Bulacan State University

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City of Malolos, Bulacan

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[Link]

Unit Title: Chapter 2 ENERGY and CHEMISTRY

Title of the Lesson:
2.1 Renewable and Non-Renewable Energy Sources in the Philippines
2.2 Review about Energy and Work, Energy units and its transformation
2.3 Principles of Heat Flow
2.4 Measurement of Heat Flow; Calorimetry
2.5 Enthalpy and Hess Law
2.6 Standard Enthalpy of Formation
2.7 Enthalpy of Phase Change
2.8 The First Law of Thermodynamics

Duration: 3 weeks

Introduction:

Most of the chemistry applications that are important in our lives would likely
involve energy and energy transformation.
 We looked at the burning of fuels as an application of chemical combustion.
 All the batteries depend on to power portable electrical devices are based on
chemical reactions as well.

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Thermochemistry explains the basic concepts of the amount of heat absorbed

or liberated during physical or chemical reactions. To determine the energy content
of foods, food scientist utilizes the principles in thermochemistry. Biologists are
concerned with studying energy in living organisms like the metabolic combustion of
sugar into carbon dioxide and water. Chemists and physicists explore harnessing
renewable energy resources aside from using oil and gas as an alternative source to
produce energy for our commercial and personal needs. It is also the concern of
engineers to increase the energy efficiency by finding better methods to heat and
cool our homes, and cooling needs of computers and electronics, among other
applications. Understanding thermochemical principles are essential for chemists,
physicists, biologists, and geologists.
Thermochemistry is the study of the heat flow that accompanies chemical
reactions. Our discussion of this subject will focus on
 Review some basic concept about heat and energy
 The basic principles of heat flow
 The Calorimetry that explains the experimental measurement of the
magnitude and direction of heat flow
 The concept of enthalpy, H (heat content), and enthalpy change, ΔH
 The calculation of ΔH for reactions: using thermochemical equations and
enthalpies of formation.
 The relationship between heat and work other forms of energy, as expressed
by the first Law of thermodynamics.
Chapter Objectives:
After completing this module, students should be able to:
 Differentiate and identify renewable and non-renewable energy sources
 Differentiate types of energy, and describe the nature of energy changes that
accompany physical and chemical changes
 Define and distinguish the related properties of heat, thermal energy, and
temperature
 Differentiate and determine specific heat and heat capacity, and describe the
physical implications of both
 Analyze and perform calculations involving heat, specific heat, and
temperature change
 Analyze, calculate and interpret heat and related properties using typical
calorimetry data
 Balance and write thermochemical equations
 Evaluate enthalpy changes for various chemical reactions
 Discuss Hess's Law and use it to compute reaction enthalpies
 Calculate the ΔH for reactions, using thermochemical equations and
enthalpies of formation
 State the first Law of thermodynamics

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Pretest:
Name: Chemistry for Score
Course,Year&Section: Engineers MODULE 2

Instructor: Date:

Rationale: This test will assess the level of existing chemistry knowledge, which is a
prerequisite for the successful learning of this module
Multiple Choice: Shade the letter corresponding to the best answer.

1. Energy is stored as__ in the food we eat. It is the energy stored in batteries and a
match stick that lights a candle.
[A] Thermal energy [B] electrical energy
[C] Chemical energy [D] mechanical energy

2. Which is not true of heat?

[A] It always flows from higher temperature objects to lower temperature objects.
[B] It is how much energy an object contains
[C] It is energy moving from one object to another
[D] It is energy transferred due to a difference in temperature.

3. What units measure heat?

[A] joules/mole or kilojoules/mole [B] Kelvins or Celsius
[C] Joules or calories [D] joules/gram or kilojoules/gram
4. Which energy transformation occurs in burning fuels?
[A] chemical-thermal [B] electrical-mechanical
[C] electromagnetic-chemical [D] chemical-electrical

5. SI unit for energy is

[A] Watt [B] Kilogram [C] Newton [D] Joule

6. A bomb calorimeter would be more useful than a coffee-cup calorimeter in

[A] When measuring the heat capacity of a solid
[B] When measuring the specific heat of water vapor
[C] When measuring the mass of a substance
[D] None of the above
7. When one put heated metal in cold water, which statement below describes what
happens?
[A] The temperature of the metal increases.
[B] The temperature of the water increases.
[C] The temperature of the water decreases.
[D] The temperature of the metal will decrease, and the temperature of the water
will increase

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8. The heat change of a system that has 50 Joules of work done on it and suffers an
80 Joules increase in internal energy is
[A] -30 J [B] + 30 J [C] -130 J [D] +130 J

9. Increase in the __ of an object, its particles move faster, making it feel warm to
the touch. [A] Chemical [B] thermal energy
[C] Electrical energy [D] mechanical energy

10. Energy density is the amount of energy

[A] Released per gram of fuel burned
[B] Stored in a given mass of a substance or system
[C] Stored in a given volume of a substance
[D] all of the above

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Lesson Proper/Course Methodology

2.1 RENEWABLE AND NON-RENEWABLE ENERGY SOURCES IN THE

PHILIPPINES

Renewable energy (clean energy) comes from natural processes, or sources

replenished continuously at a higher rate than consumed. The sources of renewable
energy are blowing wind, and shining sunlight, produce energy in the form of
electricity, heat, and transportation fuel.
There are four reasons why renewable energy is being pushed as the future's power
source. The sources are abundant; they can are everywhere: air, water, oceans,
land, underground, and even from outer space.

