:
−
pOH = − log [OH ] (8.5.8)
10

− −pOH
[OH ] = 10 (8.5.9)

The constant K can also be expressed using this notation, where pK

w w = − log Kw .
Because a neutral solution has [OH ] = 1.0 × 10 , the pOH of a neutral solution is 7.00. Consequently, the sum of the pH and
− −7

the pOH for a neutral solution at 25 °C is 7.00 + 7.00 = 14.00. We can show that the sum of pH and pOH is equal to 14.00 for any
aqueous solution at 25 °C by taking the negative logarithm of both sides of Equation 8.5.5:

− log10 Kw = pKw (8.5.10)

+ −
= − log([ H3 O ][OH ]) (8.5.11)

+ −
= (− log[ H3 O ]) + (− log[OH ]) (8.5.12)

= pH + pOH (8.5.13)

Thus at any temperature, pH + pOH = pK , so at 25 °C, where K = 1.0 × 10

w , pH + pOH = 14.00. More generally, the pH
w
−14

of any neutral solution is half of the pK at that temperature. The relationship among pH, pOH, and the acidity or basicity of a
w

solution is summarized graphically in Figure 8.5.1 over the common pH range of 0 to 14. Notice the inverse relationship between
the pH and pOH scales.

8.5.2 [Link]
 Figure 8.5.1 : The Inverse Relationship between the pH and pOH Scales. As pH decreases, [H ] and the acidity increase. As +

pOH increases, [OH ] and the basicity decrease. Common substances have pH values that range from extremely acidic to
−

extremely basic.

For any neutral solution, pH + pOH = 14.00 (at 25 °C) with pH=pOH=7.
Example 8.5.1
The Kw for water at 100 °C is 4.99 × 10 . Calculate pK for water at this temperature and the pH and the pOH for a neutral
−13
w

aqueous solution at 100 °C. Report pH and pOH values to two decimal places.
Given: K w

Asked for: pK , pH, and pOH

w

Strategy:
A. Calculate pK by taking the negative logarithm of K .
w w

B. For a neutral aqueous solution, [H O ] = [OH ] . Use this relationship and Equation 8.5.5 to calculate [H
3
+ −
3O
+
] and
[OH ]. Then determine the pH and the pOH for the solution.
−

Solution:
A
Because pK is the negative logarithm of Kw, we can write
w

−13
p Kw = − log Kw = − log(4.99 × 10 ) = 12.302 (8.5.14)

The answer is reasonable: K is between 10

w
−13
and 10 −12
, so pK must be between 12 and 13.
w

B
Equation 8.5.5 shows that Kw = [ H3 O
+
][OH
−
] . Because [ H3 O
+
] = [OH
−
] in a neutral solution, we can let
] = [OH ] :
+ −
x = [ H3 O

8.5.3 [Link]
 + −
Kw = [ H3 O ][OH ]

2
= (x)(x) = x

−−
−
x = √Kw

− −−−−−−−− −
−13
= √ 4.99 × 10

−7
= 7.06 × 10 M

Because x is equal to both [H3O

+
] and [OH −
,
]

−7
pH = pOH = − log(7.06 × 10 )

= 6.15 (to two decimal places)

We could obtain the same answer more easily (without using logarithms) by using the pK . In this case, we know that w

pK w= 12.302, and from Equation 8.5.13, we know that p K = pH + pOH . Because pH = pOH in a neutral solution, we
w

can set pH = pOH = y . Solving to two decimal places we obtain the following:

pKw = pH + pOH

= y +y

= 2y

pKw
y =
2

12.302
=
2

= 6.15 = pH = pOH

Exercise 8.5.1
Humans maintain an internal temperature of about 37 °C. At this temperature, K = 3.55 × 10 w
−14
. Calculate pK and the pH
w

and the pOH of a neutral solution at 37 °C. Report pH and pOH values to two decimal places.

Answer
p Kw = 13.45

pH = pOH = 6.73

Summary
Water is amphiprotic: it can act as an acid by donating a proton to a base to form the hydroxide ion, or as a base by accepting a
proton from an acid to form the hydronium ion (H O ). The autoionization of liquid water produces OH and H O ions. The
3
+ −
3
+

equilibrium constant for this reaction is called the ion-product constant of liquid water (Kw) and is defined as
= [ H O ][OH ] . At 25 °C, K is 1.0 × 10 ; hence pH + pOH = pK = 14.00 .
+ − −14
K w 3 w w

For any neutral solution, pH + pOH = 14.00 (at 25 °C) and pH = 1/2pK . w

Ion-product constant of liquid water:

+ −
Kw = [ H3 O ][OH ]

Definition of pH:
+
pH = − log 10[ H ]

or
+ −pH
[H ] = 10

Definition of pOH :

8.5.4 [Link]
 −
pOH = − log10 [OH ]

or
− −pOH
[OH ] = 10

Relationship among pH, pOH , and pK : w

p Kw = pH + pOH

Contributors
Modified by Tom Neils (Grand Rapids Community College)

8.5: Autoionization of Water and pH is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

8.5.5 [Link]
8.6 - Finding the Hydronium Ion Concentration and pH of Strong and Weak Acid
Solutions
If we wish to find the hydronium ion concentration ([H3O+]) and the pH of a solution, we need to know both the strength of the
acid (or base) and the concentration of the acid (or base). We will find that we need to treat strong acids (and bases) differently than
weak acids (and bases) based on the extent to which they react with water.

Strong Acids
By definition, strong acids are those acids with a K ≥ 1 . using this definition, we assume that strong acids will react completely
a

with water, so that every molecule of acid reacts with a molecule of water to produce a hydronium ion and the conjugate base.
(This assumption is, of course, not possible because there must always be at least a few particles of each reactant and each product
at equilibrium, but our assumption is a valid one when K gets to be quite a bit larger than 1.):
a

+ −
H A(aq) + H2 O(l) → H3 O + A (1)
(aq) (aq)

Based on our assumption, [H 3O

+
]eq = [H A]initial , so we can carry out the following calculation:
+
pH = −log([ H3 O ]eq ) = −log([H A]initial ) (2)

Example 1
What is the pH of a 0.175 M aqueous solution of HBr?
Solution
HBr is a strong acid (K a >1 ), so [H 3O
+
]eq = [H Br]initial . Thus, pH = -log (0.175) = 0.757

Exercise 1
What is the pH of a 0.0043 M aqueous solution of HNO3?

Answer
HNO3 is a strong acid (K a >1 ), so [H 3O
+
]eq = [H N O3 ]initial . Thus, pH = -log (0.0043) = 2.37

Strong Bases
By definition, strong bases are those bases with a K ≥ 1 . using this definition, we assume that strong bases will react completely
b

with water, so that every molecule of base reacts with a molecule of water to produce a hydroxide ion and the conjugate acid. (This
assumption is, of course, not possible because there must always be at least a few particles of each reactant and each product at
equilibrium, but our assumption is a valid one when K gets to be quite a bit larger than 1.):
b

− +
B(aq) + H2 O(l) → OH + HB (3)
(aq) (aq)

Based on our assumption, [OH −

]eq = [B]initial , so we can carry out the following calculation:
−
pOH = −log([OH ]eq ) = −log([B]initial ) (4)

To find the pH, we then subtract the pOH from 14.

Example 2
What is the pH of a 0.175 M aqueous solution of NaNH2 ?
Solution
NH2- is a strong base (K b >1 ), so [OH −
]eq = [N H
−
2
]initial . Thus, pOH = -log (0.175) = 0.757, and pH = 14.000 - 0.757 =
13.243

Exercise 2
What is the pH of a 0.0043 M aqueous solution of KOH?

1 [Link]
 Answer
KOH is a strong base (K b =1 ), so [OH −
]eq = [OH
−
]initial . Thus, pOH = -log (0.0043) = 2.37, and pH = 14.00 - 2.37 =
11.63

Weak Acids
If the acid you are working with is weak (K < 1 ), you must use a logic chart (ICE diagram) to determine the
a [ H3 O
+
] because
you cannot tell how much H O will form in solution simply by looking at the intial [H A].
3
+

Example 3
What is the pH of a 0.025 M aqueous solution of HClO?
Solution
C lO
−
is a weak base with Kb = 3.5 x 10
−8
. The law of mass action for the reaction of H C lO with water is
− +
[C lO ][ H3 O ]
−8
3.5 x 10 =
[H C lO]

The ICE diagram will look like this:

HClO H2O ⇌ ClO- H3O+

0.025 - 0 0

-n - +n +n

0.025-n - n n

Thus,
[n][n]
−8
3.5 x 10 = (5)
[0.025 − n]

which rearranges to
2 −8 −10
0 =n + 3.5 x 10 n − 8.75 x 10 (6)

using the quadratic formula, the answer can be found to be 2.96 x 10-5 M H3O+. Thus the pH is -log(2.96 x 10-5) = 4.53

Exercise 3
What is the pH of a 0.111 M aqueous solution of acetic acid? K a = 1.8 × 10
−5

Answer
pH = 2.85

Weak Bases
If the base you are working with is weak (K < 1 ), you must use a logic chart (ICE diagram) to determine the [OH
b
−
] because you
cannot tell how much OH will form in solution simply by looking at the intial [B].
−

Example 4
What is the pH of a 0.025 M aqueous solution of NaClO?
Solution
C lO
−
is a weak base with Kb = 2.9 x 10
−7
. The law of mass action for the reaction of C lO
−
with water is
−
[H C lO][OH ]
−7
2.9 x 10 =
−
[C lO ]

The ICE diagram will look like this:

2 [Link]
 ClO- H2O ⇌ HClO OH-

0.025 - 0 0

-n - +n +n

0.025-n - n n

Thus,
[n][n]
−7
2.9 x 10 = (7)
[0.025 − n]

which rearranges to
2 −7 −9
0 =n + 2.9 x 10 n − 7.25 x 10 (8)

using the quadratic formula, the answer can be found to be 2.68 x 10-5 M OH-. Thus the pOH is -log(2.68 x 10-5) = 4.57, and the
pH is 14.00 -4.57 = 9.43.

Exercise 4
What is the pH of a 0.045 M aqueous solution of sodium phosphate. K b = 2.8 × 10
−2

Answer
12.38

Contributor
Tom Neils (Grand Rapids Community College)

8.6 - Finding the Hydronium Ion Concentration and pH of Strong and Weak Acid Solutions is shared under a CC BY-NC-SA 4.0 license and was
authored, remixed, and/or curated by LibreTexts.

3 [Link]
8.7: The Acid-Base Properties of Ions and Salts
Skills to Develop
To understand hydrolysis
To predict the effect a given ion will have on the pH of a solution

Depending on the acid–base properties of its component ions, a salt can dissolve in water to produce a neutral solution, a basic
solution, or an acidic solution.
When a salt such as N aC l dissolves in water, it produces Na
+

(aq)
and C l −

(aq)
ions. Using a Lewis approach, the Na
+
ion can be
viewed as an acid because it is an electron pair acceptor, although its low charge and relatively large radius make it a very weak
acid (Ka < 1 x 10-14) . The C l ion is the conjugate base of the strong acid H C l, so it has essentially no basic character (Kb < 1 x
−

10-14). Consequently, dissolving N aC l in water has no effect on the pH of a solution, and the solution remains neutral.
Now let's compare this behavior to the behavior of aqueous solutions of potassium cyanide and sodium acetate. Again, the cations (
K
+
and N a ) have essentially no acidic character, but the anions (C N and C H C O ) are weak bases that can react with water
+ −
3
−
2

because they are the conjugate bases of the weak acids H C N and acetic acid, respectively and they have Ka > 1 x 10-14.
− ⇀ −
CN + H2 O(l) ↽− H C N(aq) + OH (8.7.1)
(aq) (aq)

2 ⇀ −
C H3 C O + H2 O(l) ↽− C H3 C O2 H(aq) + OH (8.7.2)
2(aq) (aq)

Neither reaction proceeds very far to the right as written because the formation of the weaker acid–base pair is favored. Both
H C N and acetic acid are stronger acids than water, and hydroxide is a stronger base than either acetate or cyanide, so in both

cases, the equilibrium lies to the left. Nonetheless, each of these reactions generates enough hydroxide ions to produce a basic
solution. For example, the pH of a 0.1 M solution of sodium acetate or potassium cyanide at 25°C is 8.8 or 11.1, respectively.
From Table 8.7.1 and Figure 8.7.1, we can see that C N is a stronger base (pK = 4.79) than acetate (pK = 9.24), which is
−
b b

consistent with KC N producing a more basic solution than sodium acetate at the same concentration.
In contrast, the conjugate acid of a weak base should be a weak acid (Equation 8.7.3). For example, ammonium chloride and
pyridinium chloride are salts produced by reacting ammonia and pyridine, respectively, with H C l. As you already know, the
chloride ion is such a weak base that it does not react with water. In contrast, the cations of the two salts are weak acids that react
with water because they have a Kb > 1 x 10-14. The reactions are as follows:
+ ⇀ +
NH + H2 O(l) ↽− H H3(aq) + H3 O (8.7.3)
4(aq) (aq)

+ ⇀ +
C5 H5 N H + H2 O(l) ↽− C5 H5 N H(aq) + H3 O (8.7.4)
(aq) (aq)

Equation 8.7.3 indicates that H O is a stronger acid than either N H or C H N H , and conversely, ammonia and pyridine are
3
+ +
4 5 5
+

both stronger bases than water. The equilibrium will therefore lie far to the left in both cases, favoring the weaker acid–base pair.
The H O concentration produced by the reactions is great enough, however, to decrease the pH of the solution significantly: the
3
+

pH of a 0.10 M solution of ammonium chloride or pyridinium chloride at 25°C is 5.13 or 3.12, respectively. This is consistent with

the information shown in Figure 16.2, indicating that the pyridinium ion is more acidic than the ammonium ion.
What happens with aqueous solutions of a salt such as ammonium acetate, where both the cation and the anion can react separately
with water to produce an acid and a base, respectively? According to Figure 16.10, the ammonium ion will lower the pH, while
according to Equation 8.7.4, the acetate ion will raise the pH. This particular case is unusual, in that the cation is as strong an acid
as the anion is a base (Ka ≈ Kb). Consequently, the two effects cancel, and the solution remains neutral. With salts in which the
cation is a stronger acid than the anion is a base, the final solution has a pH < 7.00. Conversely, if the cation is a weaker acid than
the anion is a base, the final solution has a pH > 7.00.
Solutions of simple salts of metal ions can also be acidic, even though a metal ion cannot donate a proton directly to water to
produce H O . Instead, a metal ion can act as a Lewis acid and interact with water, a Lewis base, by coordinating to a lone pair of
3
+

electrons on the oxygen atom to form a hydrated metal ion (part (a) in Figure 8.7.1). A water molecule coordinated to a metal ion is
more acidic than a free water molecule for two reasons. First, repulsive electrostatic interactions between the positively charged
metal ion and the partially positively charged hydrogen atoms of the coordinated water molecule make it easier for the coordinated
water to lose a proton.

8.7.1 [Link]
Second, the positive charge on the Al ion attracts electron density from the oxygen atoms of the water molecules, which
3+

decreases the electron density in the O– H bonds, as shown in part (b) in Figure 8.7.1. With less electron density between the O
atoms and the H atoms, the O– H bonds are weaker than in a free H O molecule, making it easier to lose a H ion.
2
+

Figure 8.7.1 : Effect of a Metal Ion on the Acidity of Water (a) Reaction of the metal ion Al with water to form the hydrated
3+

metal ion is an example of a Lewis acid–base reaction. (b) The positive charge on the aluminum ion attracts electron density from
the oxygen atoms, which shifts electron density away from the O–H bonds. The decrease in electron density weakens the O–H
bonds in the water molecules and makes it easier for them to lose a proton.
The magnitude of this effect depends on the following two factors (Figure 8.7.2):
1. The charge on the metal ion. A divalent ion (M ) has approximately twice as strong an effect on the electron density in a
2+

coordinated water molecule as a monovalent ion (M ) of the same radius.

+

2. The radius of the metal ion. For metal ions with the same charge, the smaller the ion, the shorter the internuclear distance to the
oxygen atom of the water molecule and the greater the effect of the metal on the electron density distribution in the water
molecule.

Figure 8.7.2 : The Effect of the Charge and Radius of a Metal Ion on the Acidity of a Coordinated Water Molecule. The contours
show the electron density on the O atoms and the H atoms in both a free water molecule (left) and water molecules coordinated to
Na , Mg , and Al ions. These contour maps demonstrate that the smallest, most highly charged metal ion (Al ) causes the
+ 2+ 3+ 3+

greatest decrease in electron density of the O–H bonds of the water molecule. Due to this effect, the acidity of hydrated metal ions
increases as the charge on the metal ion increases and its radius decreases.
Thus aqueous solutions of small, highly charged metal ions, such as Al 3+
and F e , are acidic:
3+

3+ 2+ +
[Al(H2 O)6 ] ⇌ [Al(H2 O)5 (OH )] +H (8.7.5)
(aq) (aq) (aq)

8.7.2 [Link]
The [Al(H O) ] ion has a pK of 5.0, making it almost as strong an acid as acetic acid. Because of the two factors described
2 6
3+
a

previously, the most important parameter for predicting the effect of a metal ion on the acidity of coordinated water molecules is
the charge-to-radius ratio of the metal ion.

Solutions of small, highly charged metal ions in water are acidic.

Reactions such as those discussed in this section, in which a salt reacts with water to give an acidic or basic solution, are often
called hydrolysis reactions. Using a separate name for this type of reaction is unfortunate because it suggests that they are somehow
different. In fact, hydrolysis reactions are just acid–base reactions in which the acid is a cation or the base is an anion; they obey the
same principles and rules as all other acid–base reactions.

A hydrolysis reaction is an acid–base reaction.

Example 8.7.1
Predict whether aqueous solutions of these compounds are acidic, basic, or neutral.
a. KNO 3

b. CrBr 3

c. Na SO
2 4

Given: compound
Asked for: acidity or basicity of aqueous solution
Strategy:
A. Assess the acid–base properties of the cation and the anion. If the cation is a weak Lewis acid, it will not affect the pH of the
solution. If the cation is the conjugate acid of a weak base or a relatively highly charged metal cation, however, it will react
with water to produce an acidic solution.
B. f the anion is the conjugate base of a strong acid, it will not affect the pH of the solution. If, however, the anion is the
conjugate base of a weak acid, the solution will be basic.
Solution:
a
A. The K cation has a small positive charge (+1) and a relatively large radius (because it is in the fourth row of the periodic
+

table), so its Ka < 1 x 10-14. It will not hydrolyze water or affect the pH.
B. The N O − anion is the conjugate base of a strong acid, so it has essentially no basic character (Kb < 1 x 10-14).
3

C. Hence neither the cation nor the anion will react with water to produce H or OH , and the solution will be neutral.
+ −

b.
A. The C r ion is a relatively highly charged metal cation that should behave similarly to the Al
3+ 3+
ion and form the
[C r(H 2O) ] complex, which will behave as a weak acid:
6
3+

3+
C r(H2 O)6 ] −
↽⇀ C r(H O) (OH )]2+ +H
+
2 5
(aq) (aq) (aq)

(Ka > 1 x 10-14)

B. The Br anion is a very weak base (it is the conjugate base of the strong acid H Br), so it does not affect the pH of the
−

solution (Kb < 1 x 10-14).

C. Hence the solution will be acidic.
c.
A. The N a ion, like the K , is a very weak acid (Ka < 1 x 10-14), so it should not affect the acidity of the solution.
+ +

B. In contrast, SO is the conjugate base of H SO , which is a weak acid. Hence the SO ion, with a Kb > 1 x 10-14, will
2−

4
−

4
2−

react with water as shown in Figure 16.6.

C. The solution will be slightly basic.

Exercise 8.7.1

8.7.3 [Link]
 Predict whether aqueous solutions of the following are acidic, basic, or neutral.
a. KI
b. F e(C lO 4 )2

c. N aH S

Answer a
neutral
Answer b
acidic
Answer c
basic (due to the reaction of HS with water to form H
−
2
S and OH )−

Summary
A salt can dissolve in water to produce a neutral, a basic, or an acidic solution, depending on whether it contains the conjugate base
of a weak acid as the anion (A ), the conjugate acid of a weak base as the cation (BH ), or both. Salts that contain small, highly
− +

charged metal ions produce acidic solutions in water. The reaction of a salt with water to produce an acidic or a basic solution is
called a hydrolysis reaction.

Key Takeaways
Acid–base reactions always contain two conjugate acid–base pairs.
Each acid and each base has an associated ionization constant that corresponds to its acid or base strength.

Contributors
Modified by Tom Neils (Grand Rapids Community College)

8.7: The Acid-Base Properties of Ions and Salts is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

8.7.4 [Link]
8.8: Buffers: Solutions That Resist pH Change
Skills to Develop
To understand how adding a common ion affects the position of an acid–base equilibrium.
To know how to use the Henderson-Hasselbalch approximation to calculate the pH of a buffer.