Non Renewable energy (dirty energy) comes from fossils like coal, gas, and oil. The
sources of this dirty energy are only available in limited amounts and may take a
longer period to fill up or replenish. The fuel like gasoline or gas that propels car's
engine comes from a finite source refined from crude oil derived from fossil fuels.
The use of non-renewable energy sources can endanger human health and the
environment. Oil drilling may result in stripping the natural mines. Fracking is a
mining method that breaks or cracks shale rocks to extract oil or gas inside it. This
technology causes water pollution and earthquakes. The burning of coal pollutes the
air and contributes to global warming.

As a tropical archipelago, the Philippines can generate a lot of energy from

natural resources. In recent years, solar panels have come to the forefront of cost
efficiency with regular consumers.

The Philippines utilizes energy from renewable resources for a long while
now. Filipino people recognize the importance of using renewable energies as a
better alternative to coal and oil from fossil fuels. The following are the renewable
energies found in the Philippines and the power plant's geographic location.

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Renewable Energy Spots in the Philippines

Hydroelectric Power is moving water, and it is a powerful source of energy. The

Philippines use two methods to harness power; dam storage or impoundment and
run-of-river. While impoundment uses human-made dams to store water, run-of-
river relies on flowing bodies of water like waterfalls. Both methods turn a turbine to
generate power. There are hydroelectric power plants in Misamis Oriental, Lanao
del Norte, Bukidnon, Davao del Sur, Lanao del Norte, Bohol, Ilocos Sur, Nueva
Ecija, Pangasinan, Benguet, Laguna, and Bulacan.
Geothermal energy comes from the earth's core. Geothermal energy

Geothermal energy comes from the heat below the surface of the earth. Flash
steaming extracts steam pulls water with a temperature greater than 182 °C using
steam pipes. The superheated steam powers the turbines and generates energy
while the condensed water is recycled. The other way to utilize steam is the binary
cycle process. The process uses water at a lower temperature than steam from
below the earth. The extracted water boils and is pumped through a heat exchanger
where it boils another liquid that powers the turbine. There are geothermal plants in
Laguna, Sorsogon, Albay, Batangas, Negros Occidental, Leyte, and North Cotabato.

Solar energy is the source of energy through industrial-sized photovoltaic plants in

the country. The country recently incorporated a large scale solar farm in a region
that receives a high amount of sunlight each year. The Philippines' major solar farms
are in Cavite, Pampanga, Ilocos Norte, and Cagayan de Oro.

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Wind Energy uses the wind, or moving air turns the propeller blades of a turbine
through a rotor that produces electricity. There are wind power plants Ilocos Norte,
Rizal, Guimaras, and Aklan.

Biomass energy is similar to fossil fuel. The burning biomass boils water to produce
steam that will drive a generator. The Philippines is an agricultural area, thereby
abundant in natural resources of biomass source coconut husks, bagasse from
sugarcane, and rice husks. There are biomass power plants in Isabela, Nueva Ecija,
Rizal, Laguna, Isabela, and Metro Manila.

The Philippines' various electricity sources are coal, oil, natural gas, biomass,
hydroelectric, solar, wind, and geothermal sources. According to the 2016 report of
the Department of Energy, the installed capacity of renewable energy was about
6,859 megawatts (MW) were 3,618 MW (52%) is from hydropower, 1,916 MW
(28%) geothermal, 865 MW (11%) solar, 427 MW (6%) wind, and 233 MW (3%).

According to the energy department, 32% of the country's total installed

generation capacity is renewable energy. About 116 renewable energy facilities
currently exist in the Philippines. In the last decade, the Philippines has seen a 45%
increase in the installed renewable generation capacity. Based on the 2030 targets,
40% of the country's total installed capacity will be renewables.

2.2 Review about Energy and Work, Energy units and its transformation

Energy is related to work because it the capacity to supply heat or do work.

Work (w), in general, is the action of a force causing an object to move through a
distance while in thermodynamics, work is done by a system if the system transfers
the energy to its surrounding. Work is energy in transit.
Different forms of energy, like internal energy, potential energy, and kinetic
energy, are properties of a system. The energy in its various forms are:

Potential Energy and Kinetic Energy

We encounter energy's two broad categories as potential energy and kinetic

energy. Potential energy is associated with the configuration, relative position,
magnetic, elastic, and electrical nature of matter, while kinetic energy is associated
with motion.

Let us consider a space shuttle ride in the Enchanted Kingdom. A space

shuttle car gains potential energy on a macroscopic scale as it moves up the inclined
track because it acquires a higher position relative to the ground. The pull of gravity
is attracting it downward (Gravitational Potential energy).
Note that the pull of gravity is not the only force responsible for objects having
energy associated with their positions. The force of attraction and repulsion between
electrical charges also lead to potential energy (Electrical Potential energy), it is
because of the consideration of the structure of atoms and molecules. When the
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space shuttle car heads down the first hill, it transforms gravitational potential energy
into kinetic energy. (Kinetic energy = ½mv2). The discussion above shows kinetic
and potential energy on a macroscopic scale.

Considering energy at a microscopic level, all substances and objects, from

a log of wood or fuels to the paper used in printed books, possessed these same
energy forms because any substance or object is composed of atoms and
molecules. All of these atoms and molecules have kinetic energy because of their
constant motion, and they also possess potential energy due to the various forces
they exert on one another. These combined kinetic and potential energies of the
atoms and molecules that make up an object constitute its internal energy. Thus the
space shuttle cars have three primary forms of energy: kinetic (from their
motion), potential (from their position relative to the ground), and internal
(from the molecules that compose the materials).