Buffers are solutions that maintain a relatively constant pH when an acid or a base is added. They therefore protect, or “buffer,”
other molecules in solution from the effects of the added acid or base. Buffers contain either a weak acid (H A) and its conjugate
base (A ) or a weak base (B ) and its conjugate acid (BH ), and they are critically important for the proper functioning of
− +

biological systems. In fact, every biological fluid is buffered to maintain its physiological pH.

The Common Ion Effect with Acids and Bases

To understand how buffers work, let’s look first at how the ionization equilibrium of a weak acid is affected by adding either the
conjugate base of the acid or a strong acid (a source of H ). Le Chatelier’s principle can be used to predict the effect on the
+

equilibrium position of the solution. A typical buffer used in biochemistry laboratories contains acetic acid and a salt such as
sodium acetate. The dissociation reaction of acetic acid is as follows:
− +
C H3 C O2 H (aq) ⇋ C H3 C O (aq) + H (aq) (8.8.1)

and the equilibrium constant expression is as follows:

+
[H ][C H3 C O2 ]
Ka = (8.8.2)
[C H3 C O2 H ]

Sodium acetate (C H C O N a) is a strong electrolyte that ionizes completely in aqueous solution to produce N a and C H C O
3 2
+
3
−

ions. If sodium acetate is added to a solution of acetic acid, Le Chatelier’s principle predicts that the equilibrium in Equation 8.8.1
will shift to the left, consuming some of the added C H C O and some of the H ions originally present in solution.
3
−

2
+

Because N a is a spectator ion, it has no effect on the position of the equilibrium and can be ignored. The addition of sodium
+

acetate produces a new equilibrium composition, in which [H ] is less than the initial value. Because [H ] has decreased, the pH
+ +

will be higher. Thus adding a salt of the conjugate base to a solution of a weak acid increases the pH. This makes sense because
sodium acetate is a base, and adding any base to a solution of a weak acid should increase the pH.
If we instead add a strong acid such as H C l to the system, [H ] increases. Once again the equilibrium is temporarily disturbed,
+

but the excess H ions react with the conjugate base (C H C O ), whether from the parent acid or sodium acetate, to drive the
+
3
−

equilibrium to the left. The net result is a new equilibrium composition that has a lower [C H C O ] than before. In both cases,
3
−

only the equilibrium composition has changed; the ionization constant K for acetic acid remains the same. Adding a strong
a

electrolyte that contains one ion in common with a reaction system that is at equilibrium, in this case C H C O , will therefore 3
−

shift the equilibrium in the direction that reduces the concentration of the common ion. The shift in equilibrium is via the common
ion effect.

Adding a common ion to a system at equilibrium affects the equilibrium composition, but
not the ionization constant.
Now let’s suppose we have a buffer solution that contains equimolar concentrations of a weak base (B ) and its conjugate acid (
BH
+
). The general equation for the ionization of a weak base is as follows:
+ −
B(aq) + H2 O(l) ⇋ BH (aq) + OH (aq) (8.8.3)

If the equilibrium constant for the reaction as written in Equation 8.8.3 is small, for example Kb = 10
−5
, then the equilibrium
1
constant for the reverse reaction is very large: K = = 10
5
. Adding a strong base such as OH
−
to the solution therefore
Kb

causes the equilibrium in Equation 8.8.3 to shift to the left, consuming the added OH . As a result, the OH ion concentration in
− −

solution remains relatively constant, and the pH of the solution changes very little. Le Chatelier’s principle predicts the same
outcome: when the system is stressed by an increase in the OH ion concentration, the reaction will proceed to the left to
−

counteract the stress.

If the pK of the base is 5.0, the pK of its conjugate acid is
b a

8.8.1 [Link]
 p Ka = p Kw − p Kb = 14.0– 5.0 = 9.0. (8.8.4)

Thus the equilibrium constant for ionization of the conjugate acid is even smaller than that for ionization of the base. The ionization
reaction for the conjugate acid of a weak base is written as follows:
+ +
BH (aq) + H2 O(l) ⇋ B(aq) + H3 O (aq) (8.8.5)

Again, the equilibrium constant for the reverse of this reaction is very large: K = 1/Ka = 109. If a strong acid is added, it is
neutralized by reaction with the base as the reaction in Equation 8.8.5 shifts to the left. As a result, the H ion concentration does
+

not increase very much, and the pH changes only slightly. In effect, a buffer solution behaves somewhat like a sponge that can
absorb H and OH ions, thereby preventing large changes in pH when appreciable amounts of strong acid or base are added to a
+ −

solution.
The buffer acid will always react with any added (intruder) base such as OH-, to remove that OH-. The net result of the reaction is
[buf f er base]
that water is produced and the ratio of is increased:
[buf f er acid]

+ −
BH (aq) + OH (aq) ⇌ B(aq) + H2 O(l) (8.8.6)

The buffer base will always react with any added (intruder) acid such as H3O+, to remove that H3O+. The net result of the reaction
[buf f er base]
is that water is produced and the ratio of is decreased:
[buf f er acid]

+ +
B(aq) + H3 O (aq) ⇌ BH (aq) + H2 O(l) (8.8.7)

Rather than changing the pH dramatically and making the solution acidic, the added H+ ions react to make molecules of a weak
acid. Figure 8.8.1 illustrates both actions of a buffer made from the conjugate pair HAn/An-.

Figure 8.8.1 : The Actions of Buffers. Buffers can react with both strong acids (top) and strong bases (side) to minimize large
changes in pH.

Calculating the pH of a Buffer

The pH of a buffer can be calculated from the concentrations of the weak acid and the weak base used to prepare it, the
concentration of the conjugate base and conjugate acid, and the pK or pK of the weak acid or weak base. The procedure is
a b

analogous to that used in Example 8.8.1 to calculate the pH of a solution containing known concentrations of formic acid and
formate.

8.8.2 [Link]
An alternative method frequently used to calculate the pH of a buffer solution is based on a rearrangement of the equilibrium
equation for the dissociation of a weak acid. The simplified ionization reaction is H A ⇋ H + A , for which the equilibrium
+ −

constant expression is as follows:

+ −
[H ][ A ]
Ka = (8.8.8)
[H A]

This equation can be rearranged as follows:

[H A]
+
[H ] = Ka (8.8.9)
−
[A ]

Taking the logarithm of both sides and multiplying both sides by −1,
[H A]
+
− log[ H ] = − log Ka − log( ) (8.8.10)
−
[A ]

−
[A ]
= − log Ka + log( ) (8.8.11)
[H A]

Replacing the negative logarithms in Equation 8.8.11,

−
[A ]
pH = p Ka + log( ) (8.8.12)
[H A]

or, more generally,

[base]
pH = p Ka + log( ) (8.8.13)
[acid]

Equation 8.8.12 and Equation 8.8.13 are both forms of the Henderson-Hasselbalch approximation, named after the two early 20th-
century chemists who first noticed that this rearranged version of the equilibrium constant expression provides an easy way to
calculate the pH of a buffer solution. In general, the validity of the Henderson-Hasselbalch approximation may be limited to
solutions whose concentrations are at least 100 times greater than their K values. a

There are three special cases where the Henderson-Hasselbalch approximation is easily interpreted without the need for
calculations:
[base] = [acid] : Under these conditions,
[base]
=1 (8.8.14)
[acid]

in Equation 8.8.13. Because log 1 = 0,

pH = pKa (8.8.15)

regardless of the actual concentrations of the acid and base. Recall that this corresponds to the midpoint in the titration of a
weak acid or a weak base.
[base]/[acid] = 10: In Equation 8.8.13, because log 10 = 1,

pH = p Ka + 1. (8.8.16)

[base]/[acid] = 100 : In Equation 8.8.13, because log 100 = 2,

pH = p Ka + 2. (8.8.17)

Each time we increase the [base]/[acid] ratio by 10, the pH of the solution increases by 1 pH unit. Conversely, if the [base]/[acid]
ratio is 0.1, then pH = pK − 1. Each additional factor-of-10 decrease in the [base]/[acid] ratio causes the pH to decrease by 1 pH
a

unit.

If [base] = [acid] for a buffer, then pH = pK . Changing this ratio by a factor of 10 either way changes the pH by ±1 unit.
a

8.8.3 [Link]
Example 8.8.2
What is the pH of a solution that contains
a. 0.135 M H C O H and 0.215 M H C O N a? (The pK of formic acid is 3.75.)
2 2 a

b. 0.0135 M H C O H and 0.0215 M H C O N a?

2 2

c. 0.119 M pyridine and 0.234 M pyridine hydrochloride? (The pK of pyridine is 8.77.)

b

Given: concentration of acid, conjugate base, and pK ; concentration of base, conjugate acid, and pK
a b

Asked for: pH
Strategy:
Substitute values into either form of the Henderson-Hasselbalch approximation (Equation 8.8.12 or Equation ) to
8.8.13

calculate the pH.

Solution:
According to the Henderson-Hasselbalch approximation (Equation 8.8.12), the pH of a solution that contains both a weak acid
and its conjugate base is
pH = p Ka + log([A−]/[H A]). (8.8.18)

A
Inserting the given values into the equation,
0.215
pH = 3.75 + log( )
0.135

= 3.75 + log 1.593

= 3.95

This result makes sense because the [A

−
]/[H A] ratio is between 1 and 10, so the pH of the buffer must be between the pKa

(3.75) and pK + 1 , or 4.75.

a

B
This is identical to part (a), except for the concentrations of the acid and the conjugate base, which are 10 times lower. Inserting
the concentrations into the Henderson-Hasselbalch approximation,
0.0215
pH = 3.75 + log( )
0.0135

= 3.75 + log 1.593

= 3.95

This result is identical to the result in part (a), which emphasizes the point that the pH of a buffer depends only on the ratio of
the concentrations of the conjugate base and the acid, not on the magnitude of the concentrations. Because the [A−]/[HA] ratio is
the same as in part (a), the pH of the buffer must also be the same (3.95).
C
In this case, we have a weak base, pyridine (Py), and its conjugate acid, the pyridinium ion (H P y ). We will therefore use
+

Equation 8.8.13, the more general form of the Henderson-Hasselbalch approximation, in which “base” and “acid” refer to the
appropriate species of the conjugate acid–base pair. We are given [base] = [Py] = 0.119 M and [acid] = [H P y ] = 0.234 M. +

We also are given pK = 8.77 for pyridine, but we need pK for the pyridinium ion. Recall that the pK of a weak base and
b a b

the pK of its conjugate acid are related:

a

p Ka + p Kb = p Kw . (8.8.19)

Thus pK for the pyridinium ion is

a p Kw − p Kb = 14.00 − 8.77 = 5.23 . Substituting this pKa value into the Henderson-
Hasselbalch approximation,

8.8.4 [Link]
 [
[base]
pH = p Ka + log( )
[acid]

0.119
= 5.23 + log( )
0.234

= 5.23 −0.294

= 4.94

\]
Once again, this result makes sense: the [B]/[BH +
] ratio is about 1/2, which is between 1 and 0.1, so the final pH must be
between the pK (5.23) and pK − 1 , or 4.23.
a a

Exercise 8.8.2
What is the pH of a solution that contains
a. 0.333 M benzoic acid and 0.252 M sodium benzoate?
b. 0.050 M trimethylamine and 0.066 M trimethylamine hydrochloride?
The pK of benzoic acid is 4.20, and the pK of trimethylamine is also 4.20.
a b

Answer a
4.08
Answer b
9.68

The Henderson-Hasselbalch approximation ((Equation 8.8.12) can also be used to calculate the pH of a buffer solution after adding
a given amount of strong acid or strong base, as demonstrated in Example 8.8.3.

Example 8.8.3
The buffer solution in Example 8.8.2 contained 0.135 M H C O 2H and 0.215 M H C O 2N a and had a pH of 3.95.
a. What is the final pH if 5.00 mL of 1.00 M H C l are added to 100 mL of this solution?
b. What is the final pH if 5.00 mL of 1.00 M N aOH are added?
Given: composition and pH of buffer; concentration and volume of added acid or base
Asked for: final pH
Strategy:
A. Calculate the amounts of formic acid and formate present in the buffer solution using the procedure from Example 8.8.1.
Then calculate the amount of acid or base added.
B. Construct a table showing the amounts of all species after the neutralization reaction. Use the final volume of the solution to
calculate the concentrations of all species. Finally, substitute the appropriate values into the Henderson-Hasselbalch
approximation (Equation 8.8.13) to obtain the pH.
Solution:
The added H C l (a strong acid) or N aOH (a strong base) will react completely with formate (a weak base) or formic acid (a
weak acid), respectively, to give formic acid or formate and water. We must therefore calculate the amounts of formic acid and
formate present after the neutralization reaction.
A We begin by calculating the millimoles of formic acid and formate present in 100 mL of the initial pH 3.95 buffer:
The millimoles of H +
in 5.00 mL of 1.00 M HCl is as follows:
B Next, we construct a table of initial amounts, changes in amounts, and final amounts:

8.8.5 [Link]
 2− +
HC O (aq) + H (aq) → H C O2 H (aq) (8.8.20)

2− +
HCO (aq) H (aq) HCO2 H(aq)

Initial 21.5 mmol 5.00 mmol 13.5 mmol

Change −5.00 mmol −5.00 mmol +5.00 mmol

Final 16.5 mmol ∼0 mmol 18.5 mmol

The final amount of H in solution is given as “∼0 mmol.” For the purposes of the stoichiometry calculation, this is essentially
+

true, but remember that the point of the problem is to calculate the final [H ] and thus the pH. We now have all the information
+

we need to calculate the pH. We can use either the lengthy procedure of Example 8.8.1 or the Henderson–Hasselbach
approximation. Because we have performed many equilibrium calculations in this chapter, we’ll take the latter approach. The
Henderson-Hasselbalch approximation requires the concentrations of H C O and H C O H , which can be calculated using the
−

2
2

number of millimoles (n ) of each and the total volume (V T ). Substituting these values into the Henderson-Hasselbalch
approximation,
−
[H C O ] n − / Vf n −

2 H C O2 H C O2
pH = p Ka + log( ) = p Ka + log( ) = p Ka + log( ) (8.8.21)
[H C O2 H ] nH C O H / Vf nH C O2 H
2

Because the total volume appears in both the numerator and denominator, it cancels. We therefore need to use only the ratio of
the number of millimoles of the conjugate base to the number of millimoles of the weak acid. So
nH C O− 16.5 mmol
2
pH = p Ka + log( ) = 3.75 + log( ) = 3.75 −0.050 = 3.70 (8.8.22)
nH C O 18.5 mmol
2H

Once again, this result makes sense on two levels. First, the addition of H C lhas decreased the pH from 3.95, as expected.
Second, the ratio of H C O to H C O H is slightly less than 1, so the pH should be between the pK and pK − 1.
−
2 2 a a

A The procedure for solving this part of the problem is exactly the same as that used in part (a). We have already calculated the
numbers of millimoles of formic acid and formate in 100 mL of the initial pH 3.95 buffer: 13.5 mmol of H C O H and 21.5 2

mmol of H C O . The number of millimoles of OH in 5.00 mL of 1.00 M N aOH is as follows:

−

2
−

B With this information, we can construct a table of initial amounts, changes in amounts, and final amounts.
− −
H C O2 H (aq) + OH (aq) → H C O (aq) + H2 O(l) (8.8.23)
2

− −
HC O2 H(aq) OH HC O (aq)
2

Initial 13.5 mmol 5.00 mmol 21.5 mmol

Change −5.00 mmol −5.00 mmol +5.00 mmol

Final 8.5 mmol ∼0 mmol 26.5 mmol

The final amount of OH in solution is not actually zero; this is only approximately true based on the stoichiometric
−

calculation. We can calculate the final pH by inserting the numbers of millimoles of both H C O and H C O H into the −

2
2

simplified Henderson-Hasselbalch expression used in part (a) because the volume cancels:
n −
26.5 mmol
H C O2
pH = p Ka + log( ) = 3.75 + log( ) = 3.75 + 0.494 = 4.24 (8.8.24)
nH C O2 H 8.5 mmol

Once again, this result makes chemical sense: the pH has increased, as would be expected after adding a strong base, and the
final pH is between the pK and pK + 1, as expected for a solution with a H C O /H C O H ratio between 1 and 10.
a a
−
2 2

8.8.6 [Link]
 Exercise 8.8.3
The buffer solution from Example 8.8.2 contained 0.119 M pyridine and 0.234 M pyridine hydrochloride and had a pH of 4.94.
a. What is the final pH if 12.0 mL of 1.5 M N aOH are added to 250 mL of this solution?
b. What is the final pH if 12.0 mL of 1.5 M H C l are added?

Answer a
5.30
Answer b
4.42

Only the amounts (in moles or millimoles) of the acidic and basic components of the buffer are needed to use the Henderson-
Hasselbalch approximation, not their concentrations.

The results obtained in Example 8.8.3 and its corresponding exercise demonstrate how little the pH of a well-chosen buffer
solution changes despite the addition of a significant quantity of strong acid or strong base. Suppose we had added the same
amount of H C l or N aOH solution to 100 mL of an unbuffered solution at pH 3.95 (corresponding to 1.1 × 10 M HCl). In this
−4

case, adding 5.00 mL of 1.00 M H C l would lower the final pH to 1.32 instead of 3.70, whereas adding 5.00 mL of 1.00 M N aOH
would raise the final pH to 12.68 rather than 4.24. (Try verifying these values by doing the calculations yourself.) Thus the
presence of a buffer significantly increases the ability of a solution to maintain an almost constant pH.

The most effective buffers contain equal concentrations of an acid and its conjugate base.
A buffer that contains approximately equal amounts of a weak acid and its conjugate base in solution is equally effective at
neutralizing either added base or added acid. This is shown in Figure 8.8.2 for an acetic acid/sodium acetate buffer. Adding a given
amount of strong acid shifts the system along the horizontal axis to the left, whereas adding the same amount of strong base shifts
the system the same distance to the right. In either case, the change in the ratio of C H C O to C H C O H from 1:1 reduces the
3
−
2 3 2

buffer capacity of the solution.

Figure 8.8.2 : Distribution Curve Showing the Fraction of Acetic Acid Molecules and Acetate Ions as a Function of pH in a
Solution of Acetic Acid. The pH range over which the acetic acid/sodium acetate system is an effective buffer (the darker shaded
region) corresponds to the region in which appreciable concentrations of both species are present (pH 3.76–5.76, corresponding to
pH = p K ± 1 ).
a

8.8.7 [Link]
Blood: A Most Important Buffer
Metabolic processes produce large amounts of acids and bases, yet organisms are able to maintain an almost constant internal pH
because their fluids contain buffers. This is not to say that the pH is uniform throughout all cells and tissues of a mammal. The
internal pH of a red blood cell is about 7.2, but the pH of most other kinds of cells is lower, around 7.0. Even within a single cell,
different compartments can have very different pH values. For example, one intracellular compartment in white blood cells has a
pH of around 5.0.
Because no single buffer system can effectively maintain a constant pH value over the entire physiological range of approximately
pH 5.0 to 7.4, biochemical systems use a set of buffers with overlapping ranges. The most important of these is the C O /H C O 2
−
3

system, which dominates the buffering action of blood plasma.