Much of an object's internal energy, be it a space shuttle car or a piece of

coal, is associated with the potential energy arising from the atoms' relative positions
that make up the object. The breaking or making of chemical bonds changes this
potential energy. When bonds break in the reactants during chemical reactions, and
new bonds form in the products. If the amount of energy released in the bond
making is more significant than that consumed in bond breaking, the overall process
gives off energy. The liberation of energy is an example of chemical energy, and
the harnessing of chemical energy is an essential aspect of the overlap between
chemistry and engineering.

At times, we find it useful to have more specific terms for various forms of
energy.
Radiant energy is analogous with light or electromagnetic radiation. The
sun’s radiant energy is ultimately responsible for the majority of energy resources on
this planet.
Mechanical energy is related to the movement of macroscopic objects.
Thermal energy refers to the molecular level motion of atoms and
molecules.)
Electrical energy is because of the movement of charge (usually electron) in
a metal.
Nuclear energy is associated with the energy released in nuclear fusion and
fission processes, a form of potential energy related to protons and neutrons'
arrangement in atomic nuclei.
Thermal Energy, Temperature, and Heat
Thermal energy refers to kinetic energy associated with atoms and
molecules' random motion, while the temperature is the quantitative comparison of
how cold or hot an object is. Absolute zero is the coldest theoretical temperature

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where the atoms and molecules have zero kinetic energy. The higher average kinetic
energy of the atoms and molecules (vibrating fast) in an object means the object is
"hot." Slow-moving atoms and molecules mean low kinetic energy, then the object is
"cold."
Changing the quantity or the amount of thermal energy in a sample of matter
will change temperature or phase change. If there is no phase change like vaporizing
or melting or chemical reaction, an increase in the amount of thermal energy will
result in its temperature to increase. Similarly, the absence of chemical reaction or
phase change like freezing or condensation occurs. A decrease in the amount of
thermal energy in a sample of matter will decrease its temperature.
It is the expected behavior of most substances to expand as their temperature
increases and contract as their temperature decreases. The expansion and
contraction of matter can measure temperature changes. Thermometers depend on
the expansion and contraction of substances in response to temperature changes.
 In a thermometer (alcohol or mercury), the liquid (dyed red for visibility)
contracts when cooled and expands when heated, and the glass tube
containing the liquid also expands.
 In a bimetallic thermometer, two different metals (brass and steel) form a two-
layered strip. Cooling or heating the bimetallic material, brass contracts or
expands more than the other metal steel, resulting in the strip of metals to
uncoil or coil. Alcohol and bimetallic thermometers have a calibrated scale
that indicates the temperature.

Heat (q) refers to the transfer of thermal energy between two bodies because
of the temperature difference. Heat flow increases one body's thermal energy at low
temperature and decreases the other body's thermal energy. Consider a substance
(H) at high temperature (and high thermal energy) and a low temperature (and low
thermal energy) substance (L). The atoms and molecules in substance H have a
higher average kinetic energy than those in substance L. If we place substance H in
contact with substance L, the thermal energy will spontaneously flow from substance
H to substance L. The temperature of substance H will decrease, as well as the
average kinetic energy of its molecules, the temperature of substance L will
increase, and its molecules' average kinetic energy. When the two substances reach
the same temperature, the heat flow ceases, and thermal equilibrium is reached.
(Figure 2.1)

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Substances undergoing chemical reactions and physical changes can release

or absorb heat. A chemical reaction or change that liberates heat is an exothermic
process. Consider the combustion reaction in an acetylene torch where energy is
liberated in the form of light as evidence by the torch's flame. A chemical reaction or
change that absorbs heat is an endothermic process. Consider a cold pack used to
treat muscle strains provides an example of an endothermic process. The reaction
between water and salt-like ammonium nitrate (the substances in the cold pack)
absorbs heat, leading to a cold sensation.
The second form of energy transfer is work. Work is the transfer of energy
done by a force in moving a mass some distance against resistance. Lifting a set of
roller coaster cars a hill against the pull of gravity is an example of work. If we
consider macroscopic samples, we are viewing work in terms of mechanical energy.
Work, however, involves a broader range of phenomena than just the mechanical
movement of macroscopic objects. The most common type of work in chemical
processes is pressure-volume work (PV-work).
 Work is done when a gas expands.
 Suppose gas inside an inflated balloon will expand into the large
volume of the room. In that case, if released before it is tied off, it flies
around because the flying balloon has mass, and it is easy to see that
the expanding gas is doing work on the balloon: this is pressure-
volume work.
 To burn gasoline in a car engine is a more productive example of work
being done by a chemical reaction. Gasoline is a complex mixture of
hydrocarbons. The energy required to propel a car is the energy
released from those hydrocarbons' combustion in the engine cylinders.
Hydrocarbon + O2 (g) → CO2 (g) + H2O (g)
The combustion process produces carbon dioxide and water vapor, and those
gases do. PV work as they expand against the piston in the cylinder. This PV-
work is then transmitted through the drive train to move the car.

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Energy/Work Units

We use a wide variety of units when measuring and discussing energy, and
various disciplines of science and engineering tend to favor particular choices of
units. The three units of energy and work are:

1. JOULE (J) - The SI unit of energy is the joule (J), and 1 joule is equal
to 1 kg m2/s2. Realizing that work should have units of energy helps us
to make sense of this unit. Work is force (F) times the distance (s)
parallel to the force, and force is mass (m) times acceleration (a). Thus,
work is

2. CALORIE (cal) is the energy needed to change one gram of water

temperature from 14.5 to 15.5 °C. A source of frequent confusion in
comparing energy units is that the Calorie (nutritional Calorie) reported
for foods is a kilocalorie. The amount of energy in food has the unit's
nutritional Calorie (Calorie) is the energy unit used to quantify the
amount of energy derived from foods' metabolism. One Calorie (note
the use of capital letter C) is equal to 1000 calories (1 kcal), it is the
same as the amount of energy needed to heat 1 kg of water by 1 °C.
(The food Calorie uses an uppercase "C.") Thus, 1 Calorie is
equivalent to 4184 J, or 4.184 kJ.

3. BRITISH THERMAL UNIT (BTU) - Btu, which is the unit used in some
engineering disciplines. The amount of energy needed to change the
temperature of one pound of water by 1°F.

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2.3 Principles of Heat Flow

In any discussion of heat flow, it is essential to distinguish between the
system and surroundings. The system is that part of the universe on which we are
after. It might be a sample of water in contact with a hot plate in a simple case. The
surroundings, which exchange energy with the system, make up, in principle, the
rest of the universe. For all practical purposes, however, they include only those
materials in close contact with the system. In Figure 2.2, the surroundings consist of
the hot plate, the beaker holding the water sample, and the air (surrounding it).
When a chemical reaction occurs, the system consists of the substances involved,
reactants, and products. All other materials in contact with the system like the
container (beaker, test tube), in which the reaction takes place, and the air are the
surrounding.

Direction and Sign of Heat Flow

Consider the setup in Figure 2.2 again. Turning on the hot plate (surrounding),
there is a flow of heat from the surroundings into the system, 50.0 g of water
(system). This situation states that the heat flow, q, for the system is a positive
quantity.

When heat flows into a system, its temperature rises. In this case, the
temperature of the 50.0-g water sample might increase from 50.00C to 80.00C. When
the hot plate is shut off, the hot water gives off heat to the surrounding air. q for the
system, in this case, is a negative quantity.

As usually the case, the system's temperature drops when heat flows out of it
into the surroundings. The 50.0-g water sample might cool from 80.00C back to
50.00C.

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This same reasoning can happen to a reaction in which the system consists of
the reaction mixture (products and reactants). We can distinguish between an
endothermic process and an exothermic process.
• An endothermic process (q > 0), in which heat flows from the surroundings
into the reaction system.
An example is the melting of ice:
H2O(s) → H2O (l) q > 0
The melting of ice absorbs heat from the surroundings, which might be the water in
a glass of iced milk tea. The surroundings' temperature drops, perhaps from 250C to
30 C, as they give up heat to the system.
• An exothermic process (q < 0), in which heat flows from the reaction system
into the surroundings. A familiar example is the combustion of methane, the
primary component of natural gas.
CH4 (g) + 2O2 (g) → CO2 (g) 1 2H2O (l) q < 0
This reaction evolves heat to the surroundings, the air around a Bunsen burner in the
laboratory, or a baked cake in a gas oven. In either case, the effect of heat transfer is
to raise the temperature of the surroundings.
The magnitude of Heat Flow
A quantity of heat is the thermal energy required to raise the temperature of a
given mass. But the amount of thermal energy needed to raise the temperature of a
substance varies for different materials. We have two options for expressing the
amount of material: by mass or by moles.

The specific heat capacity or simply specific heat of a material is the

quantity of heat needed to raise a unit mass's temperature by one degree. In
equation form,

Similarly, the molar heat capacity or simply heat capacity is a physical

property that describes the amount of heat required to raise one mole of a
substance's temperature by 1°C. So if we choose to express the amount of material
in terms of moles rather than mass m, our equation changes only slightly. If gram-
mole is the unit of mass, the number of moles (n) is

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(The subscript p on indicates that this is the heat capacity at constant

pressure. Under other conditions, such as constant volume, the heat capacity's value
may differ slightly.)
Either equation provides the same information about the heat needed to
produce a given change in temperature. As long as we know the substance's molar
mass, it should be simple to convert the specific heat and the molar heat capacity.
Table 2.1 below provides a list of specific heats and molar heat capacities for a few
materials.
Table 2.1 Specific heat and molar heat capacities for some common
substances
Specific heat, c Molar Heat Capacity, Cp
Substance (state) ( ) )
Al(s) 0.900 24.3

Cu(s) 0.385 24.5

H2O(s) ice 2.093 37.7

H2O() water 4.184 75.3

H2O(g) steam 2.03 36.4

Ca(s) 0.653 26.2

Fe(s) 0.444 24.8

Hg(g) 0.138 27.7

CO2(g) 0.843 37.1

C6H6(ℓ), benzene 1.740 136

C6H6(g), benzene 1.040 81.6

C2H5OH(ℓ), ethanol 2.376 113

C2H5OH(g), ethanol 0.954 420

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(C2H5)2O(ℓ) diethyl ether 3.740 172

(C2H5)2O(g)diethyl ether 2.350 108

Note that water has a much higher heat capacity than the metals shown in this table. This is
true for most metals.

Sample Problem 2.1. Calculate the quantity of heat lost if 1.40 mol of H2O (liquid)
cools from 100. 00C to 30. 00C and that of 1.40 mol steam at 200. 00C cools to 110.
00C
Given: For H2O (liquid)

For H2O (gas)

Required: the amount of heat q for both water and steam

Solution for

25.2 g

( ) ( )

For

25.2 g

= ( )

Discussion: The negative sign shows that heat flows from the water and steam (system) to the
surroundings.