The acid–base equilibrium in the C O 2 /H C O
−

3
buffer system is usually written as follows:
+ −
H2 C O3 (aq) ⇋ H (aq) + H C O (aq) (8.8.25)
3

with K = 4.5 × 10 and pK = 6.35 at 25°C. In fact, Equation 8.8.25 is a grossly oversimplified version of the C O /H C O
a
−7
a 2
−

system because a solution of C O in water contains only rather small amounts of H C O . Thus Equation 8.8.25 does not allow us
2 2 3

to understand how blood is actually buffered, particularly at a physiological temperature of 37°C. As shown in Equation 8.8.26,
C O is in equilibrium with H C O , but the equilibrium lies far to the left, with an H C O /C O ratio less than 0.01 under most
2 2 3 2 3 2

conditions:
C O2 (aq) + H2 O(l) ⇋ H2 C O3 (aq) (8.8.26)

with K' = 4.0 × 10 at 37°C. The true pK of carbonic acid at 37°C is therefore 3.70, not 6.35, corresponding to a K of
−3
a a

2.0 × 10 , which makes it a much stronger acid than Equation 8.8.25 suggests. Adding Equation 8.8.26 and Equation 8.8.25 and
−4

canceling H C O from both sides give the following overall equation for the reaction of C O with water to give a proton and the
2 3 2

bicarbonate ion:
C O2 (aq) + H2 O(l) ⇋ H2 C O3 (aq) (8.8.26)

with K ′
= 4.0 × 10
−3
(37°C )

+ −
H2 C O3 (aq) ⇋ H (aq) + H C O (aq) (8.8.25)
3

with K a = 2.0 × 10
−4
(37°C )

+ −
C O2 (aq) + H2 O(l) ⇋ H (aq) + H C O (aq) (8.8.27)
3

with K = 8.0 × 10 −7
(37°C )

The K value for the reaction in Equation 8.8.27 is the product of the true ionization constant for carbonic acid (K ) and the a

equilibrium constant (K) for the reaction of C O (aq) with water to give carbonic acid. The equilibrium equation for the reaction of
2

C O with water to give bicarbonate and a proton is therefore

2

+ −
[H ][H C O ]
3 −7
K = = 8.0 × 10 (8.8.28)
[C O2 ]

The presence of a gas in the equilibrium constant expression for a buffer is unusual. According to Henry’s law,
[C O2 ] = kPC O (8.8.29)
2

where k is the Henry’s law constant for C O , which is 3.0 × 10 2

−5
M /mmH g at 37°C. Substituting this expression for [C O 2] in
Equation 8.8.28,
+ −
[H ][H C O ]
3
K = (8.8.30)
−5
(3.0 × 10 M /mmH g)(PC O )
2

where P C O2 is in mmHg. Taking the negative logarithm of both sides and rearranging,
−
[H C O ]
3
pH = 6.10 + log( ) (8.8.31)
−5
(3.0 × 10 M /mm H g) (PC O )
2

8.8.8 [Link]
Thus the pH of the solution depends on both the C O pressure over the solution and [H C O ]. Figure 8.8.4 plots the relationship
2
−
3

between pH and [H C O ] under physiological conditions for several different values of P

−
3
, with normal pH and [H C O ]
C O2
−
3

values indicated by the dashed lines.

Figure 8.8.4 : Buffering in Blood: pH versus [H C O ] Curves for Buffers with Different Values of P
−
3
. Only those combinations
C O2

of pH and [H C O ] that lie on a given line are allowed for the particular value of P
−
3
indicated. Normal values of blood plasma
C O2

pH and [H C O ] are indicated by dashed lines.

−
3

According to Equation 8.8.27, adding a strong acid to the C O /H C O system causes [H C O ] to decrease as H C O is
2
−

3
−

3
−

converted to C O . Excess C O is released in the lungs and exhaled into the atmosphere, however, so there is essentially no change
2 2

in PC O2 . Because the change in [H C O ]/P

−

3
is small, Equation 8.8.31 predicts that the change in pH will also be rather small.
C O2

Conversely, if a strong base is added, the OH reacts with CO2 to form [H C O ], but C O is replenished by the body, again
− −

3 2

limiting the change in both [H C O ]/P

−

3
and pH. The C O /H C O buffer system is an example of an open system, in which
C O2 2
−

the total concentration of the components of the buffer change to keep the pH at a nearly constant value.
If a passenger steps out of an airplane in Denver, Colorado, for example, the lower P at higher elevations (typically 31 mmHg
C O2

at an elevation of 2000 m versus 40 mmHg at sea level) causes a shift to a new pH and [H C O ]. The increase in pH and decrease
−
3

in [H C O ] in response to the decrease in P

−
3
are responsible for the general malaise that many people experience at high
C O2

altitudes. If their blood pH does not adjust rapidly, the condition can develop into the life-threatening phenomenon known as
altitude sickness.

Summary
Buffers are solutions that resist a change in pH after adding an acid or a base. Buffers contain a weak acid (H A) and its conjugate
weak base (A ). Adding a strong electrolyte that contains one ion in common with a reaction system that is at equilibrium shifts
−

the equilibrium in such a way as to reduce the concentration of the common ion. The shift in equilibrium is called the common ion
effect. Buffers are characterized by their pH range and buffer capacity. The useful pH range of a buffer depends strongly on the
chemical properties of the conjugate weak acid–base pair used to prepare the buffer (the K or K ), whereas its buffer capacity
a b

depends solely on the concentrations of the species in the solution. The pH of a buffer can be calculated using the Henderson-
Hasselbalch approximation, which is valid for solutions whose concentrations are at least 100 times greater than their K values. a

Because no single buffer system can effectively maintain a constant pH value over the physiological range of approximately 5 to
7.4, biochemical systems use a set of buffers with overlapping ranges. The most important of these is the C O /H C O system,
2
−
3

which dominates the buffering action of blood plasma.

8.8: Buffers: Solutions That Resist pH Change is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

8.8.9 [Link]
8.9 Buffer Capacity and Buffer Range
Buffer Capacity
Buffers are characterized by the pH range over which they can maintain a more or less constant pH and by their buffer capacity, the
amount of strong acid or base that can be absorbed before the pH changes significantly. Although the useful pH range of a buffer
depends strongly on the chemical properties of the weak acid and weak base used to prepare the buffer (i.e., on K ), its buffer
capacity depends solely on the concentrations of the species in the buffered solution. The more concentrated the buffer solution, the
greater its buffer capacity. As illustrated in Figure 1, when N aOH is added to solutions that contain different concentrations of an
acetic acid/sodium acetate buffer, the observed change in the pH of the buffer is inversely proportional to the concentration of the
buffer. If the buffer capacity is 10 times larger, then the buffer solution can absorb 10 times more strong acid or base before
undergoing a significant change in pH.

Figure 1 : Effect of Buffer Concentration on the Capacity of a Buffer

A buffer maintains a relatively constant pH when acid or base is added to a solution. The addition of even tiny volumes of 0.10 M
N aOH to 100.0 mL of distilled water results in a very large change in pH. As the concentration of a 50:50 mixture of sodium

acetate/acetic acid buffer in the solution is increased from 0.010 M to 1.00 M, the change in the pH produced by the addition of the
same volume of N aOH solution decreases steadily. For buffer concentrations of at least 0.500 M, the addition of even 25 mL of
the N aOH solution results in only a relatively small change in pH.

Selecting proper components for desired pH

Buffers function best when the pKa of the conjugate weak acid used is close to the desired working range of the buffer. This turns
out to be the case when the concentrations of the conjugate acid and conjugate base are approximately equal (within about a factor
of 10). For example, we know the Ka for hydroflouric acid is 6.6 x 10-4 so its pKa= -log(6.6 x 10-4) = 3.18. So, a hydrofluoric acid
buffer would work best in a buffer range of around pH = 3.18.
For the weak base ammonia (NH3), the value of Kb is 1.8x10-5, implying that the Ka for the dissociation of its conjugate acid,
NH4+, is Kw/Kb=10-14/1.8x10-5 = 5.6x10-10. Thus, the pKa for NH4+ = 9.25, so buffers using NH4+/NH3 will work best around a pH
of 9.25. (It's always the pKa of the conjugate acid that determines the approximate pH for a buffer system, though this is dependent
on the pKb of the conjugate base, obviously.)
When the desired pH of a buffer solution is near the pKa of the conjugate acid being used (i.e., when the amounts of conjugate acid
and conjugate base in solution are within about a factor of 10 of each other), the Henderson-Hasselbalch equation can be applied as
a simple approximation of the solution pH, as we will see in the next section.
Example 1: HF Buffer
In this example we will continue to use the hydrofluoric acid buffer. We will discuss the process for preparing a buffer of HF at
a pH of 3.0. We can use the Henderson-Hasselbalch approximation to calculate the necessary ratio of F- and HF.

1 [Link]
 [Base]
pH = pKa + log (1)
[Acid]

[Base]
3.0 = 3.18 + log (2)
[Acid]

[Base]
log = −0.18 (3)
[Acid]

[Base]
−0.18
= 10 (4)
[Acid]

[Base]
= 0.66 (5)
[Acid]

This is simply the ratio of the concentrations of conjugate base and conjugate acid we will need in our solution. However, what
if we have 100 ml of 1 M HF and we want to prepare a buffer using NaF? How much Sodium Fluoride would we need to add in
order to create a buffer at said pH (3.0)?
We know from our Henderson-Hasselbalch calculation that the ratio of our base/acid should be equal to 0.66. From a table of
molar masses, such as a periodic table, we can calculate the molar mass of NaF to be equal to 41.99 g/mol. HF is a weak acid
with a Ka = 6.6 x 10-4 and the concentration of HF is given above as 1 M. Using this information, we can calculate the amount
of F- we need to add.
The dissociation reaction is:
− +
H F(aq) + H2 O(l) ⇌ F + H3 O (6)
(aq) (aq)

We could use ICE tables to calculate the concentration of F- from HF dissociation, but, since Ka is so small, we can approximate
that virtually all of the HF will remain undissociated, so the amount of F- in the solution from HF dissociation will be negligible.
Thus, the [HF] is about 1 M and the [F-] is close to 0. This will be especially true once we have added more F-, the addition of
which will even further suppress the dissociation of HF.
We want the ratio of Base/Acid to be 0.66, so we will need [Base]/1M = 0.66. Thus, [F-] should be about 0.66 M. For 100 mL of
solution, then, we will want to add 0.066 moles (0.1 L x 0.66 M) of F-. Since we are adding NaF as our source of F-, and since
NaF completely dissociates in water, we need 0.066 moles of NaF. Thus, 0.066 moles x 41.99 g/mol = 2.767 g.
Note that, since the conjugate acid and the conjugate base are both mixed into the same volume of solution in the buffer, the
ratio of "Base/Acid" is the same whether we use a ratio of the "concentration of base over concentration of acid," OR a ratio of
"moles of base over moles of acid." The pH of the solution does not, it turns out, depend on the volume! (This is only true so
long as the solution does not get so dilute that the autoionization of water becomes an important source of H+ or OH-. Such
dilute solutions are rarely used as buffers, however.)

References
1. Brown, et al. Chemistry:The Central Science. 11th ed. Upper Saddle River, New Jersey: Pearson/Prentice Hall, 2008.
2. Chang, Raymond. General Chemistry:The Essential Concepts. 3rd ed. New York: Mcgraw Hill, 2003
3. Petrucci, et al. General Chemistry: Principles & Modern Applications. 9th ed. Upper Saddle River, New Jersey:
Pearson/Prentice Hall, 2007.

Outside Links
Urbansky, Edward T.; Schock, Michael R. "Understanding, Deriving, and Computing Buffer Capacity." J. Chem. Educ. 2000
1640..

Contributors
Jose Pietri (UCD), Donald Land (UCD)

8.9 Buffer Capacity and Buffer Range is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

2 [Link]
8.10: Lewis Acids and Bases
 Learning Objectives

Make sure you thoroughly understand the following essential ideas which have been presented above. It is especially important
that you know the precise meanings of all the highlighted terms in the context of this topic.
Write the equation for the proton transfer reaction involving a Brønsted-Lowry acid or base, and show how it can be
interpreted as an electron-pair transfer reaction, clearly identifying the donor and acceptor.
Give an example of a Lewis acid-base reaction that does not involve protons.
Write equations illustrating the behavior of a given non-aqueous acid-base system.

The Brønsted-Lowry proton donor-acceptor concept has been one of the most successful theories of Chemistry. But as with any
such theory, it is fair to ask if this is not just a special case of a more general theory that could encompass an even broader range of
chemical science. In 1916, G.N. Lewis of the University of California proposed that the electron pair is the dominant actor in acid-
base chemistry. The Lewis theory did not become very well known until about 1923 (the same year that Brønsted and Lowry
published their work), but since then it has been recognized as a very powerful tool for describing chemical reactions of widely
different kinds and is widely used in organic and inorganic chemistry. According to Lewis,
An acid is a substance that accepts a pair of electrons, and in doing so, forms a covalent bond with the entity that supplies the
electrons.
A base is a substance that donates an unshared pair of electrons to a recipient species with which the electrons can be shared.

In modern chemistry, electron donors are often referred to as nucleophiles, while

acceptors are electrophiles.

Proton-Transfer Reactions Involve Electron-Pair Transfer

Just as any Arrhenius acid is also a Brønsted acid, any Brønsted acid is also a Lewis acid, so the various acid-base concepts are all
"upward compatible". Although we do not really need to think about electron-pair transfers when we deal with ordinary aqueous-
solution acid-base reactions, it is important to understand that it is the opportunity for electron-pair sharing that enables proton
transfer to take place.

This equation for a simple acid-base neutralization shows how the Brønsted and Lewis definitions are really just different views of
the same process. Take special note of the following points:
The arrow shows the movement of a proton from the hydronium ion to the hydroxide ion.
Note carefully that the electron-pairs themselves do not move; they remain attached to their central atoms. The electron pair on
the base is "donated" to the acceptor (the proton) only in the sense that it ends up being shared with the acceptor, rather than
being the exclusive property of the oxygen atom in the hydroxide ion.
Although the hydronium ion is the nominal Lewis acid here, it does not itself accept an electron pair, but acts merely as the
source of the proton that coordinates with the Lewis base.
The point about the electron-pair remaining on the donor species is especially important to bear in mind. For one thing, it
distinguishes a Lewis acid-base reaction from an oxidation-reduction reaction, in which a physical transfer of one or more
electrons from donor to acceptor does occur. The product of a Lewis acid-base reaction is known formally as an "adduct" or
"complex", although we do not ordinarily use these terms for simple proton-transfer reactions such as the one in the above
example. Here, the proton combines with the hydroxide ion to form the "adduct" H2O. The following examples illustrate these
points for some other proton-transfer reactions that you should already be familiar with.

8.10.1 [Link]
Another example, showing the autoprotolysis of water. Note that the conjugate base is also the adduct.

Ammonia is both a Brønsted and a Lewis base, owing to the unshared electron pair on the nitrogen. The reverse of this reaction
represents the hydrolysis of the ammonium ion.

Because HF is a weak acid, fluoride salts behave as bases in aqueous solution. As a Lewis base, F– accepts a proton from water,
which is transformed into a hydroxide ion.

The bisulfite ion is amphiprotic and can act as an electron donor or acceptor.

Acid-base Reactions without Transferring Protons

The major utility of the Lewis definition is that it extends the concept of acids and bases beyond the realm of proton transfer
reactions. The classic example is the reaction of boron trifluoride with ammonia to form an adduct:

BF + NH → F B−NH (8.10.1)
3 3 3 3

One of the most commonly-encountered kinds of Lewis acid-base reactions occurs when electron-donating ligands form
coordination complexes with transition-metal ions.

Figure 8.10.1 : The tin atom in SnCl4 can expand its valence shell by utilizing a pair of d-orbitals, changing its hybridization from
sp3 to sp3d2.

 Exercise 8.10.1

Here are several more examples of Lewis acid-base reactions that cannot be accommodated within the Brønsted or Arrhenius
models. Identify the Lewis acid and Lewis base in each reaction.
a. Al (OH)
3
+ OH
–
→ Al (OH) –
4

8.10.2 [Link]
 b. SnS + S → SnS
2
2 – 2 –
3

c. Cd(CN) + 2 CN– → Cd(CN)

2
2 +

4
+
d. AgCl + 2 NH → Ag(NH ) + Cl–
3 3 2

e. Fe + NO → Fe(NO)
2 + 2 +

2 +
f. Ni + 6 NH → Ni(NH )
2 +

3 3 5

Applications to organic reaction mechanisms

Although organic chemistry is beyond the scope of these lessons, it is instructive to see how electron donors and acceptors play a
role in chemical reactions. The following two diagrams show the mechanisms of two common types of reactions initiated by simple
inorganic Lewis acids:

In each case, the species labeled "Complex" is an intermediate that decomposes into the products, which are conjugates of the
original acid and base pairs. The electric charges indicated in the complexes are formal charges, but those in the products are "real".
In reaction 1, the incomplete octet of the aluminum atom in AlCl serves as a better electron acceptor to the chlorine atom than
3

does the isobutyl part of the base. In reaction 2, the pair of non-bonding electrons on the dimethyl ether coordinates with the
electron-deficient boron atom, leading to a complex that breaks down by releasing a bromide ion.

Non-aqueous Protonic Acid-Base Systems

We ordinarily think of Brønsted-Lowry acid-base reactions as taking place in aqueous solutions, but this need not always be the
case. A more general view encompasses a variety of acid-base solvent systems, of which the water system is only one (Table
8.10.1). Each of these has as its basis an amphiprotic solvent (one capable of undergoing autoprotolysis), in parallel with the

familiar case of water.

The ammonia system is one of the most common non-aqueous system in Chemistry. Liquid ammonia boils at –33° C, and can
conveniently be maintained as a liquid by cooling with dry ice (–77° C). It is a good solvent for substances that also dissolve in
water, such as ionic salts and organic compounds since it is capable of forming hydrogen bonds. However, many other familiar
substances can also serve as the basis of protonic solvent systems as Table 8.10.1 indicates:
Table 8.10.1 : Popular Solvent systems
solvent autoprotolysis reaction pKap

water 2 H2O → H3O+ + OH– 14

ammonia 2 NH3 → NH4+ + NH2– 33

acetic acid 2 CH3COOH → CH3COOH2+ + CH3COO– 13

ethanol 2 C2H5OH → C2H5OH2+ + C2H5O– 19

hydrogen peroxide 2 HO-OH → HO-OH2+ + HO-O– 13

hydrofluoric acid 2 HF → H2F+ + F– 10

sulfuric acid 2 H2SO4 → H3SO4+ + HSO4– 3.5

One use of nonaqueous acid-base systems is to examine the relative strengths of the strong acids and bases, whose strengths are
"leveled" by the fact that they are all totally converted into H3O+ or OH– ions in water. By studying them in appropriate non-
aqueous solvents which are poorer acceptors or donors of protons, their relative strengths can be determined.

8.10.3 [Link]
 Figure 8.10.2 : Use of non-aqueous solvents allows the study of strong acids that are hindered by the "leveling" of the solvent.

8.10: Lewis Acids and Bases is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.
10.5: Lewis Acids and Bases is licensed CC BY 3.0. Original source: [Link]

8.10.4 [Link]
8.11: Acid/Base (Exercises)
8.11: Acid/Base (Exercises) is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

8.11.1 [Link]
 CHAPTER OVERVIEW

9: Electrochemistry
9.1: Oxidation-Reduction Reactions
9.2: Standard Reduction Potentials
9.3 Cell Potential, Gibbs Free Energy, and Equilibrium
9.4: Batteries: Using Chemistry to Generate Electricity
9.5 Driving Reactant-Favored Reactions Using Electricity
9.6 Undesirable Redox Reactions

9: Electrochemistry is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

1
9.1: Oxidation-Reduction Reactions
Skills to Develop
To identify oxidation–reduction reactions in solution.

The term oxidation was first used to describe reactions in which metals react with oxygen in air to produce metal oxides. When
iron is exposed to air in the presence of water, for example, the iron turns to rust—an iron oxide. When exposed to air, aluminum
metal develops a continuous, transparent layer of aluminum oxide on its surface. In both cases, the metal acquires a positive charge
by transferring electrons to the neutral oxygen atoms of an oxygen molecule. As a result, the oxygen atoms acquire a negative
charge and form oxide ions (O2−). Because the metals have lost electrons to oxygen, they have been oxidized; oxidation is therefore
the loss of electrons. Conversely, because the oxygen atoms have gained electrons, they have been reduced, so reduction is the gain
of electrons. For every oxidation, there must be an associated reduction. Therefore, these reactions are known as oxidation-
reduction reactions, or "redox" reactions for short.

Any oxidation must ALWAYS be accompanied by a reduction and vice versa.

Originally, the term reduction referred to the decrease in mass observed when a metal oxide was heated with carbon monoxide, a
reaction that was widely used to extract metals from their ores. When solid copper(I) oxide is heated with hydrogen, for example,
its mass decreases because the formation of pure copper is accompanied by the loss of oxygen atoms as a volatile product (water
vapor). The reaction is as follows:
Cu O(s) + H (g) → 2 Cu(s) + H O(g) (9.1.1)
2 2 2

Oxidation-reduction reactions are now defined as reactions that exhibit a change in the oxidation states of one or more elements in
the reactants by a transfer of electrons, which follows the mnemonic "oxidation is loss, reduction is gain", or "oil rig". The
oxidation state of each atom in a compound is the charge an atom would have if all its bonding electrons were transferred to the
atom with the greater attraction for electrons. Atoms in their elemental form, such as O2 or H2, are assigned an oxidation state of
zero. For example, the reaction of aluminum with oxygen to produce aluminum oxide is

4 Al(s) + 3 O → 2 Al O (s) (9.1.2)

2 2 3

Each neutral oxygen atom gains two electrons and becomes negatively charged, forming an oxide ion; thus, oxygen has an
oxidation state of −2 in the product and has been reduced. Each neutral aluminum atom loses three electrons to produce an
aluminum ion with an oxidation state of +3 in the product, so aluminum has been oxidized. In the formation of Al2O3, electrons are
transferred as follows (the small overset number emphasizes the oxidation state of the elements):
0 0
3 + 2 −
4 Al + 3 O → 4 Al +6 O (9.1.3)
2

Equation 9.1.1 and Equation 9.1.2 are examples of oxidation–reduction (redox) reactions. In redox reactions, there is a net transfer
of electrons from one reactant to another. In any redox reaction, the total number of electrons lost must equal the total of electrons
gained to preserve electrical neutrality. In Equation 9.1.3, for example, the total number of electrons lost by aluminum is equal to
the total number gained by oxygen:
−
3e lost
electrons lost = 4 Al atoms ×
Al atom

−
= 12 e lost

−
2e gained
electrons gained = 6 O atoms ×
O atom

−
= 12 e gained

The same pattern is seen in all oxidation–reduction reactions: the number of electrons lost must equal the number of electrons
gained. An additional example of a redox reaction, the reaction of sodium metal with chlorine is illustrated in Figure 9.1.1.

In all oxidation–reduction (redox) reactions, the number of electrons lost equals the
number of electrons gained.

9.1.1 [Link]
Assigning Oxidation Numbers
Assigning oxidation numbers to the elements in binary ionic compounds is straightforward: the oxidation numbers of the elements
are identical to the charges on the monatomic ions. Previously, you learned how to predict the formulas of simple ionic compounds
based on the sign and magnitude of the charge on monatomic ions formed by the neutral elements. Examples of such compounds
are sodium chloride (NaCl; Figure 9.1.1), magnesium oxide (MgO), and calcium chloride (CaCl2). In covalent compounds, in
contrast, atoms share electrons. However, we can still assign oxidation states to the elements involved by treating them as if they
were ionic (that is, as if all the bonding electrons were transferred to the more attractive element). Oxidation states in covalent
compounds are somewhat arbitrary, but they are useful bookkeeping devices to help you understand and predict many reactions.

Figure 9.1.1 : The Reaction of a Neutral Sodium Atom with a Neutral Chlorine Atom. The result is the transfer of one electron
from sodium to chlorine, forming the ionic compound NaCl.
A set of rules for assigning oxidation numbers to atoms in chemical compounds follows.
Rules for Assigning Oxidation Numbers
1. The oxidation number of an atom in any pure element, whether monatomic, diatomic, or polyatomic, is zero.
2. The oxidation number of a monatomic ion is the same as its charge—for example, Na+ = +1, Cl− = −1.
3. The oxidation number of fluorine in chemical compounds is always −1. Other halogens usually have oxidation states of −1
as well, except when combined with oxygen or other halogens.
4. Hydrogen is assigned an oxidation number of +1 in its compounds with nonmetals and −1 in its compounds with metals.
5. Oxygen is normally assigned an oxidation number of −2 in compounds, with two exceptions: in compounds that contain
oxygen–fluorine or oxygen–oxygen bonds, the oxidation number of oxygen is determined by the oxidation number of the
other elements present.
6. The sum of the oxidation numbers of all the atoms in a neutral molecule or ion must equal the charge on the molecule or ion.

Nonintegral (fractional) oxidation numbers are encountered occasionally. They are

usually due to the presence of two or more atoms of the same element with different
oxidation states.
In any chemical reaction, the net charge must be conserved; that is, in a chemical reaction, the total number of electrons is constant,
just like the total number of atoms. Consistent with this, rule 1 states that the sum of the individual oxidation states of the atoms in
a molecule or ion must equal the net charge on that molecule or ion. In NaCl, for example, Na has an oxidation state of +1 and Cl is
−1. The net charge is zero, as it must be for any compound.
Rule 3 is required because fluorine attracts electrons more strongly than any other element, for reasons you will discover in Chapter
6. Hence fluorine provides a reference for calculating the oxidation states of other atoms in chemical compounds. Rule 4 reflects
the difference in chemistry observed for compounds of hydrogen with nonmetals (such as chlorine) as opposed to compounds of
hydrogen with metals (such as sodium). For example, NaH contains the H− ion, whereas HCl forms H+ and Cl− ions when
dissolved in water. Rule 5 is necessary because fluorine has a greater attraction for electrons than oxygen does; this rule also
prevents violations of rule 2. So the oxidation state of oxygen is +2 in OF2 but −½ in KO2. Note that an oxidation state of −½ for O
in KO2 is perfectly acceptable.
The reduction of copper(I) oxide shown in Equation 9.1.4 demonstrates how to apply these rules. Rule 1 states that atoms in their
elemental form have an oxidation state of zero, which applies to H2 and Cu. From rule 4, hydrogen in H2O has an oxidation state of

9.1.2 [Link]
+1, and from rule 5, oxygen in both Cu2O and H2O has an oxidation state of −2. Rule 6 states that the sum of the oxidation states in
a molecule or formula unit must equal the net charge on that compound. This means that each Cu atom in Cu2O must have a charge
of +1: 2(+1) + (−2) = 0. So the oxidation states are as follows:
+1 −2 0 0 +1 −2

Cu O (s) + H (g) → 2 Cu(s) + H 2 O (g) (9.1.4)

2 2

Assigning oxidation states allows us to see that there has been a net transfer of electrons from hydrogen (0 → +1) to copper (+1 →
0). Thus, this is a redox reaction. Once again, the number of electrons lost equals the number of electrons gained, and there is a net
conservation of charge:
−
1e lost −
electrons lost = 2 H atoms × =2e lost (9.1.5)
H atom

−
1e gained −
electrons gained = 2 C u atoms × =2e gained (9.1.6)
C u atom

Remember that oxidation states are useful for visualizing the transfer of electrons in oxidation–reduction reactions, but the
oxidation state of an atom and its actual charge are the same only for simple ionic compounds. Oxidation states are a convenient
way of assigning electrons to atoms, and they are useful for predicting the types of reactions that substances undergo.

Example 9.1.1 : Oxidation States

Assign oxidation states to all atoms in each compound.
a. sulfur hexafluoride (SF6)
b. methanol (CH3OH)
c. ammonium sulfate [(NH4)2SO4]
d. magnetite (Fe3O4)
e. ethanoic (acetic) acid (CH3CO2H)
Given: molecular or empirical formula
Asked for: oxidation states
Strategy:
Begin with atoms whose oxidation states can be determined unambiguously from the rules presented (such as fluorine, other
halogens, oxygen, and monatomic ions). Then determine the oxidation states of other atoms present according to rule 1.
Solution:
a. We know from rule 3 that fluorine always has an oxidation state of −1 in its compounds. The six fluorine atoms in sulfur
hexafluoride give a total negative charge of −6. Because rule 1 requires that the sum of the oxidation states of all atoms be zero
in a neutral molecule (here SF6), the oxidation state of sulfur must be +6:
[(6 F atoms)(−1)] + [(1 S atom) (+6)] = 0
b. According to rules 4 and 5, hydrogen and oxygen have oxidation states of +1 and −2, respectively. Because methanol has no
net charge, carbon must have an oxidation state of −2:
[(4 H atoms)(+1)] + [(1 O atom)(−2)] + [(1 C atom)(−2)] = 0
c. Note that (NH4)2SO4 is an ionic compound that consists of both a polyatomic cation (NH4+) and a polyatomic anion (SO42−)
(see Table 2.4 "Common Polyatomic Ions and Their Names"). We assign oxidation states to the atoms in each polyatomic ion
separately. For NH4+, hydrogen has an oxidation state of +1 (rule 4), so nitrogen must have an oxidation state of −3:
[(4 H atoms)(+1)] + [(1 N atom)(−3)] = +1, the charge on the NH4+ ion
For SO42−, oxygen has an oxidation state of −2 (rule 5), so sulfur must have an oxidation state of +6:
[(4 O atoms) (−2)] + [(1 S atom)(+6)] = −2, the charge on the sulfate ion
d. Oxygen has an oxidation state of −2 (rule 5), giving an overall charge of −8 per formula unit. This must be balanced by the
positive charge on three iron atoms, giving an oxidation state of +8/3 for iron:

9.1.3 [Link]
 [(4 O atoms)(−2)]+[(3 Fe atoms)(+ 8

3
) ]= 0

Fractional oxidation states are allowed because oxidation states are a somewhat arbitrary way of keeping track of electrons. In
fact, Fe3O4 can be viewed as having two Fe3+ ions and one Fe2+ ion per formula unit, giving a net positive charge of +8 per
formula unit. Fe3O4 is a magnetic iron ore commonly called magnetite. In ancient times, magnetite was known as lodestone
because it could be used to make primitive compasses that pointed toward Polaris (the North Star), which was called the
“lodestar.”
e. Initially, we assign oxidation states to the components of CH3CO2H in the same way as any other compound. Hydrogen and
oxygen have oxidation states of +1 and −2 (rules 4 and 5, respectively), resulting in a total charge for hydrogen and oxygen of
[(4 H atoms)(+1)] + [(2 O atoms)(−2)] = 0
So the oxidation state of carbon must also be zero (rule 6). This is, however, an average oxidation state for the two carbon atoms
present. Because each carbon atom has a different set of atoms bonded to it, they are likely to have different oxidation states. To
determine the oxidation states of the individual carbon atoms, we use the same rules as before but with the additional
assumption that bonds between atoms of the same element do not affect the oxidation states of those atoms. The carbon atom of
the methyl group (−CH3) is bonded to three hydrogen atoms and one carbon atom. We know from rule 4 that hydrogen has an
oxidation state of +1, and we have just said that the carbon–carbon bond can be ignored in calculating the oxidation state of the
carbon atom. For the methyl group to be electrically neutral, its carbon atom must have an oxidation state of −3. Similarly, the
carbon atom of the carboxylic acid group (−CO2H) is bonded to one carbon atom and two oxygen atoms. Again ignoring the
bonded carbon atom, we assign oxidation states of −2 and +1 to the oxygen and hydrogen atoms, respectively, leading to a net
charge of
[(2 O atoms)(−2)] + [(1 H atom)(+1)] = −3
To obtain an electrically neutral carboxylic acid group, the charge on this carbon must be +3. The oxidation states of the
individual atoms in acetic acid are thus
+1 +3 +1

C H3 C O2 H (9.1.7)
−3 −2

Thus the sum of the oxidation states of the two carbon atoms is indeed zero.

Exercise 9.1.1 : Oxidation States

Assign oxidation states to all atoms in each compound.
a. barium fluoride (BaF2)
b. formaldehyde (CH2O)
c. potassium dichromate (K2Cr2O7)
d. cesium oxide (CsO2)
e. ethanol (CH3CH2OH)

Answer a
Ba, +2; F, −1
Answer b
C, 0; H, +1; O, −2
Answer c
K, +1; Cr, +6; O, −2
Answer d
Cs, +1; O, −½
Answer e
C, −3; H, +1; C, −1; H, +1; O, −2; H, +1

9.1.4 [Link]
Types of Redox Reactions
Many types of chemical reactions are classified as redox reactions, and it would be impossible to memorize all of them. However,
there are a few important types of redox reactions that you are likely to encounter and should be familiar with. These include:
Synthesis reactions: The formation of any compound directly from the elements is a redox reaction, for example, the formation
of water from hydrogen and oxygen:
2 H (g) + O (g) → 2 H O(g) (9.1.8)
2 2 2

Decomposition reactions: Conversely, the decomposition of a compound to its elements is also a redox reaction, as in the
electrolysis of water:
2 H O(l) → 2 H (g) + O (g) (9.1.9)
2 2 2

Combustion reactions: Many chemicals combust (burn) with oxygen. In particular, organic chemicals such as hydrocarbons
burn in the presence of oxygen to produce carbon dioxide and water as the products:
CH (g) + 2 O (g) → CO (g) + 2 H O(g) (9.1.10)
4 2 2 2

The following sections describe another important class of redox reactions: single-displacement reactions of metals in solution.

Redox Reactions of Solid Metals in Aqueous Solution

A widely encountered class of oxidation–reduction reactions is the reaction of aqueous solutions of acids or metal salts with solid
metals. An example is the corrosion of metal objects, such as the rusting of an automobile (Figure 9.1.2). Rust is formed from a
complex oxidation–reduction reaction involving dilute acid solutions that contain Cl− ions (effectively, dilute HCl), iron metal, and
oxygen. When an object rusts, iron metal reacts with HCl(aq) to produce iron(II) chloride and hydrogen gas:
Fe(s) + 2 HCl(aq) → FeCl (aq) + H (g) (9.1.11)
2 2

In subsequent steps, FeCl undergoes oxidation to form a reddish-brown precipitate of Fe(OH) .

2 3

Figure 9.1.2 : Rust Formation. The corrosion process involves an oxidation–reduction reaction in which metallic iron is converted
to Fe(OH)3, a reddish-brown solid.
Many metals dissolve through reactions of this type, which have the general form
metal + acid → salt + hydrogen (9.1.12)

Some of these reactions have important consequences. For example, it has been proposed that one factor that contributed to the fall
of the Roman Empire was the widespread use of lead in cooking utensils and pipes that carried water. Rainwater, as we have seen,
is slightly acidic, and foods such as fruits, wine, and vinegar contain organic acids. In the presence of these acids, lead dissolves:
+ 2 +
Pb(s) + 2 H (aq) → Pb (aq) + H (g) (9.1.13)
2

9.1.5 [Link]
Consequently, it has been speculated that both the water and the food consumed by Romans contained toxic levels of lead, which
resulted in widespread lead poisoning and eventual madness. Perhaps this explains why the Roman Emperor Caligula appointed his
favorite horse as consul!

Single-Displacement Reactions
Certain metals are oxidized by aqueous acid, whereas others are oxidized by aqueous solutions of various metal salts. Both types of
reactions are called single-displacement reactions, in which the ion in solution is displaced through oxidation of the metal. Two
examples of single-displacement reactions are the reduction of iron salts by zinc (Equation 9.1.14) and the reduction of silver salts
by copper (Equation 9.1.15 and Figure 9.1.3):
2 + 2 +
Zn(s) + Fe (aq) → Zn (aq) + Fe(s) (9.1.14)

+ 2 +
Cu(s) + 2 Ag (aq) → Cu (aq) + 2 Ag(s) (9.1.15)

The reaction in Equation 9.1.14 is widely used to prevent (or at least postpone) the corrosion of iron or steel objects, such as nails
and sheet metal. The process of “galvanizing” consists of applying a thin coating of zinc to the iron or steel, thus protecting it from
oxidation as long as zinc remains on the object.

Figure 9.1.3 : The Single-Displacement Reaction of Metallic Copper with a Solution of Silver Nitrate. When a copper coil is
placed in a solution of silver nitrate, silver ions are reduced to metallic silver on the copper surface, and some of the copper metal
dissolves. Note the formation of a metallic silver precipitate on the copper coil and a blue color in the surrounding solution due to
the presence of aqueous Cu ions. Figure used with permission (CC BY-SA 3.0; Toby Hudson).
2 +

The Activity Series

By observing what happens when samples of various metals are placed in contact with solutions of other metals, chemists have
arranged the metals according to the relative ease or difficulty with which they can be oxidized in a single-displacement reaction.
For example, metallic zinc reacts with iron salts, and metallic copper reacts with silver salts. Experimentally, it is found that zinc
reacts with both copper salts and silver salts, producing Zn . Zinc therefore has a greater tendency to be oxidized than does iron,
+

copper, or silver. Although zinc will not react with magnesium salts to give magnesium metal, magnesium metal will react with
zinc salts to give zinc metal:
2 + 2 +
Zn(s) + Mg (aq) → Zn (aq) + Mg(s) (9.1.16)

2 + 2 +
Mg(s) + Zn (aq) → Mg (aq) + Zn(s) (9.1.17)

Magnesium has a greater tendency to be oxidized than zinc does.

Pairwise reactions of this sort are the basis of the activity series (Figure 9.1.4), which lists metals and hydrogen in order of their
relative tendency to be oxidized. The metals at the top of the series, which have the greatest tendency to lose electrons, are the
alkali metals (group 1), the alkaline earth metals (group 2), and Al (group 13). In contrast, the metals at the bottom of the series,
which have the lowest tendency to be oxidized, are the precious metals or coinage metals—platinum, gold, silver, and copper, and
mercury, which are located in the lower right portion of the metals in the periodic table. You should be generally familiar with
which kinds of metals are active metals, which have the greatest tendency to be oxidized. (located at the top of the series) and
which are inert metals, which have the least tendency to be oxidized. (at the bottom of the series).

9.1.6 [Link]
 Figure 9.1.4 : The Activity Series
When using the activity series to predict the outcome of a reaction, keep in mind that any element will reduce compounds of the
elements below it in the series. Because magnesium is above zinc in Figure 9.1.4, magnesium metal will reduce zinc salts but not
vice versa. Similarly, the precious metals are at the bottom of the activity series, so virtually any other metal will reduce precious
metal salts to the pure precious metals. Hydrogen is included in the series, and the tendency of a metal to react with an acid is
indicated by its position relative to hydrogen in the activity series. Only those metals that lie above hydrogen in the activity series
dissolve in acids to produce H2. Because the precious metals lie below hydrogen, they do not dissolve in dilute acid and therefore
do not corrode readily. Example 9.1.2 demonstrates how a familiarity with the activity series allows you to predict the products of
many single-displacement reactions.

Example 9.1.2 : Activity

Using the activity series, predict what happens in each situation. If a reaction occurs, write the net ionic equation.
a. A strip of aluminum foil is placed in an aqueous solution of silver nitrate.
b. A few drops of liquid mercury are added to an aqueous solution of lead(II) acetate.
c. Some sulfuric acid from a car battery is accidentally spilled on the lead cable terminals.
Given: reactants
Asked for: overall reaction and net ionic equation
Strategy:
A. Locate the reactants in the activity series in Figure 9.1.4 and from their relative positions, predict whether a reaction will
occur. If a reaction does occur, identify which metal is oxidized and which is reduced.
B. Write the net ionic equation for the redox reaction.
Solution:
1. A Aluminum is an active metal that lies above silver in the activity series, so we expect a reaction to occur. According to
their relative positions, aluminum will be oxidized and dissolve, and silver ions will be reduced to silver metal. B The net
ionic equation is as follows:
+ 3 +
Al(s) + 3 Ag (aq) → Al (aq) + 3 Ag(s)

Recall from our discussion of solubilities that most nitrate salts are soluble. In this case, the nitrate ions are spectator ions
and are not involved in the reaction.

9.1.7 [Link]
 2. A Mercury lies below lead in the activity series, so no reaction will occur.
3. A Lead is above hydrogen in the activity series, so the lead terminals will be oxidized, and the acid will be reduced to form
H2. B From our discussion of solubilities, recall that Pb2+ and SO42− form insoluble lead(II) sulfate. In this case, the sulfate
ions are not spectator ions, and the reaction is as follows:
+ 2 −
Pb(s) + 2 H (aq) + SO (aq) → PbSO (s) + H (g)
4 4 2

Lead(II) sulfate is the white solid that forms on corroded battery terminals.

Corroded battery terminals. The white solid is lead(II) sulfate, formed from the reaction of solid lead with a solution of sulfuric
acid.

Exercise 9.1.2
Using the activity series, predict what happens in each situation. If a reaction occurs, write the net ionic equation.
a. A strip of chromium metal is placed in an aqueous solution of aluminum chloride.
b. A strip of zinc is placed in an aqueous solution of chromium(III) nitrate.
c. A piece of aluminum foil is dropped into a glass that contains vinegar (the active ingredient is acetic acid).

Answer a
no reaction

Answer b
3+ 2+
3Zn(s) + 2C r (aq) → 3Z n (aq) + 2C r(s)

Answer c
\(2Al(s) + 6CH_3CO_2H(aq) \rightarrow 2Al^{3+}(aq) + 6CH_3CO_2^-(aq) + 3H_2(g)\

Summary
Oxidation–reduction reactions are balanced by separating the overall chemical equation into an oxidation equation and a reduction
equation. In oxidation–reduction reactions, electrons are transferred from one substance or atom to another. We can balance
oxidation–reduction reactions in solution using the oxidation state method (Table 9.1.1), in which the overall reaction is separated
into an oxidation equation and a reduction equation. There are many types of redox reactions. Single-displacement reactions are
reactions of metals with either acids or another metal salt that result in dissolution of the first metal and precipitation of a second
(or evolution of hydrogen gas). The outcome of these reactions can be predicted using the activity series (Figure 9.1.4), which
arranges metals and H2 in decreasing order of their tendency to be oxidized. Any metal will reduce metal ions below it in the
activity series. Active metals lie at the top of the activity series, whereas inert metals are at the bottom of the activity series.

9.1: Oxidation-Reduction Reactions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

9.1.8 [Link]
9.2: Standard Reduction Potentials
Skills to Develop
To use redox potentials to predict whether a reaction is spontaneous.
To balance redox reactions using half-reactions.