Sample Problem 2.2. Heating a 24.0-g aluminum (Al) can increase the temperature
by 15.0°C. Calculate the value of q for the can.
Given: = 24.0 g = 15.0oC

Required: the amount of heat q

Solution

( )

Discussion: The positive sign shows that heat flows into the system.

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Sample Problem 2.3. Cp= 75.3Jmole C (molar heat capacity of liquid water ). How
much is the heat given off if 37.5 g of water cools from 42.0 to 7.0°C?
Given: = 37.5 g = 42.0oC = 7.0oC

= ( )

Required: amount of heat q for water

Solution:

q = –5.49 × 103 J = –5.49 kJ

Discussion: Water has given off energy to the surroundings, thus the sign of heat is negative. Note
that the correct sign of q will be computed as long as we express

Sample Problem 2.4. A piece of unknown metal weighs 405 g. When the metal
piece absorbs 7.80 kJ of heat, its temperature increases from 22.4 °C to 43.6 °C.
Identify the metal by computing the specific heat of this metal.
Given:

Required: specific heat of metal,

Solution: ( )

Discussion: The computed value of the specific heat of metal matches to the specific heat of
aluminum, thus we may say that the unknown metal is aluminum.

Sample Problem 2.5. A thermal bottle containing 8.0 × 102 g of water is heated, and
the water temperature increases from 21.0°C to 85.0 °C. How much heat did the
water absorb?
Given:

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Required: amount of heat absorb by water, q

Solution:

q = (8.0 x 102 g) ( ) (85.0°C – 20.0°C)

q = 217,568 J = 218 kJ
Discussion: The water absorbed heat because the temperature increased thus q is positive.

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Name: Chemistry for Score

Course,Year&Section: Engineers MODULE 2

Instructor: Date:

Exercise 2.1
Answer the following questions and problems.
1. Consider a bonfire and a burning match stick at the same temperature, yet
one would not sit around a burning match stick on a cold evening to stay
warm. Why not?
_____________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
______________________________________________________________
2. Identify several energy transitions that take place during the typical operation
of an automobile.

3. Describe the difference between heat capacity and specific heat of a

substance.
______________________________________________________________
______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________

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Problem 1. A block of iron ( weighing 207 grams absorbs 1.50 kJ

of heat. What is the change in the temperature of the iron?

Problem 2. If 226 x 103 J of heat increases the temperature of 47.0 kg of copper

(Atomic mass = 63.55 g/mole) by 12.5°C, determine is the molar heat capacity of
copper?

Problem 3. A piece of unknown metal has a mass of 217 g. The metal absorbs 1.43
kJ of heat, its temperature increases from 20.5 °C to 35.1°C. Calculate the specific
heat of this metal, and predict its identity.

Problem 4. Determine how much heat, in joules, must be added to a 5.00 × 10 2- g

copper pan to change its temperature from 25 °C to 250 °C? The specific heat of
copper iron is 0.385 J/g °C.

Problem 5. An unknown silver/gray (92.9-g) piece of metal at 178.0°C is quickly

placed to 75.0 mL of water initially at 24.0°C. After a few minutes, both the metal and
the water have reached 29.7°C. Calculate the specific heat and the identity of the
metal. (Note: Use table 2.1 to find the specific heat of two different metals that is
close to your answer and explain how you can confidently determine the metal).

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2.4 Measurement of Heat Flow: Calorimetry

Calorimetry (derived from the Greek word 'calor' means heat and 'metron'
means measure) is the study of the measurement of heat flow associated with its
state changes due to chemical reactions, phase changes, or physical changes. It is
concerned with the heat properties in the field of chemistry and physics. The
measurement of heat uses the application of the Law of conservation of energy to an
insulated system. Laboratory experiments use devices called calorimeters. A
calorimeter is a device used to measure either specific heat capacity or the amount
of energy transferred (absorbed or liberated) in chemical reactions, phase changes,
or physical changes.
The temperature change in its surrounding measures the heat absorbed or
released by the system. The thermal equilibrium principle tells that whenever objects
are placed together in an insulated enclosure, they will eventually reach the same
temperature. If the energy is conserved, the heat lost by warm objects will be equal
to the heat gained by the cold objects.
In measuring the heat flow of a reaction, laboratory experiments use a
calorimeter with water and some materials (known heat capacity). The calorimeter
walls are insulated so that there is no exchange of heat with the surrounding air. The
heat flow is simply between the calorimeter and the reaction system. The total heat
flow is equal to the sum of the heat flow for the reaction system and the calorimeter:

Notice that if the reaction is exothermic ( must be positive;

that is, heat flows from the reaction mixture into the calorimeter. Conversely, if the
reaction is endothermic, the calorimeter gives up heat to the reaction mixture.
The equation just written is basic to calorimetric measurements. It allows
calculating the amount of heat absorbed or evolved in a reaction if the heat capacity
is known, Ccal, and the temperature change, ΔT, of the calorimeter.