In a galvanic cell, current is produced when electrons flow externally through the circuit from the anode to the cathode because of a
difference in potential energy between the two electrodes in the electrochemical cell. In the Zn/Cu system, the valence electrons in
zinc have a substantially higher potential energy than the valence electrons in copper because of shielding of the s electrons of zinc
by the electrons in filled d orbitals. Hence electrons flow spontaneously from zinc to copper(II) ions, forming zinc(II) ions and
metallic copper. Just like water flowing spontaneously downhill, which can be made to do work by forcing a waterwheel, the flow
of electrons from a higher potential energy to a lower one can also be harnessed to perform work.

Figure 9.2.1 : Potential Energy Difference in the Zn/Cu System. The potential energy of a system consisting of metallic Zn and
aqueous Cu2+ ions is greater than the potential energy of a system consisting of metallic Cu and aqueous \(Zn^{2+}\) ions. Much
of this potential energy difference is because the valence electrons of metallic Zn are higher in energy than the valence electrons of
metallic Cu. Because the Zn(s) + Cu2+(aq) system is higher in energy by 1.10 V than the Cu(s) + Zn2+(aq) system, energy is
released when electrons are transferred from Zn to Cu2+ to form Cu and Zn2+.
Because the potential energy of valence electrons differs greatly from one substance to another, the voltage of a galvanic cell
depends partly on the identity of the reacting substances. If we construct a galvanic cell similar to the one in part (a) in Figure 9.2.1
but instead of copper use a strip of cobalt metal and 1 M Co2+ in the cathode compartment, the measured voltage is not 1.10 V but
0.51 V. Thus we can conclude that the difference in potential energy between the valence electrons of cobalt and zinc is less than
the difference between the valence electrons of copper and zinc by 0.59 V.
The measured potential of a cell also depends strongly on the concentrations of the reacting species and the temperature of the
system. To develop a scale of relative potentials that will allow us to predict the direction of an electrochemical reaction and the
magnitude of the driving force for the reaction, the potentials for oxidations and reductions of different substances must be
measured under comparable conditions. To do this, chemists use the standard cell potential (E°cell), defined as the potential of a
cell measured under standard conditions—that is, with all species in their standard states (1 M for solutions, concentrated solutions
of salts (about 1 M) generally do not exhibit ideal behavior, and the actual standard state corresponds to an activity of 1 rather than
a concentration of 1 M. Corrections for non ideal behavior are important for precise quantitative work but not for the more
qualitative approach that we are taking here. 1 atm for gases, pure solids or pure liquids for other substances) and at a fixed
temperature, usually 25°C.

Measured redox potentials depend on the potential energy of valence electrons, the
concentrations of the species in the reaction, and the temperature of the system.

9.2.1 [Link]
Measuring Standard Electrode Potentials
It is physically impossible to measure the potential of a single electrode: only the difference between the potentials of two
electrodes can be measured (this is analogous to measuring absolute enthalpies or free energies). Recall that only differences in
enthalpy and free energy can be measured.) We can, however, compare the standard cell potentials for two different galvanic cells
that have one kind of electrode in common. This allows us to measure the potential difference between two dissimilar electrodes.
For example, the measured standard cell potential (E°) for the Zn/Cu system is 1.10 V, whereas E° for the corresponding Zn/Co
system is 0.51 V. This implies that the potential difference between the Co and Cu electrodes is 1.10 V − 0.51 V = 0.59 V. In fact,
that is exactly the potential measured under standard conditions if a cell is constructed with the following cell diagram:
2+ 2+
C o(s) ∣ C o (aq, 1M ) ∥ C u (aq, 1M ) ∣ C u(s) E° = 0.59 V (9.2.1)

This cell diagram corresponds to the oxidation of a cobalt anode and the reduction of Cu2+ in solution at the copper cathode.
All tabulated values of standard electrode potentials by convention are listed for a reaction written as a reduction, not as an
oxidation, to be able to compare standard potentials for different substances (Table P1). The standard cell potential (E°cell) is
therefore the difference between the tabulated reduction potentials of the two half-reactions, not their sum:
E °cell = E °cathode − E °anode (9.2.2)

In contrast, recall that half-reactions are written to show the reduction and oxidation reactions that actually occur in the cell, so the
overall cell reaction is written as the sum of the two half-reactions. According to Equation 9.2.2, when we know the standard
potential for any single half-reaction, we can obtain the value of the standard potential of many other half-reactions by measuring
the standard potential of the corresponding cell.

The overall cell reaction is the sum of the two half-reactions, but the cell potential is the difference between the reduction
potentials:
E °cell = E °cathode − E °anode (9.2.3)

Figure 9.2.2 : The Standard Hydrogen Electrode. The SHE consists of platinum wire that is connected to a Pt surface in contact
with an aqueous solution containing 1 M H+ in equilibrium with H2 gas at a pressure of 1 atm. In the molecular view, the Pt
surface catalyzes the oxidation of hydrogen molecules to protons or the reduction of protons to hydrogen gas. (Water is omitted for
clarity.) The standard potential of the SHE is arbitrarily assigned a value of 0 V.
Although it is impossible to measure the potential of any electrode directly, we can choose a reference electrode whose potential is
defined as 0 V under standard conditions. The standard hydrogen electrode (SHE) is universally used for this purpose and is
assigned a standard potential of 0 V. It consists of a strip of platinum wire in contact with an aqueous solution containing 1 M H+.

9.2.2 [Link]
The [H+] in solution is in equilibrium with H2 gas at a pressure of 1 atm at the Pt-solution interface (Figure 9.2.2 ). Protons are
reduced or hydrogen molecules are oxidized at the Pt surface according to the following equation:
+ −
2H + 2e ⇌ H2(g) (9.2.4)
(aq)

One especially attractive feature of the SHE is that the Pt metal electrode is not consumed during the reaction.

Figure 9.2.3 : Determining a Standard Electrode Potential Using a Standard Hydrogen Electrode. The voltmeter shows that the
standard cell potential of a galvanic cell consisting of a SHE and a Zn/Zn2+ couple is E° = 0.76 V. Because the zinc electrode in
cell

this cell dissolves spontaneously to form Zn2+(aq) ions while H+(aq) ions are reduced to H2 at the platinum surface, the standard
electrode potential of the Zn2+/Zn couple is −0.76 V.
Figure 9.2.3 shows a galvanic cell that consists of a SHE in one beaker and a Zn strip in another beaker containing a solution of
Zn2+ ions. When the circuit is closed, the voltmeter indicates a potential of 0.76 V. The zinc electrode begins to dissolve to form
Zn2+, and H+ ions are reduced to H2 in the other compartment. Thus the hydrogen electrode is the cathode, and the zinc electrode is
the anode. The diagram for this galvanic cell is as follows:
2+ +
Z n(s) ∣ Z n ∥ H (aq, 1M ) ∣ H2 (g, 1atm) ∣ P t(s) (9.2.5)
(aq)

The half-reactions that actually occur in the cell and their corresponding electrode potentials are as follows:
cathode:
+ −
2H + 2e → H2(g) E °cathode = 0V (9.2.6)
(aq)

anode:
2+ −
Z n(s) → Z n + 2e E °anode = −0.76 V (9.2.7)
(aq)

overall:
+ 2+
Z n(s) + 2 H → Zn + H2(g) (9.2.8)
(aq) (aq)

E °cell = E °cathode − E °anode = 0.76 V (9.2.9)

Although the reaction at the anode is an oxidation, by convention its tabulated E° value is reported as a reduction potential. The
potential of a half-reaction measured against the SHE under standard conditions is called the standard electrode potential for that

9.2.3 [Link]
[Link] this example, the standard reduction potential for Zn2+(aq) + 2e− → Zn(s) is −0.76 V, which means that the
standard electrode potential for the reaction that occurs at the anode, the oxidation of Zn to Zn2+, often called the Zn/Zn2+ redox
couple, or the Zn/Zn2+ couple, is −(−0.76 V) = 0.76 V. We must therefore subtract E°anode from E°cathode to obtain
E °cell : 0 V − (−0.76 V ) = 0.76 V (9.2.10)

Because electrical potential is the energy needed to move a charged particle in an electric field, standard electrode potentials for
half-reactions are intensive properties and do not depend on the amount of substance involved. Consequently, E° values are
independent of the stoichiometric coefficients for the half-reaction, and, most important, the coefficients used to produce a
balanced overall reaction do not affect the value of the cell potential.

E° values do NOT depend on the stoichiometric coefficients for a half-reaction, because it

is an intensive property.

Standard Electrode Potentials

To measure the potential of the Cu/Cu2+ couple, we can construct a galvanic cell analogous to the one shown in Figure 9.2.3 but
containing a Cu/Cu2+ couple in the sample compartment instead of Zn/Zn2+. When we close the circuit this time, the measured
potential for the cell is negative (−0.34 V) rather than positive. The negative value of E° indicates that the direction of
cell

spontaneous electron flow is the opposite of that for the Zn/Zn2+ couple. Hence the reactions that occur spontaneously, indicated by
a positive E° , are the reduction of Cu2+ to Cu at the copper electrode. The copper electrode gains mass as the reaction proceeds,
cell

and H2 is oxidized to H+ at the platinum electrode. In this cell, the copper strip is the cathode, and the hydrogen electrode is the
anode. The cell diagram therefore is written with the SHE on the left and the Cu2+/Cu couple on the right:
+ 2+
P t(s) ∣ H2 (g, 1atm) ∣ H (aq, 1 M ) ∥ C u (aq, 1M ) ∣ C u(s) (9.2.11)

The half-cell reactions and potentials of the spontaneous reaction are as follows:
Cathode:
2+ −
Cu (aq) + 2 e → C u(g) E °cathode = 0.34 V (9.2.12)

Anode:
+ −
H2(g) → 2 H + 2e E °anode = 0 V (9.2.13)
(aq)

Overall:
2+ +
H2(g) + C u → 2H + C u(s) (9.2.14)
(aq) (aq)

E °cell = E °cathode − E °anode = 0.34 V (9.2.15)

Thus the standard electrode potential for the Cu2+/Cu couple is 0.34 V.

Calculating Standard Cell Potentials

The standard cell potential for a redox reaction (E°cell) is a measure of the tendency of reactants in their standard states to form
products in their standard states; consequently, it is a measure of the driving force for the reaction, which earlier we called voltage.
We can use the two standard electrode potentials we found earlier to calculate the standard potential for the Zn/Cu cell represented
by the following cell diagram:
2+ 2+
Zn(s) ∣ Z n (aq, 1M ) ∥ C u (aq, 1M ) ∣ C u(s) (9.2.16)

We know the values of E°anode for the reduction of Zn2+ and E°cathode for the reduction of Cu2+, so we can calculate E° cell :
cathode:
2+ −
Cu + 2e → C u(s) E °cathode = 0.34 V (9.2.17)
(aq)

anode:
2+ −
Z n(s) → Z n (aq, 1M ) + 2 e E °anode = −0.76 V (9.2.18)

9.2.4 [Link]
 overall:
2+ 2+
Z n(s) + C u → Zn + C u(s) (9.2.19)
(aq) (aq)

E °cell = E °cathode − E °anode = 1.10 V (9.2.20)

This is the same value that is observed experimentally. If the value of E° is positive, the reaction will occur spontaneously as
cell

written. If the value of E° cell is negative, then the reaction is not spontaneous, and it will not occur as written under standard
conditions; it will, however, proceed spontaneously in the opposite direction. As we shall see in Section 20.9, this does not mean
that the reaction cannot be made to occur at all under standard conditions. With a sufficient input of electrical energy, virtually any
reaction can be forced to occur. Example 9.2.2 and its corresponding exercise illustrate how we can use measured cell potentials to
calculate standard potentials for redox couples.

A positive E° means that the reaction will occur spontaneously as written. A negative
cell

E° cellmeans that the reaction will proceed spontaneously in the opposite direction.
Example 9.2.1
A galvanic cell with a measured standard cell potential of 0.27 V is constructed using two beakers connected by a salt bridge.
One beaker contains a strip of gallium metal immersed in a 1 M solution of GaCl3, and the other contains a piece of nickel
immersed in a 1 M solution of NiCl2. The half-reactions that occur when the compartments are connected are as follows:
cathode: Ni2+(aq) + 2e− → Ni(s)
anode: Ga(s) → Ga3+(aq) + 3e−
If the potential for the oxidation of Ga to Ga3+ is 0.55 V under standard conditions, what is the potential for the oxidation of Ni
to Ni2+?
Given: galvanic cell, half-reactions, standard cell potential, and potential for the oxidation half-reaction under standard
conditions
Asked for: standard electrode potential of reaction occurring at the cathode
Strategy:
A. Write the equation for the half-reaction that occurs at the anode along with the value of the standard electrode potential for
the half-reaction.
B. Use Equation 9.2.2 to calculate the standard electrode potential for the half-reaction that occurs at the cathode. Then reverse
the sign to obtain the potential for the corresponding oxidation half-reaction under standard conditions.
Solution:
A We have been given the potential for the oxidation of Ga to Ga3+ under standard conditions, but to report the standard
electrode potential, we must reverse the sign. For the reduction reaction Ga3+(aq) + 3e− → Ga(s), E°anode = −0.55 V.
B Using the value given for E° and the calculated value of E°anode, we can calculate the standard potential for the reduction
cell

of Ni2+ to Ni from Equation 9.2.2:

E °cell = E °cathode − E °anode

0.27 V = E°cathode − (−0.55 V)

E°cathode = −0.28 V
This is the standard electrode potential for the reaction Ni2+(aq) + 2e− → Ni(s). Because we are asked for the potential for the
oxidation of Ni to Ni2+ under standard conditions, we must reverse the sign of E°cathode. Thus E° = −(−0.28 V) = 0.28 V for the
oxidation. With three electrons consumed in the reduction and two produced in the oxidation, the overall reaction is not
balanced. Recall, however, that standard potentials are independent of stoichiometry.

Exercise 9.2.1
A galvanic cell is constructed with one compartment that contains a mercury electrode immersed in a 1 M aqueous solution of
mercuric acetate H g(C H C O ) and one compartment that contains a strip of magnesium immersed in a 1 M aqueous solution
3 2 2

of M gC l . When the compartments are connected, a potential of 3.22 V is measured and the following half-reactions occur:
2

9.2.5 [Link]
 cathode: Hg2+(aq) + 2e− → Hg(l)
anode: Mg(s) → Mg2+(aq) + 2e−
If the potential for the oxidation of Mg to Mg2+ is 2.37 V under standard conditions, what is the standard electrode potential for
the reaction that occurs at the anode?

Answer
0.85 V

Summary
Redox reactions can be balanced using the half-reaction method. The standard cell potential is a measure of the driving force for
the reaction. E ° = E °
cell cathode− E° anode The flow of electrons in an electrochemical cell depends on the identity of the reacting
substances, the difference in the potential energy of their valence electrons, and their concentrations. The potential of the cell under
standard conditions (1 M for solutions, 1 atm for gases, pure solids or liquids for other substances) and at a fixed temperature
(25°C) is called the standard cell potential (E°cell). Only the difference between the potentials of two electrodes can be measured.
By convention, all tabulated values of standard electrode potentials are listed as standard reduction potentials. The overall cell
potential is the reduction potential of the reductive half-reaction minus the reduction potential of the oxidative half-reaction (E°cell
= E°cathode − E°anode). The potential of the standard hydrogen electrode (SHE) is defined as 0 V under standard conditions. The
potential of a half-reaction measured against the SHE under standard conditions is called its standard electrode potential. The
standard cell potential is a measure of the driving force for a given redox reaction. All E° values are independent of the
stoichiometric coefficients for the half-reaction. Redox reactions can be balanced using the half-reaction method, in which the
overall redox reaction is divided into an oxidation half-reaction and a reduction half-reaction, each balanced for mass and charge.
The half-reactions selected from tabulated lists must exactly reflect reaction conditions. In an alternative method, the atoms in each
half-reaction are balanced, and then the charges are balanced. Whenever a half-reaction is reversed, the sign of E° corresponding to
that reaction must also be reversed. If E° is positive, the reaction will occur spontaneously under standard conditions. If E°
cell cell

is negative, then the reaction is not spontaneous under standard conditions, although it will proceed spontaneously in the opposite
direction. The potential of an indicator electrode is related to the concentration of the substance being measured, whereas the
potential of the reference electrode is held constant. Whether reduction or oxidation occurs depends on the potential of the sample
versus the potential of the reference electrode. In addition to the SHE, other reference electrodes are the silver–silver chloride
electrode; the saturated calomel electrode (SCE); the glass electrode, which is commonly used to measure pH; and ion-selective
electrodes, which depend on the concentration of a single ionic species in solution. Differences in potential between the SHE and
other reference electrodes must be included when calculating values for E°.

9.2: Standard Reduction Potentials is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

9.2.6 [Link]
9.3 Cell Potential, Gibbs Free Energy, and Equilibrium
Skills to Develop
To understand the relationship between cell potential and the equilibrium constant.
To use cell potentials to calculate solution concentrations.

Changes in reaction conditions can have a tremendous effect on the course of a redox reaction. For example, under standard conditions,
the reaction of Co(s) with Ni2+(aq) to form Ni(s) and Co2+(aq) occurs spontaneously, but if we reduce the concentration of Ni2+ by a factor
of 100, so that [Ni2+] is 0.01 M, then the reverse reaction occurs spontaneously instead. The relationship between voltage and
concentration is one of the factors that must be understood to predict whether a reaction will be spontaneous.

The Relationship between Cell Potential & Free Energy

Electrochemical cells convert chemical energy to electrical energy and vice versa. The total amount of energy produced by an
electrochemical cell, and thus the amount of energy available to do electrical work, depends on both the cell potential and the total number
of electrons that are transferred from the reductant to the oxidant during the course of a reaction. The resulting electric current is measured
in coulombs (C), an SI unit that measures the number of electrons passing a given point in 1 s. A coulomb relates energy (in joules) to
electrical potential (in volts). Electric current is measured in amperes (A); 1 A is defined as the flow of 1 C/s past a given point (1 C = 1
A·s):
1 J
= 1 C = A⋅s (1)
1 V

In chemical reactions, however, we need to relate the coulomb to the charge on a mole of electrons. Multiplying the charge on the electron
by Avogadro’s number gives us the charge on 1 mol of electrons, which is called the faraday (F), named after the English physicist and
chemist Michael Faraday (1791–1867):
23
6.02214 × 10
−19
F = (1.60218 × 10 C) ( ) (2)
−
1 mol e
4 − −
= 9.64855 × 10 C/mol e ≃ 96, 486/(V ⋅ mol e ) (3)

The total charge transferred from the reductant to the oxidant is therefore nF, where n is the number of moles of electrons.
Michael Faraday (1791–1867)
Faraday was a British physicist and chemist who was arguably one of the greatest experimental scientists in history. The son of a
blacksmith, Faraday was self-educated and became an apprentice bookbinder at age 14 before turning to science. His experiments in
electricity and magnetism made electricity a routine tool in science and led to both the electric motor and the electric generator. He
discovered the phenomenon of electrolysis and laid the foundations of electrochemistry. In fact, most of the specialized terms
introduced in this chapter (electrode, anode, cathode, and so forth) are due to Faraday. In addition, he discovered benzene and invented
the system of oxidation state numbers that we use today. Faraday is probably best known for “The Chemical History of a Candle,” a
series of public lectures on the chemistry and physics of flames.

The maximum amount of work that can be produced by an electrochemical cell (w max ) is equal to the product of the cell potential (E
cell
∘
)
and the total charge transferred during the reaction (nF):

wmax = nF Ecell (4)

Work is expressed as a negative number because work is being done by a system (an electrochemical cell with a positive potential) on its
surroundings.
The change in free energy (ΔG) is also a measure of the maximum amount of work that can be performed during a chemical process (
ΔG = w max). Consequently, there must be a relationship between the potential of an electrochemical cell and ΔG; this relationship is as
follows:
ΔG = −nF Ecell (5)

A spontaneous redox reaction is therefore characterized by a negative value of ΔG and a positive value of E , consistent with our
∘
cell

earlier discussions. When both reactants and products are in their standard states, the relationship between ΔG° and E is as follows: ∘
cell

∘ ∘
ΔG = −nF E (6)
cell

A spontaneous redox reaction is characterized by a negative value of ΔG°, which corresponds to a positive value of E°cell.

1 [Link]
 Example 1
Suppose you want to prepare elemental bromine from bromide using the dichromate ion as an oxidant. Using the data in Table P2,
calculate the free-energy change (ΔG°) for this redox reaction under standard conditions. Is the reaction spontaneous?
Given: redox reaction
Asked for: ΔG° for the reaction and spontaneity
Strategy:
A. From the relevant half-reactions and the corresponding values of E°, write the overall reaction and calculate E°cell.
B. Determine the number of electrons transferred in the overall reaction. Then use Equation 6 to calculate ΔG°. If ΔG° is negative,
then the reaction is spontaneous.
Solution:
A As always, the first step is to write the relevant half-reactions and use them to obtain the overall reaction and the magnitude of E°.
From Table P2, we can find the reduction and oxidation half-reactions and corresponding E° values:
2− + − 3+ ∘
cathode: C r2 O (aq) + 14 H (aq) + 6 e → 2C r (aq) + 7 H2 O(l) E = 1.23 V (7)
7 cathode

− − ∘
anode: 2Br (aq) → Br2 (aq) + 2 e E = 1.09 V (8)
anode

To obtain the overall balanced chemical equation, we must multiply both sides of the oxidation half-reaction by 3 to obtain the same
number of electrons as in the reduction half-reaction, remembering that the magnitude of E° is not affected:
2− + − 3+ ∘
cathode: C r2 O (aq) + 14 H (aq) + 6 e → 2C r (aq) + 7 H2 O(l) E = 1.23 V (9)
7 cathode
− − ∘
anode: 6Br (aq) → 3Br2 (aq) + 6 e E = 1.09 V (10)
anode

2− − + 3+ ∘
overall: C r2 O (aq) + 6Br (aq) + 14 H (aq) → 2C r (aq) + 3Br2 (aq) + 7 H2 O(l) E = 0.14 V (11)
7 cell

B We can now calculate ΔG° using Equation 6. Because six electrons are transferred in the overall reaction, the value of n is 6:
∘ ∘
ΔG = −(n)(F )(E ) = −(6 mole)[96, 468 J/(V ⋅ mol)(0.14 V)] (12)
cell

4
= −8.1 ×10 J (13)
2−
= −81 kJ/mol Cr2 O (14)
7

Thus ΔG° is −81 kJ for the reaction as written, and the reaction is spontaneous.

Exercise 1
Use the data in Table P2 to calculate ΔG° for the reduction of ferric ion by iodide:
3 + − 2 +
2 Fe (aq) + 2 I (aq) → 2 Fe (aq) + I (s)
2

Is the reaction spontaneous?

Answer
−44 kJ/mol I2; yes

Potentials for the Sums of Half-Reactions

Although Table P2 list several half-reactions, many more are known. When the standard potential for a half-reaction is not available, we
can use relationships between standard potentials and free energy to obtain the potential of any other half-reaction that can be written as
the sum of two or more half-reactions whose standard potentials are available. For example, the potential for the reduction of Fe3+(aq) to
Fe(s) is not listed in the table, but two related reductions are given:
3+ − 2+ ∘
Fe (aq) + e → Fe (aq) E = +0.77V (15)

2+ − ∘
Fe (aq) + 2 e → F e(aq) E = −0.45V (16)

Although the sum of these two half-reactions gives the desired half-reaction, we cannot simply add the potentials of two reductive half-
reactions to obtain the potential of a third reductive half-reaction because E° is not a state function. However, because ΔG° is a state
function, the sum of the ΔG° values for the individual reactions gives us ΔG° for the overall reaction, which is proportional to both the
potential and the number of electrons (n) transferred. To obtain the value of E° for the overall half-reaction, we first must add the values of
ΔG° (= −nFE°) for each individual half-reaction to obtain ΔG° for the overall half-reaction:

2 [Link]
 3+ − 2+ ∘
Fe (aq) + e → Fe (aq) ΔG = −(1)(F )(0.77 V) (17)

2+ − ∘
Fe (aq) + 2 e → Fe(s) ΔG = −(2)(F )(−.045 V) (18)
3+ − ∘
Fe (aq) + 3 e → Fe(s) ΔG = [−(1)(F )(0.77 V)] + [−(2)(F )(−0.45 V)] (19)

Solving the last expression for ΔG° for the overall half-reaction,
∘
ΔG = F [(−0.77V ) + (−2)(−0.45V )] = F (0.13V ) (20)

Three electrons (n = 3) are transferred in the overall reaction, so substituting into Equation 6 and solving for E° gives the following:
∘ ∘
ΔG = −nF E (21)
cell

∘
F (0.13 V) = −(3)(F )(E ) (22)
cell

0.13 V
∘
E =− = −0.043 V (23)
3

This value of E° is very different from the value that is obtained by simply adding the potentials for the two half-reactions (0.32 V) and
even has the opposite sign.

Values of E° for half-reactions cannot be added to give E° for the sum of the half-reactions; only
values of ΔG° = −nFE°cell for half-reactions can be added.

The Relationship between Cell Potential & the Equilibrium Constant

We can use the relationship between ΔG and the equilibrium constant K, to obtain a relationship between E and K . Recall that for a
∘ ∘
cell

general reaction of the type aA + bB → cC + dD , the standard free-energy change and the equilibrium constant are related by the
following equation:
ΔG° = −RT ln K (24)

Given the relationship between the standard free-energy change and the standard cell potential (Equation 6), we can write
∘
−nF E = −RT ln K (25)
cell

Rearranging this equation,

RT
∘
E =( ) ln K (26)
cell
nF

For T = 298 K, Equation 25 can be simplified as follows:

RT [8.314 J/(mol ⋅ K)(298 K)] 0.0591 V
∘
E =( ) ln K = [ ] 2.303 log K = ( ) log K (27)
cell
nF n[96, 486 J/(V ⋅ mol)] n

Thus E is directly proportional to the logarithm of the equilibrium constant. This means that large equilibrium constants correspond to
∘
cell

large positive values of E and vice versa.

∘
cell

Example 2
Use the data in Table P2 to calculate the equilibrium constant for the reaction of metallic lead with PbO2 in the presence of sulfate ions
to give PbSO4 under standard conditions. (This reaction occurs when a car battery is discharged.) Report your answer to two significant
figures.
Given: redox reaction
Asked for: K
Strategy:
A. Write the relevant half-reactions and potentials. From these, obtain the overall reaction and E°cell.
B. Determine the number of electrons transferred in the overall reaction. Use Equation 27 to solve for log K and then K .
Solution:
A The relevant half-reactions and potentials from Table P2 are as follows:
2− + − ∘
cathode: PbO2 (s) + SO (aq) + 4 H (aq) + 2 e → PbSO4 (s) + 2 H2 O(l) E = 1.69 V (28)
4 cathode

2− − ∘
anode: Pb(s) + SO (aq) → PbSO4 (s) + 2 e E = −0.36 V (29)
4 anode

2− + ∘
overall: Pb(s) + PbO2 (s) + 2SO (aq) + 4 H (aq) → 2PbSO4 (s) + 2 H2 O(l) E = 2.05 V (30)
4 cell

3 [Link]
 B Two electrons are transferred in the overall reaction, so n = 2. Solving Equation 27 for log K and inserting the values of n and E°,
∘
nE 2(2.05 V)
log K = = = 69.37 (31)
0.0591 V 0.0591 V
69
K = 2.3 × 10 (32)

Thus the equilibrium lies far to the right, favoring a discharged battery (as anyone who has ever tried unsuccessfully to start a car after
letting it sit for a long time will know).

Exercise 3
Use the data in Table P2 to calculate the equilibrium constant for the reaction of Sn2+(aq) with oxygen to produce Sn4+(aq) and water
under standard conditions. Report your answer to two significant figures. The reaction is as follows:
2+ + 4+
2S n + O2(g) + 4 H ⇌ 2S n + 2 H2 O(l) (33)
(aq) (aq) (aq)

Answer
73
1.2 × 10

Figure 1 summarizes the relationships that we have developed based on properties of the system—that is, based on the equilibrium
constant, standard free-energy change, and standard cell potential—and the criteria for spontaneity (ΔG° < 0). Unfortunately, these criteria
apply only to systems in which all reactants and products are present in their standard states, a situation that is seldom encountered in the
real world. A more generally useful relationship between cell potential and reactant and product concentrations, as we are about to see,
uses the relationship between ΔG and the reaction quotient Q.

Figure 1 : The Relationships among Criteria for Thermodynamic Spontaneity. The three properties of a system that can be used to predict
the spontaneity of a redox reaction under standard conditions are K, ΔG°, and E°cell. If we know the value of one of these quantities, then
these relationships enable us to calculate the value of the other two. The signs of ΔG° and E°cell and the magnitude of K determine the
direction of spontaneous reaction under standard conditions.

Summary
A coulomb (C) relates electrical potential, expressed in volts, and energy, expressed in joules. The current generated from a redox reaction
is measured in amperes (A), where 1 A is defined as the flow of 1 C/s past a given point. The faraday (F) is Avogadro’s number multiplied
by the charge on an electron and corresponds to the charge on 1 mol of electrons. The product of the cell potential and the total charge is
the maximum amount of energy available to do work, which is related to the change in free energy that occurs during the chemical
process. Adding together the ΔG values for the half-reactions gives ΔG for the overall reaction, which is proportional to both the potential
and the number of electrons (n) transferred. Spontaneous redox reactions have a negative ΔG and therefore a positive Ecell. Because the
equilibrium constant K is related to ΔG, E°cell and K are also related. Large equilibrium constants correspond to large positive values of
E°.

9.3 Cell Potential, Gibbs Free Energy, and Equilibrium is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by
LibreTexts.

4 [Link]
9.4: Batteries: Using Chemistry to Generate Electricity
Because galvanic cells can be self-contained and portable, they can be used as batteries and fuel cells. A battery (storage cell) is a galvanic cell (or
a series of galvanic cells) that contains all the reactants needed to produce electricity. In contrast, a fuel cell is a galvanic cell that requires a constant
external supply of one or more reactants to generate electricity. In this section, we describe the chemistry behind some of the more common types of
batteries and fuel cells.

Batteries
There are two basic kinds of batteries: disposable, or primary, batteries, in which the electrode reactions are effectively irreversible and which cannot
be recharged; and rechargeable, or secondary, batteries, which form an insoluble product that adheres to the electrodes. These batteries can be
recharged by applying an electrical potential in the reverse direction. The recharging process temporarily converts a rechargeable battery from a
galvanic cell to an electrolytic cell.
Batteries are cleverly engineered devices that are based on the same fundamental laws as galvanic cells. The major difference between batteries and
the galvanic cells we have previously described is that commercial batteries use solids or pastes rather than solutions as reactants to maximize the
electrical output per unit mass. The use of highly concentrated or solid reactants has another beneficial effect: the concentrations of the reactants and
the products do not change greatly as the battery is discharged; consequently, the output voltage remains remarkably constant during the discharge
process. This behavior is in contrast to that of the Zn/Cu cell, whose output decreases logarithmically as the reaction proceeds (Figure 9.4.1). When
a battery consists of more than one galvanic cell, the cells are usually connected in series—that is, with the positive (+) terminal of one cell
connected to the negative (−) terminal of the next, and so forth. The overall voltage of the battery is therefore the sum of the voltages of the
individual cells.

Figure 9.4.1 : Three Kinds of Primary (Nonrechargeable) Batteries. (a) A Leclanché dry cell is actually a “wet cell,” in which the electrolyte is an
acidic water-based paste containing MnO2, NH4Cl, ZnCl2, graphite, and starch. Though inexpensive to manufacture, the cell is not very efficient in
producing electrical energy and has a limited shelf life. (b) In a button battery, the anode is a zinc–mercury amalgam, and the cathode can be either
HgO (shown here) or Ag2O as the oxidant. Button batteries are reliable and have a high output-to-mass ratio, which allows them to be used in
applications such as calculators and watches, where their small size is crucial. (c) A lithium–iodine battery consists of two cells separated by a
metallic nickel mesh that collects charge from the anodes. The anode is lithium metal, and the cathode is a solid complex of I2. The electrolyte is a
layer of solid LiI that allows Li+ ions to diffuse from the cathode to the anode. Although this type of battery produces only a relatively small current,
it is highly reliable and long-lived.

The major difference between batteries and the galvanic cells is that commercial typically batteries use solids or pastes rather than solutions as
reactants to maximize the electrical output per unit mass. An obvious exception is the standard car battery which used solution phase chemistry.

Leclanché Dry Cell

The dry cell, by far the most common type of battery, is used in flashlights, electronic devices such as the Walkman and Game Boy, and many other
devices. Although the dry cell was patented in 1866 by the French chemist Georges Leclanché and more than 5 billion such cells are sold every year,
the details of its electrode chemistry are still not completely understood. In spite of its name, the Leclanché dry cell is actually a “wet cell”: the
electrolyte is an acidic water-based paste containing M nO , N H C l, ZnC l , graphite, and starch (part (a) in Figure 9.4.1). The half-reactions at
2 4 2

the anode and the cathode can be summarized as follows:

cathode (reduction):
+ −
2M nO2(s) + 2N H + 2e → M n2 O3(s) + 2N H3(aq) + H2 O(l) (9.4.1)
4(aq)

9.4.1 [Link]
 anode (oxidation):
2+ −
Z n(s) → Z n + 2e (9.4.2)
(aq)

The Zn ions formed by the oxidation of

2+
Zn(s) at the anode react with N H3 formed at the cathode and −
Cl ions present in solution, so the
overall cell reaction is as follows:
overall:

2M nO2(s) + 2N H4 C l(aq) + Z n(s) → M n2 O3(s) + Zn(N H3 )2 C l2(s) + H2 O(l) (9.4.3)

The dry cell produces about 1.55 V and is inexpensive to manufacture. It is not, however, very efficient in producing electrical energy because only
the relatively small fraction of the M nO that is near the cathode is actually reduced and only a small fraction of the zinc cathode is actually
2

consumed as the cell discharges. In addition, dry cells have a limited shelf life because the Zn anode reacts spontaneously with N H C l in the 4

electrolyte, causing the case to corrode and allowing the contents to leak out.

Source: Photo courtesy of Mitchclanky2008, [Link]

The alkaline battery is essentially a Leclanché cell adapted to operate under alkaline, or basic, conditions. The half-reactions that occur in an
alkaline battery are as follows:
cathode (reduction)
− −
2M nO2(s) + H2 O(l) + 2 e → M n2 O3(s) + 2OH (9.4.4)
(aq)

anode (oxidation):
− −
Z n(s) + 2OH → ZnO(s) + H2 O(l) + 2 e (9.4.5)
(aq)

overall:

Z n(s) + 2M nO2(s) → ZnO(s) + M n2 O3(s) (9.4.6)

This battery also produces about 1.5 V, but it has a longer shelf life and more constant output voltage as the cell is discharged than the Leclanché dry
cell. Although the alkaline battery is more expensive to produce than the Leclanché dry cell, the improved performance makes this battery more
cost-effective.

Button Batteries
Although some of the small button batteries used to power watches, calculators, and cameras are miniature alkaline cells, most are based on a
completely different chemistry. In these "button" batteries, the anode is a zinc–mercury amalgam rather than pure zinc, and the cathode uses either
H gO or Ag O as the oxidant rather than M nO (part (b) in Figure 9.4.1).
2 2

Button batteries. Photo courtesy of Gerhard H Wrodnigg, Images used with permission from Wikipedia
The cathode and overall reactions and cell output for these two types of button batteries are as follows:
cathode (Hg):
− −
H gO(s) + H2 O(l) + 2 e → H g(l) + 2OH (9.4.7)
(aq)

overall (Hg):

9.4.2 [Link]
 Z n(s) + 2H gO(s) → H g(l) + ZnO(s) (9.4.8)

with E cell = 1.35 V

cathode (Ag):
− −
Ag2 O(s) + H2 O(l) + 2 e → 2Ag(s) + 2OH (9.4.9)
(aq)

overall (Ag):

Z n(s) + 2Ag2 O(s) → 2Ag(s) + ZnO(s) (9.4.10)

with E cell = 1.6 V

The major advantages of the mercury and silver cells are their reliability and their high output-to-mass ratio. These factors make them ideal for
applications where small size is crucial, as in cameras and hearing aids. The disadvantages are the expense and the environmental problems caused
by the disposal of heavy metals, such as H g and Ag .

Lithium–Iodine Battery
None of the batteries described above is actually “dry.” They all contain small amounts of liquid water, which adds significant mass and causes
potential corrosion problems. Consequently, substantial effort has been expended to develop water-free batteries. One of the few commercially
successful water-free batteries is the lithium–iodine battery. The anode is lithium metal, and the cathode is a solid complex of I . Separating them
2

is a layer of solid LiI, which acts as the electrolyte by allowing the diffusion of Li+ ions. The electrode reactions are as follows:
cathode (reduction):
− −
I2(s) + 2 e → 2I (LiI)
(9.4.11)

anode (oxidation):
+ −
2Li(s) → 2Li + 2e (9.4.12)
(LiI)

overall:
2Li(s) + I2(s) → 2Li I(s) (9.4.13)

with E cell = 3.5 V

Cardiac pacemaker: An x-ray of a patient showing the location and size of a pacemaker powered by a lithium–iodine battery.
As shown in part (c) in Figure 9.4.1, a typical lithium–iodine battery consists of two cells separated by a nickel metal mesh that collects charge from
the anode. Because of the high internal resistance caused by the solid electrolyte, only a low current can be drawn. Nonetheless, such batteries have
proven to be long-lived (up to 10 yr) and reliable. They are therefore used in applications where frequent replacement is difficult or undesirable, such
as in cardiac pacemakers and other medical implants and in computers for memory protection. These batteries are also used in security transmitters
and smoke alarms. Other batteries based on lithium anodes and solid electrolytes are under development, using T iS , for example, for the cathode.
2

Dry cells, button batteries, and lithium–iodine batteries are disposable and cannot be recharged once they are discharged. Rechargeable batteries, in
contrast, offer significant economic and environmental advantages because they can be recharged and discharged numerous times. As a result,
manufacturing and disposal costs drop dramatically for a given number of hours of battery usage. Two common rechargeable batteries are the
nickel–cadmium battery and the lead–acid battery, which we describe next.

Nickel–Cadmium (NiCad) Battery

The nickel–cadmium, or NiCad, battery is used in small electrical appliances and devices like drills, portable vacuum cleaners, and AM/FM digital
tuners. It is a water-based cell with a cadmium anode and a highly oxidized nickel cathode that is usually described as the nickel(III) oxo-hydroxide,
NiO(OH). As shown in Figure 9.4.2, the design maximizes the surface area of the electrodes and minimizes the distance between them, which
decreases internal resistance and makes a rather high discharge current possible.

9.4.3 [Link]
 Figure 9.4.2 : The Nickel–Cadmium (NiCad) Battery, a Rechargeable Battery. NiCad batteries contain a cadmium anode and a highly oxidized
nickel cathode. This design maximizes the surface area of the electrodes and minimizes the distance between them, which gives the battery both a
high discharge current and a high capacity.
The electrode reactions during the discharge of a N iC ad battery are as follows:
cathode (reduction):
− −
2N iO(OH )(s) + 2 H2 O(l) + 2 e → 2N i(OH )2(s) + 2OH (9.4.14)
(aq)

anode (oxidation):
− −
C d(s) + 2OH → C d(OH )2(s) + 2 e (9.4.15)
(aq)

overall:
C d(s) + 2N iO(OH )(s) + 2 H2 O(l) → C d(OH )2(s) + 2N i(OH )2(s) (9.4.16)

Ecell = 1.4V

Because the products of the discharge half-reactions are solids that adhere to the electrodes [Cd(OH)2 and 2Ni(OH)2], the overall reaction is readily
reversed when the cell is recharged. Although NiCad cells are lightweight, rechargeable, and high capacity, they have certain disadvantages. For
example, they tend to lose capacity quickly if not allowed to discharge fully before recharging, they do not store well for long periods when fully
charged, and they present significant environmental and disposal problems because of the toxicity of cadmium.
A variation on the NiCad battery is the nickel–metal hydride battery (NiMH) used in hybrid automobiles, wireless communication devices, and
mobile computing. The overall chemical equation for this type of battery is as follows:
N iO(OH )(s) + M H → N i(OH )2(s) + M(s) (9.4.17)

The NiMH battery has a 30%–40% improvement in capacity over the NiCad battery; it is more environmentally friendly so storage, transportation,
and disposal are not subject to environmental control; and it is not as sensitive to recharging memory. It is, however, subject to a 50% greater self-
discharge rate, a limited service life, and higher maintenance, and it is more expensive than the NiCad battery.

Directive 2006/66/EC of the European Union prohibits the placing on the market of portable batteries that contain more than 0.002% of cadmium
by weight. The aim of this directive was to improve "the environmental performance of batteries and accumulators"

Lead–Acid (Lead Storage) Battery

The lead–acid battery is used to provide the starting power in virtually every automobile and marine engine on the market. Marine and car batteries
typically consist of multiple cells connected in series. The total voltage generated by the battery is the potential per cell (E°cell) times the number of
cells.