Coffee-Cup Calorimeter
Chemistry laboratory experiments use a simple coffee-cup calorimeter (figure
2.2(a)). It is made of two-layered Styrofoam cups partially filled with water and a
tightly-fitting cover with a thermometer hole. The polystyrene foam is a good
insulator; there is very little heat flow through its walls. Therefore, we say that the
water absorbs all the heat liberated by the calorimeter's reaction. To a good degree
of approximation, the coffee-cup calorimeter's heat capacity is that of the water:

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( )

Sample Problem 2.6: Dissolving calcium chloride, CaCl2, in water maintains the
vegetables' firmness in canned vegetables. The reaction is:

CaCl2 (s) → Ca2+ (aq) + 2Cl- (aq)

Upon addition of 1.50 grams of calcium chloride in a calorimeter containing 75.0

grams of water at 26.50C, increases the temperature to 28.50C. We assume that the
water absorbs all the heat given off by the reaction.
a. Calculate heat for the reaction system.
b. Determine the mass of CaCl2 added to change the solution's temperature to
11.00 C?
Given: a.

b. if ΔT = 11.00 C
Required: a. heat of reaction, b. mass of CaCl2 to be added
Solution: a.

( )

627.6 J

Therefore:
b.

( )

To compute for mass use as a conversion factor

( )
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Therefore:

For reactions in which the products reach high temperatures and reactions
involving gases, a coffee-cup calorimeter cannot be used, since gases would escape
from the cup and the cup cannot withstand high temperatures. The bomb calorimeter
is more applicable to use.

Bomb Calorimeter (shown in figure 2.3 (b) ) consists of a large outer container
made of a metal that does not readily conduct heat. A known amount sample of the
reactant(s) is placed inside the heavy-walled metal vessel called a steel bomb to use
it. It is then sealed and put into the insulated outer container filled with sufficient
water to cover the bomb completely, and the entire apparatus is closed.

The initial temperature is measured precisely. An electric current is run into

the inner container to burn the sample. The temperature readings of water in the
outer container can then be used to find the sample's energy of combustion.

An experimental method to measure heat using Bomb Calorimeter:

1. Calibration of the calorimeter in which a known amount of heat is generated in
the apparatus. The calibration can be done either by burning a known amount
of a well-characterized material or by resistive heating. A known amount of
current is passed through a wire that heats due to its electrical resistance. The
entire calorimeter's heat capacity may be obtained by measuring the change
in temperature of the surroundings resulting from a known heat input.

( ).

Where:

Note that no mass or number of moles term here for the quantity of material. The
calorimeter constant is the heat capacity of a particular object (or set of objects)
rather than that of a material. It may help to think of it as the heat capacity “per
calorimeter” (unique to each calorimeter).
2. The second step is the actual measurement, in which we determine the
amount of heat absorbed or released in the reaction of a known amount of
material. Once the calorimeter constant is known, we are ready to use the
calorimeter for our actual measurement. We place a known amount of
reactant(s) into the calorimeter, initiate the reaction, and then measure the
calorimeter's resulting temperature change. The calorimeter constant allows
us to determine the amount of heat released or absorbed in the reaction.

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(a) (b)
Figure 2.3. Calorimeters range from (a) simple, inexpensive Coffee-cup calorimeter for student’s
use in the laboratory to (b) Bomb Calorimeter, expensive, more accurate models for industry and
research.

Sample Problem 2.7. A bomb calorimeter is to be used to compare the energy

content of some fuels. In the calorimeter's calibration, an electrical resistance heater
supplies 120.0 J of heat, and there is a temperature increase of 0.950°C. Then 0.245
g of a particular fuel is burned in the same calorimeter, the temperature increases by
5.23°C. Compute the energy density of this fuel, which is the amount of energy
liberated per gram of fuel burned.

Given: For calibration:

For experiment:

Required: energy density of fuel =

Solution: The calibration step allows us to determine the calorimeter constant

The amount of heat liberated from the fuel can be determined using

Note: no water is involved in the problem, therefore:

Finally, we divide this heat by the mass of fuel generated to arrive at the
required energy density.

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Discussion: This problem illustrates the need to be careful with signs in thermodynamic calculations.
Because the burning of fuel releases heat, q for the fuel should be negative. However, the energy
density would be reported positively, resulting in the additional negative sign in the final step.

Sample Problem 2.8. Hydrogen chloride is used in etching semiconductors. The

reaction of hydrogen and chlorine gases produces hydrogen chloride.

H2 (g) + Cl2 (g) → 2 HCl (g)

When 1.00 g of H2 reacts completely with Cl2 in a bomb calorimeter with a

heat capacity of 5.15 kJ/0C, the bomb's temperature rises from 20.0 0C to 29.820C.
The calorimeter can hold 1.00 kg of water. Calculate the heat evolved by the
reaction?
Given:

Required: heat for the reaction

Solution:

( )

Discussion: The negative heat of reaction means that energy is evolved or given off. The
amount of hydrogen gas (1.00 g) that reacted is not relevant to the solution of this problem.

2.5 STANDARD ENTHALPY of REACTION (H) and HESS’S LAW

Enthalpy is the amount of heat flow into and out of a system in a constant-
pressure process, represented by the symbol H and defined as E + PV. It is an
extensive property; thus, its magnitude depends on the amount of substance
present.
It is impossible to determine the enthalpy of a substance, so it's the enthalpy
change, ΔH, that we measure. If a given chemical or physical process is carried out
at constant pressure with the only work done caused by expansion or contraction,
then the heat flow (qp) and enthalpy change (ΔH) for the process are equal. The
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enthalpy change or enthalpy of reaction, ΔH, is the difference between the

products' enthalpies and the reactants' enthalpies:

In other words, the enthalpy of reaction is the quantity of heat exchanged

between the system and its surroundings when chemical reactions occur. The heat
will tend to flow until the system and surroundings are at the same temperature.
• When the system absorbs heat in a chemical reaction, the process is
endothermic (it feels cold).