9.4.4 [Link]
 Figure 9.4.3 : One Cell of a Lead–Acid Battery. The anodes in each cell of a rechargeable battery are plates or grids of lead containing spongy
lead metal, while the cathodes are similar grids containing powdered lead dioxide (PbO2). The electrolyte is an aqueous solution of sulfuric acid.
The value of E° for such a cell is about 2 V. Connecting three such cells in series produces a 6 V battery, whereas a typical 12 V car battery contains
six cells in series. When treated properly, this type of high-capacity battery can be discharged and recharged many times over.
As shown in Figure 9.4.3, the anode of each cell in a lead storage battery is a plate or grid of spongy lead metal, and the cathode is a similar grid
containing powdered lead dioxide (P bO ). The electrolyte is usually an approximately 37% solution (by mass) of sulfuric acid in water, with a
2

density of 1.28 g/mL (about 4.5 M H SO ). Because the redox active species are solids, there is no need to separate the electrodes. The electrode
2 4

reactions in each cell during discharge are as follows:

cathode (reduction):
− + −
P b O2(s) + H S O + 3H + 2e → P bS O4(s) + 2 H2 O(l) (9.4.18)
4(aq) (aq)

with E ∘
cathode
= 1.685 V

anode (oxidation):
− + −
P b(s) + H S O → P bS O4(s) + H + 2e (9.4.19)
4(aq) (aq)

with E ∘
anode
= −0.356 V

overall:
− +
P b(s) + P b O2(s) + 2H S O + 2H → 2P bS O4(s) + 2 H2 O(l) (9.4.20)
4(aq) (aq)

and E ∘
cell
= 2.041 V

As the cell is discharged, a powder of P bSO forms on the electrodes. Moreover, sulfuric acid is consumed and water is produced, decreasing the
4

density of the electrolyte and providing a convenient way of monitoring the status of a battery by simply measuring the density of the electrolyte.
This is often done with the use of a hydrometer.

9.4.5 [Link]
 How to use A battery Hydrometer To Test For A Fully Charged Lead A…
A…

A hydrometer can be used to test the specific gravity of each cell as a measure of its state of charge ([Link]
v=SRcOqfL6GqQ).
When an external voltage in excess of 2.04 V per cell is applied to a lead–acid battery, the electrode reactions reverse, and P bSO is converted back
4

to metallic lead and P bO . If the battery is recharged too vigorously, however, electrolysis of water can occur:
2

2 H2 O(l) → 2 H2(g) + O2(g) (9.4.21)

This results in the evolution of potentially explosive hydrogen gas. The gas bubbles formed in this way can dislodge some of the P bSO or P bO4 2

particles from the grids, allowing them to fall to the bottom of the cell, where they can build up and cause an internal short circuit. Thus the
recharging process must be carefully monitored to optimize the life of the battery. With proper care, however, a lead–acid battery can be discharged
and recharged thousands of times. In automobiles, the alternator supplies the electric current that causes the discharge reaction to reverse.

Fuel Cells
A fuel cell is a galvanic cell that requires a constant external supply of reactants because the products of the reaction are continuously removed.
Unlike a battery, it does not store chemical or electrical energy; a fuel cell allows electrical energy to be extracted directly from a chemical reaction.
In principle, this should be a more efficient process than, for example, burning the fuel to drive an internal combustion engine that turns a generator,
which is typically less than 40% efficient, and in fact, the efficiency of a fuel cell is generally between 40% and 60%. Unfortunately, significant cost
and reliability problems have hindered the wide-scale adoption of fuel cells. In practice, their use has been restricted to applications in which mass
may be a significant cost factor, such as US manned space vehicles.

9.4.6 [Link]
Figure 9.4.4 : A Hydrogen Fuel Cell Produces Electrical Energy Directly from a Chemical Reaction. Hydrogen is oxidized to protons at the anode,
and the electrons are transferred through an external circuit to the cathode, where oxygen is reduced and combines with H to form water. A solid
+

electrolyte allows the protons to diffuse from the anode to the cathode. Although fuel cells are an essentially pollution-free means of obtaining
electrical energy, their expense and technological complexity have thus far limited their applications.
These space vehicles use a hydrogen/oxygen fuel cell that requires a continuous input of H2(g) and O2(g), as illustrated in Figure 9.4.4 . The
electrode reactions are as follows:
cathode (reduction):
+ −
O2(g) + 4 H + 4e → 2 H2 O(g) (9.4.22)

anode (oxidation):
+ −
2 H2(g) → 4 H + 4e (9.4.23)

overall:
2 H2(g) + O2(g) → 2 H2 O(g) (9.4.24)

The overall reaction represents an essentially pollution-free conversion of hydrogen and oxygen to water, which in space vehicles is then collected
and used. Although this type of fuel cell should produce 1.23 V under standard conditions, in practice the device achieves only about 0.9 V. One of
the major barriers to achieving greater efficiency is the fact that the four-electron reduction of O (g) at the cathode is intrinsically rather slow, which
2

limits current that can be achieved. All major automobile manufacturers have major research programs involving fuel cells: one of the most
important goals is the development of a better catalyst for the reduction of O (g) .2

Summary
Commercial batteries are galvanic cells that use solids or pastes as reactants to maximize the electrical output per unit mass. A battery is a contained
unit that produces electricity, whereas a fuel cell is a galvanic cell that requires a constant external supply of one or more reactants to generate
electricity. One type of battery is the Leclanché dry cell, which contains an electrolyte in an acidic water-based paste. This battery is called an
alkaline battery when adapted to operate under alkaline conditions. Button batteries have a high output-to-mass ratio; lithium–iodine batteries consist
of a solid electrolyte; the nickel–cadmium (NiCad) battery is rechargeable; and the lead–acid battery, which is also rechargeable, does not require the
electrodes to be in separate compartments. A fuel cell requires an external supply of reactants as the products of the reaction are continuously
removed. In a fuel cell, energy is not stored; electrical energy is provided by a chemical reaction.

9.4: Batteries: Using Chemistry to Generate Electricity is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

9.4.7 [Link]
9.5 Driving Reactant-Favored Reactions Using Electricity
Skills to Develop
To understand electrolysis and describe it quantitatively.

In this chapter, we have described various galvanic cells in which a spontaneous chemical reaction is used to generate electrical
energy. In an electrolytic cell, however, the opposite process, called electrolysis, occurs: an external voltage is applied to drive a
nonspontaneous reaction. In this section, we look at how electrolytic cells are constructed and explore some of their many
commercial applications.

Electrolytic Cells
If we construct an electrochemical cell in which one electrode is copper metal immersed in a 1 M Cu2+ solution and the other
electrode is cadmium metal immersed in a 1 M C d solution and then close the circuit, the potential difference between the two
2+

compartments will be 0.74 V. The cadmium electrode will begin to dissolve (Cd is oxidized to Cd2+) and is the anode, while
metallic copper will be deposited on the copper electrode (Cu2+ is reduced to Cu), which is the cathode (Figure 1a).

Figure 1 : An Applied Voltage Can Reverse the Flow of Electrons in a Galvanic Cd/Cu Cell. (a) When compartments that contain a
Cd electrode immersed in 1 M Cd2+(aq) and a Cu electrode immersed in 1 M Cu2+(aq) are connected to create a galvanic cell,
Cd(s) is spontaneously oxidized to Cd2+(aq) at the anode, and Cu2+(aq) is spontaneously reduced to Cu(s) at the cathode. The
potential of the galvanic cell is 0.74 V. (b) Applying an external potential greater than 0.74 V in the reverse direction forces
electrons to flow from the Cu electrode [which is now the anode, at which metallic Cu(s) is oxidized to Cu2+(aq)] and into the Cd
electrode [which is now the cathode, at which Cd2+(aq) is reduced to Cd(s)]. The anode in an electrolytic cell is positive because
electrons are flowing from it, whereas the cathode is negative because electrons are flowing into it.
The overall reaction is as follows:
2 + 2 +
Cd(s) + Cu (aq) → Cd (aq) + Cu(s) (1)

with E °cell = 0.74 V

This reaction is thermodynamically spontaneous as written (ΔG° < 0):

∘ ∘
ΔG = −nF E (2)
cell

−
= −(2 mol e )[96, 486 J/(V ⋅ mol)](0.74 V) (3)

= −140 kJ (per mole Cd) (4)

1 [Link]
In this direction, the system is acting as a galvanic cell.

In an electrolytic cell, an external voltage is applied to drive a nonspontaneous reaction.

The reverse reaction, the reduction of Cd2+ by Cu, is thermodynamically nonspontaneous and will occur only with an input of 140
kJ. We can force the reaction to proceed in the reverse direction by applying an electrical potential greater than 0.74 V from an
external power supply. The applied voltage forces electrons through the circuit in the reverse direction, converting a galvanic cell to
an electrolytic cell. Thus the copper electrode is now the anode (Cu is oxidized), and the cadmium electrode is now the cathode
(Cd2+ is reduced) (Figure 1b). The signs of the cathode and the anode have switched to reflect the flow of electrons in the circuit.
The half-reactions that occur at the cathode and the anode are as follows:
cathode:
2 + −
Cd (aq) + 2 e → Cd(s) (5)

with E ∘
cathode
= −0.40 V

anode:
2 + −
Cu(s) → Cu (aq) + 2 e (6)

with E ∘
anode
= 0.34 V

Overall:
2 + 2 +
Cd (aq) + Cu(s) → Cd(s) + Cu (aq) (7)

with E ∘
cell
= −0.74 V

Because E < 0 , the overall reaction—the reduction of C d by C u—clearly cannot occur spontaneously and proceeds only
∘
cell
2+

when sufficient electrical energy is applied. The differences between galvanic and electrolytic cells are summarized in Table 1.
Table 1 : Comparison of Galvanic and Electrolytic Cells
Property Galvanic Cell Electrolytic Cell

ΔG <0 >0

Ecell >0 <0

Electrode Process

anode oxidation oxidation

cathode reduction reduction

Sign of Electrode

anode − +

cathode + −

Electrolytic Reactions
At sufficiently high temperatures, ionic solids melt to form liquids that conduct electricity extremely well due to the high
concentrations of ions. If two inert electrodes are inserted into molten N aC l, for example, and an electrical potential is applied,
Cl
−
is oxidized at the anode, and N a is reduced at the cathode. The overall reaction is as follows:
+

2 NaCl(l) → 2 Na(l) + Cl (g) (8)

2

This is the reverse of the formation of NaCl from its elements. The product of the reduction reaction is liquid sodium because the
melting point of sodium metal is 97.8°C, well below that of N aC l (801°C). Approximately 20,000 tons of sodium metal are
produced commercially in the United States each year by the electrolysis of molten N aC l in a Downs cell (Figure 2). In this

2 [Link]
specialized cell, C aC l (melting point = 772°C) is first added to the
2 N aC l to lower the melting point of the mixture to about
600°C, thereby lowering operating costs.

Figure 2 : A Downs Cell for the Electrolysis of Molten NaCl. The electrolysis of a molten mixture of NaCl and CaCl2 results in the
formation of elemental sodium and chlorine gas. Because sodium is a liquid under these conditions and liquid sodium is less dense
than molten sodium chloride, the sodium floats to the top of the melt and is collected in concentric capped iron cylinders
surrounding the cathode. Gaseous chlorine collects in the inverted cone over the anode. An iron screen separating the cathode and
anode compartments ensures that the molten sodium and gaseous chlorine do not come into contact.
Similarly, in the Hall–Heroult process used to produce aluminum commercially, a molten mixture of about 5% aluminum oxide
(Al2O3; melting point = 2054°C) and 95% cryolite (Na3AlF6; melting point = 1012°C) is electrolyzed at about 1000°C, producing
molten aluminum at the cathode and CO2 gas at the carbon anode. The overall reaction is as follows:

2Al2 O3(l) + 3 C(s) → 4Al(l) + 3C O2(g) (9)

Oxide ions react with oxidized carbon at the anode, producing CO2(g).
There are two important points to make about these two commercial processes and about the electrolysis of molten salts in general.
1. The electrode potentials for molten salts are likely to be very different from the standard cell potentials listed in Table P2, which
are compiled for the reduction of the hydrated ions in aqueous solutions under standard conditions.
2. Using a mixed salt system means there is a possibility of competition between different electrolytic reactions. When a mixture
of NaCl and CaCl2 is electrolyzed, Cl− is oxidized because it is the only anion present, but either Na+ or Ca2+ can be reduced.
Conversely, in the Hall–Heroult process, only one cation is present that can be reduced (Al3+), but there are three species that
can be oxidized: C, O2−, and F−.
In the Hall–Heroult process, C is oxidized instead of O2− or F− because oxygen and fluorine are more electronegative than carbon,
which means that C is a weaker oxidant than either O2 or F2. Similarly, in the Downs cell, we might expect electrolysis of a
NaCl/CaCl2 mixture to produce calcium rather than sodium because Na is slightly less electronegative than Ca (χ = 0.93 versus
1.00, respectively), making Na easier to oxidize and, conversely, Na+ more difficult to reduce. In fact, the reduction of Na+ to Na is
the observed reaction. In cases where the electronegativities of two species are similar, other factors, such as the formation of
complex ions, become important and may determine the outcome.

3 [Link]
Electrolysis can also be used to drive the thermodynamically nonspontaneous decomposition of water into its constituent elements:
H2 and O2. However, because pure water is a very poor electrical conductor, a small amount of an ionic solute (such as H2SO4 or
Na2SO4) must first be added to increase its electrical conductivity. Inserting inert electrodes into the solution and applying a
voltage between them will result in the rapid evolution of bubbles of H2 and O2 (Figure 3).

Figure 3 : The Electrolysis of Water. Applying an external potential of about 1.7–1.9 V to two inert electrodes immersed in an
aqueous solution of an electrolyte such as H2SO4 or Na2SO4 drives the thermodynamically nonspontaneous decomposition of water
into H2 at the cathode and O2 at the anode.
The reactions that occur are as follows:
cathode:
+ − ∘
2H + 2e → H2(g) E = 0V (10)
(aq) cathode

anode:
− ∘
2 H2 O(l) → O2(g) + 4H +(aq) +4 e E = 1.23 V (11)
anode

overall:
∘
2 H2 O(l) → O2(g) + 2 H2(g) E = −1.23 V (12)
cell

For a system that contains an electrolyte such as Na2SO4, which has a negligible effect on the ionization equilibrium of liquid
water, the pH of the solution will be 7.00 and [H+] = [OH−] = 1.0 × 10−7. Assuming that P = P = 1 atm, we can use the
O2 H2

standard potentials to calculate E for the overall reaction:

0.0591 V
∘ 2
Ecell = E −( ) log(PO2 P ) (13)
cell H2
n

0.0591 V
Ecell = −1.23 V − ( ) log(1) = −1.23 V (14)
4

Thus Ecell is −1.23 V, which is the value of E°cell if the reaction is carried out in the presence of 1 M H+ rather than at pH 7.0.
In practice, a voltage about 0.4–0.6 V greater than the calculated value is needed to electrolyze water. This added voltage, called an
overvoltage, represents the additional driving force required to overcome barriers such as the large activation energy for the
formation of a gas at a metal surface. Overvoltages are needed in all electrolytic processes, which explain why, for example,
approximately 14 V must be applied to recharge the 12 V battery in your car.
In general, any metal that does not react readily with water to produce hydrogen can be produced by the electrolytic reduction of an
aqueous solution that contains the metal cation. The p-block metals and most of the transition metals are in this category, but metals
in high oxidation states, which form oxoanions, cannot be reduced to the metal by simple electrolysis. Active metals, such as
aluminum and those of groups 1 and 2, react so readily with water that they can be prepared only by the electrolysis of molten salts.
Similarly, any nonmetallic element that does not readily oxidize water to O2 can be prepared by the electrolytic oxidation of an
aqueous solution that contains an appropriate anion. In practice, among the nonmetals, only F2 cannot be prepared using this

4 [Link]
method. Oxoanions of nonmetals in their highest oxidation states, such as NO3−, SO42−, PO43−, are usually difficult to reduce
electrochemically and usually behave like spectator ions that remain in solution during electrolysis.

In general, any metal that does not react readily with water to produce hydrogen can be
produced by the electrolytic reduction of an aqueous solution that contains the metal
cation.

Electroplating
In a process called electroplating, a layer of a second metal is deposited on the metal electrode that acts as the cathode during
electrolysis. Electroplating is used to enhance the appearance of metal objects and protect them from corrosion. Examples of
electroplating include the chromium layer found on many bathroom fixtures or (in earlier days) on the bumpers and hubcaps of
cars, as well as the thin layer of precious metal that coats silver-plated dinnerware or jewelry. In all cases, the basic concept is the
same. A schematic view of an apparatus for electroplating silverware and a photograph of a commercial electroplating cell are
shown in Figure 4.

Figure 3 : Electroplating. (a) Electroplating uses an electrolytic cell in which the object to be plated, such as a fork, is immersed in
a solution of the metal to be deposited. The object being plated acts as the cathode, on which the desired metal is deposited in a
thin layer, while the anode usually consists of the metal that is being deposited (in this case, silver) that maintains the solution
concentration as it dissolves. (b) In this commercial electroplating apparatus, a large number of objects can be plated
simultaneously by lowering the rack into the Ag+ solution and applying the correct potential.
The half-reactions in electroplating a fork, for example, with silver are as follows:
cathode (fork):
+
Ag + e− → Ag(s) E °cathode = 0.80V (15)
(aq)

anode (silver bar):

+
Ag(s) → Ag E °anode = 0.80V (16)
(aq)

The overall reaction is the transfer of silver metal from one electrode (a silver bar acting as the anode) to another (a fork acting as
the cathode). Because E°cell = 0 V, it takes only a small applied voltage to drive the electroplating process. In practice, various other
substances may be added to the plating solution to control its electrical conductivity and regulate the concentration of free metal
ions, thus ensuring a smooth, even coating.

5 [Link]
Summary
In electrolysis, an external voltage is applied to drive a nonspontaneous reaction. The quantity of material oxidized or reduced can
be calculated from the stoichiometry of the reaction and the amount of charge transferred. Relationship of charge, current and time:

C = A×t

In electrolysis, an external voltage is applied to drive a nonspontaneous reaction. Electrolysis can also be used to produce H2 and
O2 from water. In practice, an additional voltage, called an overvoltage, must be applied to overcome factors such as a large
activation energy and a junction potential. Electroplating is the process by which a second metal is deposited on a metal surface,
thereby enhancing an object’s appearance or providing protection from corrosion. The amount of material consumed or produced in
a reaction can be calculated from the stoichiometry of an electrolysis reaction, the amount of current passed, and the duration of the
electrolytic reaction.

9.5 Driving Reactant-Favored Reactions Using Electricity is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated
by LibreTexts.

6 [Link]
9.6 Undesirable Redox Reactions
Skills to Develop
To understand the process of corrosion.

Corrosion is a galvanic process by which metals deteriorate through oxidation—usually but not always to their oxides. For
example, when exposed to air, iron rusts, silver tarnishes, and copper and brass acquire a bluish-green surface called a patina. Of
the various metals subject to corrosion, iron is by far the most important commercially. An estimated $100 billion per year is spent
in the United States alone to replace iron-containing objects destroyed by corrosion. Consequently, the development of methods for
protecting metal surfaces from corrosion constitutes a very active area of industrial research. In this section, we describe some of
the chemical and electrochemical processes responsible for corrosion. We also examine the chemical basis for some common
methods for preventing corrosion and treating corroded metals.

Corrosion is a REDOX process.

Under ambient conditions, the oxidation of most metals is thermodynamically spontaneous, with the notable exception of gold and
platinum. Hence it is actually somewhat surprising that any metals are useful at all in Earth’s moist, oxygen-rich atmosphere. Some
metals, however, are resistant to corrosion for kinetic reasons. For example, aluminum in soft-drink cans and airplanes is protected
by a thin coating of metal oxide that forms on the surface of the metal and acts as an impenetrable barrier that prevents further
destruction. Aluminum cans also have a thin plastic layer to prevent reaction of the oxide with acid in the soft drink. Chromium,
magnesium, and nickel also form protective oxide films. Stainless steels are remarkably resistant to corrosion because they usually
contain a significant proportion of chromium, nickel, or both.
In contrast to these metals, when iron corrodes, it forms a red-brown hydrated metal oxide (Fe2O3•xH2O), commonly known as
rust, that does not provide a tight protective film (Figure 1). Instead, the rust continually flakes off to expose a fresh metal surface
vulnerable to reaction with oxygen and water. Because both oxygen and water are required for rust to form, an iron nail immersed
in deoxygenated water will not rust—even over a period of several weeks. Similarly, a nail immersed in an organic solvent such as
kerosene or mineral oil saturated with oxygen will not rust because of the absence of water.

Figure 1 : Rust, the Result of Corrosion of Metallic Iron. Iron is oxidized to Fe2+(aq) at an anodic site on the surface of the iron,
which is often an impurity or a lattice defect. Oxygen is reduced to water at a different site on the surface of the iron, which acts as
the cathode. Electrons are transferred from the anode to the cathode through the electrically conductive metal. Water is a solvent
for the Fe2+ that is produced initially and acts as a salt bridge. Rust (Fe2O3•xH2O) is formed by the subsequent oxidation of Fe2+
by atmospheric oxygen.
In the corrosion process, iron metal acts as the anode in a galvanic cell and is oxidized to Fe2+; oxygen is reduced to water at the
cathode. The relevant reactions are as follows:
at cathode:

1 [Link]
 + −
O2(g) + 4 H + 4e → 2 H2 O(l) E° = 1.23 V (1)
(aq)

at anode:
2+ −
F e(s) → F e + 2e E° = −0.45 V (2)
(aq)

overall:
+ 2+
2F e(s) + O2(g) + 4 H → 2F e + 2 H2 O(l) E° = 1.68 V (3)
(aq) (aq)

The Fe2+ ions produced in the initial reaction are then oxidized by atmospheric oxygen to produce the insoluble hydrated oxide
containing Fe3+, as represented in the following equation:
2+ +
4F e + O2(g) + (2 + 4x)H2 O → 2F e2 O3 ⋅ x H2 O + 4 H (4)
(aq) (aq)

The sign and magnitude of E° for the corrosion process (Equation 3) indicate that there is a strong driving force for the oxidation of
iron by O2 under standard conditions (1 M H+). Under neutral conditions, the driving force is somewhat less but still appreciable (E
= 1.25 V at pH 7.0). Normally, the reaction of atmospheric CO2 with water to form H+ and HCO3− provides a low enough pH to
enhance the reaction rate, as does acid rain. Automobile manufacturers spend a great deal of time and money developing paints that
adhere tightly to the car’s metal surface to prevent oxygenated water, acid, and salt from coming into contact with the underlying
metal. Unfortunately, even the best paint is subject to scratching or denting, and the electrochemical nature of the corrosion process
means that two scratches relatively remote from each other can operate together as anode and cathode, leading to sudden
mechanical failure (Figure 2).

Figure 2 : Small Scratches in a Protective Paint Coating Can Lead to the Rapid Corrosion of Iron. Holes in a protective coating
allow oxygen to be reduced at the surface with the greater exposure to air (the cathode), while metallic iron is oxidized to Fe2+(aq)
at the less exposed site (the anode). Rust is formed when Fe2+(aq) diffuses to a location where it can react with atmospheric
oxygen, which is often remote from the anode. The electrochemical interaction between cathodic and anodic sites can cause a large
pit to form under a painted surface, eventually resulting in sudden failure with little visible warning that corrosion has occurred.

Prophylactic Protection
One of the most common techniques used to prevent the corrosion of iron is applying a protective coating of another metal that is
more difficult to oxidize. Faucets and some external parts of automobiles, for example, are often coated with a thin layer of
chromium using an electrolytic process. With the increased use of polymeric materials in cars, however, the use of chrome-plated
steel has diminished in recent years. Similarly, the “tin cans” that hold soups and other foods are actually made of steel coated with
a thin layer of tin. Neither chromium nor tin is intrinsically resistant to corrosion, but both form protective oxide coatings.

2 [Link]
 Figure 3 : Galvanic Corrosion. If iron is in contact with a more corrosion-resistant metal such as tin, copper, or lead, the other
metal can act as a large cathode that greatly increases the rate of reduction of oxygen. Because the reduction of oxygen is coupled
to the oxidation of iron, this can result in a dramatic increase in the rate at which iron is oxidized at the anode. Galvanic corrosion
is likely to occur whenever two dissimilar metals are connected directly, allowing electrons to be transferred from one to the other.
As with a protective paint, scratching a protective metal coating will allow corrosion to occur. In this case, however, the presence of
the second metal can actually increase the rate of corrosion. The values of the standard electrode potentials for Sn2+ (E° = −0.14 V)
and Fe2+ (E° = −0.45 V) in Table P2 show that Fe is more easily oxidized than Sn. As a result, the more corrosion-resistant metal
(in this case, tin) accelerates the corrosion of iron by acting as the cathode and providing a large surface area for the reduction of
oxygen (Figure 3). This process is seen in some older homes where copper and iron pipes have been directly connected to each
other. The less easily oxidized copper acts as the cathode, causing iron to dissolve rapidly near the connection and occasionally
resulting in a catastrophic plumbing failure.

Cathodic Protection
One way to avoid these problems is to use a more easily oxidized metal to protect iron from corrosion. In this approach, called
cathodic protection, a more reactive metal such as Zn (E° = −0.76 V for Zn2+ + 2e−→ Zn) becomes the anode, and iron becomes
the cathode. This prevents oxidation of the iron and protects the iron object from corrosion. The reactions that occur under these
conditions are as follows:
− +
O2(g) + 4 e + 4H → 2 H2 O(l) (5)
(aq)

reduction at cathode

2+ −
Z n(s) → Z n + 2e (6)
(aq)

oxidation at anode

+ 2+
2Z n(s) + O2(g) + 4 H → 2Z n + 2 H2 O(l) (7)
(aq) (aq)

overall

The more reactive metal reacts with oxygen and will eventually dissolve, “sacrificing” itself to protect the iron object. Cathodic
protection is the principle underlying galvanized steel, which is steel protected by a thin layer of zinc. Galvanized steel is used in
objects ranging from nails to garbage cans.

Crystalline surface of a hot-dip galvanized steel surface. This served both as prophylactic protection (protecting the underlying
steel from the oxygen in the air) and cathodic protection (once exposed, the zinc will oxidize before the underlying steel).

3 [Link]
In a similar strategy, sacrificial electrodes using magnesium, for example, are used to protect underground tanks or pipes (Figure
4 ). Replacing the sacrificial electrodes is more cost-effective than replacing the iron objects they are protecting.

Figure 4 : The Use of a Sacrificial Electrode to Protect Against Corrosion. Connecting a magnesium rod to an underground steel
pipeline protects the pipeline from corrosion. Because magnesium (E° = −2.37 V) is much more easily oxidized than iron (E° =
−0.45 V), the Mg rod acts as the anode in a galvanic cell. The pipeline is therefore forced to act as the cathode at which oxygen is
reduced. The soil between the anode and the cathode acts as a salt bridge that completes the electrical circuit and maintains
electrical neutrality. As Mg(s) is oxidized to Mg2+ at the anode, anions in the soil, such as nitrate, diffuse toward the anode to
neutralize the positive charge. Simultaneously, cations in the soil, such as H+ or NH4+, diffuse toward the cathode, where they
replenish the protons that are consumed as oxygen is reduced. A similar strategy uses many miles of somewhat less reactive zinc
wire to protect the Alaska oil pipeline.

Example 1
Suppose an old wooden sailboat, held together with iron screws, has a bronze propeller (recall that bronze is an alloy of copper
containing about 7%–10% tin).
a. If the boat is immersed in seawater, what corrosion reaction will occur? What is E°cell?
b. How could you prevent this corrosion from occurring?
Given: identity of metals
Asked for: corrosion reaction, E°cell, and preventive measures
Strategy:
A. Write the reactions that occur at the anode and the cathode. From these, write the overall cell reaction and calculate E°cell.
B. Based on the relative redox activity of various substances, suggest possible preventive measures.
Solution:
a. A According to Table P2, both copper and tin are less active metals than iron (i.e., they have higher positive values of E°
than iron). Thus if tin or copper is brought into electrical contact by seawater with iron in the presence of oxygen, corrosion
will occur. We therefore anticipate that the bronze propeller will act as the cathode at which O is reduced, and the iron
2

screws will act as anodes at which iron dissolves:

+ − ∘
cathode: O2 (s) + 4 H (aq) + 4 e → 2 H2 O(l) E = 1.23 V (8)
cathode

2+ − ∘
anode: Fe(s) → F e + 2e E = −0.45 V (9)
anode

+ 2+ ∘
overall: 2Fe(s) + O2 (g) + 4 H (aq) → 2F e (aq) + 2 H2 O(l) E = 1.68 V (10)
overall

Over time, the iron screws will dissolve, and the boat will fall apart.
b. B Possible ways to prevent corrosion, in order of decreasing cost and inconvenience, are as follows: disassembling the boat
and rebuilding it with bronze screws; removing the boat from the water and storing it in a dry place; or attaching an
inexpensive piece of zinc metal to the propeller shaft to act as a sacrificial electrode and replacing it once or twice a year.
Because zinc is a more active metal than iron, it will act as the sacrificial anode in the electrochemical cell and dissolve
(Equation 7).

4 [Link]
 Zinc sacrificial anode (rounded object screwed to underside of hull) used to prevent corrosion on the screw in a boat via
cathodic protection. Image by Rémi Kaupp and used with permission.

Exercise 1
Suppose the water pipes leading into your house are made of lead, while the rest of the plumbing in your house is iron. To
eliminate the possibility of lead poisoning, you call a plumber to replace the lead pipes. He quotes you a very low price if he can
use up his existing supply of copper pipe to do the job.
a. Do you accept his proposal?
b. What else should you have the plumber do while at your home?

Answer a
Not unless you plan to sell the house very soon because the Cu/Fe pipe joints will lead to rapid corrosion.
Answer a
Any existing Pb/Fe joints should be examined carefully for corrosion of the iron pipes due to the Pb–Fe junction; the less
active Pb will have served as the cathode for the reduction of O2, promoting oxidation of the more active Fe nearby.

Summary
Corrosion is a galvanic process that can be prevented using cathodic protection. The deterioration of metals through oxidation is a
galvanic process called corrosion. Protective coatings consist of a second metal that is more difficult to oxidize than the metal
being protected. Alternatively, a more easily oxidized metal can be applied to a metal surface, thus providing cathodic protection of
the surface. A thin layer of zinc protects galvanized steel. Sacrificial electrodes can also be attached to an object to protect it.

9.6 Undesirable Redox Reactions is shared under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by LibreTexts.

5 [Link]
Index
A group P
accuracy 1.2: A First Look at the Periodic Table period
1.6: Limits on Measurements 1.2: A First Look at the Periodic Table
alkali metal H Physical change
1.2: A First Look at the Periodic Table halogen 1.3: The Classification of Matter
alkaline earth metal 1.2: A First Look at the Periodic Table Potential Energy
1.2: A First Look at the Periodic Table heat 1.4: A First Look at Energy
1.4: A First Look at Energy precision
C heterogeneous mixture 1.6: Limits on Measurements
calorie 1.3: The Classification of Matter pressure
1.4: A First Look at Energy homogeneous mixture 1.3: The Classification of Matter
chemical change 1.3: The Classification of Matter
1.3: The Classification of Matter R
compound J rounding
1.3: The Classification of Matter joule 1.6: Limits on Measurements
conversion factors 1.4: A First Look at Energy
1.7: Dimensional Analysis S
Crystallization K semimetal
1.3: The Classification of Matter kinetic energy 1.2: A First Look at the Periodic Table
1.4: A First Look at Energy significant figures
D 1.6: Limits on Measurements
Dimensional Analysis L solid
1.7: Dimensional Analysis law of conservation of energy 1.3: The Classification of Matter
distillation 1.4: A First Look at Energy
1.3: The Classification of Matter liquid T
1.3: The Classification of Matter temperature
E 1.4: A First Look at Energy
element M thermal energy
1.3: The Classification of Matter mass 1.4: A First Look at Energy
exact number 1.3: The Classification of Matter thermochemistry
1.6: Limits on Measurements matter 1.4: A First Look at Energy
Exercises 1.3: The Classification of Matter
1.8: Matter, Measurement, and Problem Solving mechanical work U
(Exercises)
3.11 Practice Problems
1.4: A First Look at Energy uncertainty
5.7 Chemical Reactions and Aqueous Reactions
metal 1.6: Limits on Measurements
(Exercises) 1.2: A First Look at the Periodic Table
V
F N VSEPR
Fahrenheit noble gas 3.10 Shapes of Molecules - VSEPR Theory and
1.7: Dimensional Analysis 1.2: A First Look at the Periodic Table Valence Bond Theory
nonmetal
G 1.2: A First Look at the Periodic Table W
gas weight
1.3: The Classification of Matter 1.3: The Classification of Matter

1 [Link]
Glossary
Sample Word 1 | Sample Definition 1

1 [Link]
Detailed Licensing
Overview
Title: CHM 120 - Survey of General Chemistry(Neils)
Webpages: 105
Applicable Restrictions: Noncommercial
All licenses found:
CC BY-NC-SA 4.0: 86.7% (91 pages)
Undeclared: 7.6% (8 pages)
CC BY 4.0: 3.8% (4 pages)
Public Domain: 1% (1 page)
CC BY-SA 4.0: 1% (1 page)

By Page
CHM 120 - Survey of General Chemistry(Neils) - CC BY- 2.10 Quantum Mechanics and The Atom - CC BY-
NC-SA 4.0 NC-SA 4.0
Front Matter - CC BY-NC-SA 4.0 2.11 Trends of the Periodic Table - CC BY-NC-SA 4.0
TitlePage - Undeclared 2.12 Example Problems - CC BY-NC-SA 4.0
InfoPage - Undeclared 3: Chemical Formulas and Bonding - CC BY-NC-SA 4.0
Table of Contents - Undeclared 3.1 An Atomic-Level Perspective of Ionic and
Licensing - Undeclared Covalent Compounds - CC BY-NC-SA 4.0
1: Matter and Energy - CC BY-NC-SA 4.0 3.2 Composition of Compounds - CC BY-NC-SA 4.0
3.3 Chemical Bonds - CC BY-NC-SA 4.0
1.1 The Terms of Science - CC BY-NC-SA 4.0
3.4 Ionic Compounds: Formulas and Names - CC BY-
1.2: A First Look at the Periodic Table - CC BY-NC-
NC-SA 4.0
SA 4.0
3.5 Covalently-Bonded Species: Formulas and Names
1.3: The Classification of Matter - CC BY-NC-SA 4.0
- CC BY-NC-SA 4.0
1.4: A First Look at Energy - CC BY-NC-SA 4.0
3.6 Electronegativity and Bond Polarity - CC BY-NC-
1.5: Making Measurements - CC BY 4.0
SA 4.0
1.6: Limits on Measurements - CC BY 4.0
3.7 Lewis Structures - CC BY-NC-SA 4.0
1.7: Dimensional Analysis - CC BY 4.0
3.8 Resonance and Formal Charge Revisited - CC BY-
1.8: Matter, Measurement, and Problem Solving
NC-SA 4.0
(Exercises) - CC BY-NC-SA 4.0
3.9 Exceptions to the Octet Rule - CC BY-NC-SA 4.0
2: Atomic Structure - CC BY-NC-SA 4.0
3.10 Shapes of Molecules - VSEPR Theory and
2.1: Modern Atomic Theory and the Laws That Led Valence Bond Theory - CC BY-NC-SA 4.0
to It - CC BY-NC-SA 4.0 3.11 Practice Problems - CC BY-NC-SA 4.0
2.2 The Structure of the Atom - CC BY 4.0
4: Intermolecular Forces, Phases, and Solutions - CC BY-
2.3 Molar Mass - Counting Atoms by Weighing
NC-SA 4.0
Them - CC BY-NC-SA 4.0
2.4 Nuclear Reactions - CC BY-NC-SA 4.0 4.1 Water in Zero Gravity - an Introduction to
2.5 The Belt of Stability - Predicting the Type of Intermolecular Forces - Public Domain
Radioactivity - CC BY-NC-SA 4.0 4.2 Intermolecular Forces - CC BY-NC-SA 4.0
2.6 Half-lives and the Rate of Radioactive Decay - 4.3 Application of IMFs: Evaporation, Vapor
CC BY-NC-SA 4.0 Pressure, and Boiling Points - CC BY-NC-SA 4.0
2.7 Mass Defect - The Source of Nuclear Energy - 4.4: Intermolecular Forces in Action: Surface
CC BY-NC-SA 4.0 Tension, Viscosity, and Capillary Action - CC BY-
2.8 Nuclear Energy - Fission and Fusion - CC BY-NC- NC-SA 4.0
SA 4.0 4.5: Solids, Liquids, and Gases: A Molecular
2.9 The Nature of Light - CC BY-NC-SA 4.0 Comparison - CC BY-NC-SA 4.0
4.6 Phase Changes - CC BY-NC-SA 4.0

1 [Link]
 4.7: Pressure: The Result of Particle Collisions - CC 7.6: The First Law of Thermodynamics - CC BY-NC-
BY-NC-SA 4.0 SA 4.0
4.8: Gases - CC BY-NC-SA 4.0 7.7: Enthalpy: The Heat Evolved in a Chemical
4.9 Solutions - What Mixes Together and Why - CC Reaction at Constant Pressure - CC BY-NC-SA 4.0
BY-SA 4.0 7.8 Quantifying Heat - CC BY-NC-SA 4.0
4.10 Factors Affecting Solubility - CC BY-NC-SA 4.0 7.9: Entropy and the Second Law of
4.11 Suspensions and Colloids - CC BY-NC-SA 4.0 Thermodynamics - CC BY-NC-SA 4.0
4.12 Practice Problems - CC BY-NC-SA 4.0 7.10: Gibbs Free Energy - CC BY-NC-SA 4.0
Intermolecular Forces - CC BY-NC-SA 4.0 7.11 Gibbs Free Energy and Equilibrium - CC BY-
5: The Numbers Game - Solutions and Stoichiometry - NC-SA 4.0
CC BY-NC-SA 4.0 What we are studying - CC BY-NC-SA 4.0
5.1 Expressing Solution Concentration - CC BY-NC- 8: Acids and Bases - CC BY-NC-SA 4.0
SA 4.0 8.1: An Introduction to Acids and Bases - CC BY-NC-
5.2 Types of Aqueous Solutions and Solubility - CC SA 4.0
BY-NC-SA 4.0 8.2: Brønsted-Lowry Acids and Bases - CC BY-NC-
5.3 Colligative Properties and Freezing Point SA 4.0
Depression and Boiling Point Elevation and Osmosis 8.3 Lewis Acids and Bases - CC BY-NC-SA 4.0
- CC BY-NC-SA 4.0 8.4: Acid Strength and the Acid Dissociation
5.4 Writing and Balancing Chemical Equations - CC Constant (Ka) - CC BY-NC-SA 4.0
BY-NC-SA 4.0 8.5: Autoionization of Water and pH - CC BY-NC-SA
5.4a Example How Much Carbon Dioxide - 4.0
Undeclared 8.6 - Finding the Hydronium Ion Concentration and
pH of Strong and Weak Acid Solutions - CC BY-NC-
5.5 Limiting Reactant and Theoretical Yield and
SA 4.0
Percent Yield - CC BY-NC-SA 4.0
8.7: The Acid-Base Properties of Ions and Salts - CC
5.6 Representing Aqueous Reactions Molecular and
BY-NC-SA 4.0
Ionic and Complete Ionic Equations - CC BY-NC-SA
8.8: Buffers: Solutions That Resist pH Change - CC
4.0
BY-NC-SA 4.0
5.7 Chemical Reactions and Aqueous Reactions
8.9 Buffer Capacity and Buffer Range - CC BY-NC-
(Exercises) - CC BY-NC-SA 4.0
SA 4.0
6: Reaction Kinetics - CC BY-NC-SA 4.0
8.10: Lewis Acids and Bases - CC BY-NC-SA 4.0
6.1: Chemical Kinetics - CC BY-NC-SA 4.0 8.11: Acid/Base (Exercises) - CC BY-NC-SA 4.0
6.2 The Effect of Concentration on Reaction Rate -
9: Electrochemistry - CC BY-NC-SA 4.0
CC BY-NC-SA 4.0
6.3: Reaction Mechanisms - CC BY-NC-SA 4.0 9.1: Oxidation-Reduction Reactions - CC BY-NC-SA
6.4: The Effect of Temperature on Reaction Rate - CC 4.0
BY-NC-SA 4.0 9.2: Standard Reduction Potentials - CC BY-NC-SA
6.5 Catalysts - CC BY-NC-SA 4.0 4.0
9.3 Cell Potential, Gibbs Free Energy, and
7: Equilibrium and Thermodynamics - CC BY-NC-SA 4.0
Equilibrium - CC BY-NC-SA 4.0
7.1: The Concept of Dynamic Equilibrium - CC BY- 9.4: Batteries: Using Chemistry to Generate
NC-SA 4.0 Electricity - CC BY-NC-SA 4.0
7.2 The Equilibrium Constant - CC BY-NC-SA 4.0 9.5 Driving Reactant-Favored Reactions Using
7.3: Calculating the Equilibrium Constant From Electricity - CC BY-NC-SA 4.0
Measured Equilibrium Concentrations - CC BY-NC- 9.6 Undesirable Redox Reactions - CC BY-NC-SA 4.0
SA 4.0
Back Matter - CC BY-NC-SA 4.0
7.4 Predicting the Direction of a Reaction - CC BY-
Index - Undeclared
NC-SA 4.0
Glossary - Undeclared
7.5 Le Châtelier’s Principle: How a System at
Detailed Licensing - Undeclared
Equilibrium Responds to Disturbances - CC BY-NC-
SA 4.0

2 [Link]