• When the system produces heat in a chemical reaction, which the system
produces heat, it is exothermic (it feels hot).

Rules for determining the enthalpy change. (Rules of thermochemistry)

The thermochemical equation is used by the chemist to represent the changes in

both matter and energy. A thermochemical equation is a balanced reaction
equation accompanied by the enthalpy change (ΔH) associated with it. The following
rules apply when we use ΔH.
1. The magnitude of enthalpy of reaction (ΔH) is directly proportional to the
reactant or product amount.
 The amount of heat that must be absorbed to boil a water sample is
directly proportional to its mass.
 The more gasoline burn in your car's engine, the more energy is
produced.

This rule allows you to find ΔH corresponding to any desired amount of reactant or
product. Consider the thermochemical equation,
H2 (g) + Cl2 (g) → 2HCl (g) ΔH = -185 (kJ) kilojoules (exothermic)

This equation indicates that when 1 mole of hydrogen gas and 1 mole of
chlorine gas at some temperature and pressure change to 2 moles of hydrochloric
acid gas at the same temperature and pressure, 185 kJ of heat are released to the
surroundings. If the coefficients of the chemical equation are multiplied by some
factor, the enthalpy change must be multiplied by that same factor (ΔH is an
extensive property)

Two-fold increase in amounts:

2H2 (g) + 2Cl2 (g) → 4HCl (g) ΔH = 2(-185kJ) = -370kJ
Two-fold decrease in amounts)
½H2 (g) + ½Cl2 (g) → HCl (g) ΔH = ½(-185kJ) = -92.5kJ

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The thermochemical equation also allows us to relate the enthalpy change to

amounts of reactants and products, leading to conversion factors such as

Similarly we can say that:

H2O(s) → H2O (l) ΔH = +6.01 kJ (endothermic)
2H2O(s) → 2H2O (l) ΔH = +12.02 kJ

Sample Problem 2.9. The Bunsen burners in your labs are fuelled by natural gas,
which is mostly methane, CH4. The thermochemical equation for the burning in
oxygen (combustion) of methane is
CH4 (g) + 2O2 → CO2 (g) + 2H2O (l) ΔH = -890.3 kJ
Calculate ΔH when 5.00 g of CH4 reacts with excess oxygen. From the
thermochemical equation above: can be used as a conversion factor
ΔH =5.00 g CH4 (
Discussion: The conversion factor can be derived from a thermochemical equation.

Sample Problem 2.10. 2.9 kJ of heat is produced when 0.0500 mole of HCl (aq)
reacts with 0.0500 mole of NaOH (aq) to form 0.0500 mole of NaCl (aq). Calculate
ΔH, the enthalpy change, per mole of acid reacting, for the acid-base reaction
HCl (aq) +NaOH (aq) →NaCl (aq) +H2O (l)
For the reaction of 0.0500-mole acid (HCl), q = -2.9 kJ, the ratio can be
used as a conversion factor to find the heat produced when 1 mole of HCl reacts:
ΔH =1 mole HCl (
The enthalpy change ΔH when 1 mole of HCl reacts is −58 kJ. In the chemical
reaction, there is 1 mole of HCl; we write the thermochemical equation as:
HCl (aq) +NaOH (aq) →NaCl (aq) +H2O (l) ΔH=-58kJ

2. The enthalpy of reaction ΔH for a reaction is equal in magnitude but

opposite in sign to ΔH for the reverse reaction. Another way to state this
rule is to say that the amount of heat evolved in a reaction is exactly equal to
the amount of heat absorbed in the reverse reaction. If 6.01 kJ of heat is
absorbed when a mole of ice melts,
H2O(s) → H2O (l) ΔH = +6.01 kJ
Then 6.01 kJ of heat should be evolved when a mole of liquid water freezes.
H2O (l) → H2O(s) ΔH = -6.01 kJ

3. The value of Δ H for a reaction is the same whether it occurs in one step
or a series of steps
Then the thermochemical equation can be expressed as the sum of two or
more equations,

Equation = equation1 + equation2 + . . .

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Then ΔH for the overall equation is the sum of the ΔH’s for the individual
equations:
ΔH = ΔH1 + ΔH2 + . . .

This relationship is referred to as Hess's Law, after Germain Hess (1802–

1850), professor of chemistry at the University of St. Petersburg, who deduced it in
1840. Hess's Law is a direct consequence of the fact that enthalpy is state
property, dependent only on initial and final states. It means that ΔH must equal
the sum of ΔH1 and ΔH2 because the final and initial states are the same for the two
processes.
Hess's Law is very convenient for obtaining values of ΔH for reactions that are
difficult to carry out in a calorimeter.

Consider the formation of the toxic gas carbon monoxide from the elements.
C(s) + ½O2 (g) → CO (g)
It is difficult, practically impossible, to measure ΔH for this reaction because
when carbon burns, the primary product is always carbon dioxide, CO 2. However, it
is possible to calculate ΔH using thermochemical data for two other reactions readily
carried out in the laboratory.
Summarizing the rules of thermochemistry:
1. ΔH is directly proportional to the amount of reactant or product.
2. ΔH changes sign when a reaction is reversed.
3. ΔH for a reaction has the same value regardless of the number of steps.

Sample Problem 2.11. When carbon is burned in a limited amount of oxygen will
result to the formation of carbon monoxide, CO, is a poisonous gas. Given the two
thermochemical equation, determine ΔH for the reaction
C(s) + ½O2 → CO (g)
Given: (1) C(s) + O2 (g) → CO2 (g) ΔH = -393.5 kJ
(2) 2CO (g) + O2 (g) → 2CO2 (g) ΔH = -566.0 kJ
Required: Calculate ΔH for the reaction C(s) + ½O2 → CO (g)
ΔH = 283.0 kJ + (-393.5) kJ = -110.5 kJ

Solution: Apply the rules above with the given equations until you arrive at two
equations that will add to provide the equation C(s) + ½O2 → CO (g)
Rule 2 in (2) 2CO2 (g) → 2CO (g) + O2 (g) ΔH = - (-566.0 kJ) (2a)
Rule 1 in (2a) CO2 (g) → CO (g) + ½O2 (g) ΔH = ½(566.0 kJ)
=283.0J

(2a) CO2 (g) → CO (g) + ½O2 (g) ΔH =283.0 kJ

(1) C(s) + O2 (g) → CO2 (g) ΔH = -393.5 kiloJoules

Add: CO2 (g) + C(s) + O2 (g) → CO (g) + ½O2 (g) + CO2 (g)
Simplify C(s) + ½O2 (g) → CO (g) ΔH = 283.0 kJ + (-393.5 kJ)
C(s) + ½O2 (g) → CO (g) ΔH = -110.5 kiloJoules

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2.6. Standard Enthalpy of Formation or Heat of Formation

A formation reaction is when exactly one mole of a chemical compound forms

from its elements in their standard states. The standard molar enthalpy of formation
of a compound, is equal to the enthalpy change when one mole of the
compound forms at a constant pressure of 1 atmosphere and a fixed temperature,
ordinarily 250C, from the free elements in their stable states at that pressure and
temperature (standard state conditions). These values are useful for computing or
predicting enthalpy changes for chemical reactions that are impractical or dangerous
to carry out; or for processes for which it is difficult to make measurements. We can
determine the enthalpy change for any reaction using Hess's Law if we have values
for the appropriate standard enthalpies of formation.

Enthalpies of formation for a variety of compounds are listed in the table

below. Notice that, with a few exceptions, enthalpies of formation are negative
quantities. It means that the formation of a compound from the elements is ordinarily
exothermic. On the other hand, when a compound decomposes to the elements,
heat usually must be absorbed. You will note from the table that there are no entries
for elemental species such as Br2 (l) and O2 (g). It is a consequence of how
enthalpies of formation are defined. In effect, the standard enthalpy of formation
of an element in its stable state at 25o C and 1 atmosphere is taken to be zero.
That is, Br2 (l) = 0 O2 (g) = 0

Applying the above principle for the heat of formation reactions:

Ag(s) + ½Cl2(g) → AgCl(s) ΔH = -127.1 kJ =

½N2 (g) + O2 (g) → NO2 (g) ΔH = +33.2 kJ =

It follows that of AgCl(s) = and of NO2 (g) = because

Cl2 (g) = Ag(s) = N2 (g) = O2 (g) = 0

Sample Problem 2.12. O3 (g), which is ozone, is formed from oxygen gas, O2 (g), by
an endothermic process. The ultraviolet radiations are the source of the energy that
drives this reaction in the upper atmosphere. Let us assume that both the reactants
and products of the reaction are in their standard states, determine the standard
enthalpy of formation, of ozone from the following information:
3O2 (g) →2O3 (g)

Required: O3 (g)

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Solution: is the enthalpy change for the formation of one mole of a

substance in its standard state from the elements in their standard states. Thus,
dividing the number of moles by two to obtain one mole O3 for O3 (g) is the
enthalpy change for the reaction:
O2 (g) →O3 (g)
For the formation of 2 mol of O3 (g), , the ratio can be
used as a conversion factor to find the heat produced when 1 mole of O3 gas is
formed, which is the enthalpy of formation of O3 gas:
( )
O3 (g) = 143kJ/mol

Sample Problem 2.13. Write the heat of formation reaction equations for:
a) C2H5OH(l)
b) Ca3(PO4)2(s)

Solution: Remember that reaction equations are for forming 1 mole of the
compound from its constituent elements under standard conditions,

a) 2C (s, graphite)+3H2 (g)+ O2 (g) → C2H5OH (l)

b) 3Ca (s) + P4 (s) + 4O2 (g) → Ca3(PO4)2(s)

Discussion: The standard state of carbon is graphite, and phosphorus exists as P 4.

Table 2.2 Standard Enthalpies of Formation at 250C (kJ/mol) of Compounds at

1 atmosphere, Aqueous Ions at 1 M

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Calculation of Enthalpy of Reaction

Enthalpies of formation can be used to calculate enthalpies of
reaction. To do this, apply this general rule:
The (standard enthalpy change), for a given thermochemical equation, is
equal to the sum of the standard enthalpies of formation of the product compounds
minus the sum of the standard enthalpies of formation of the reactant compounds.
Σ
Consider the hypothetical reaction below

The enthalpy change for this reaction may is

In applying this equation, one must consider the following rules:

• Heats of formation of elements in their standard states is zero, and they can be
omitted in the computations.
To illustrate, consider the thermochemical reaction once used to weld rails
2Al(s) + Fe2O3(s) → 2Fe(s) + Al2O3(s)

We can write, Σ

={ Al2O3(s) + - Fe2O3(s) +

= Al2O3(s) - Fe2O3(s)

• The coefficients of products and reactants in the thermochemical equation must be

taken into account.

For example, consider the reaction:

3Cu2+ (aq) + 2Al(s) → 3Cu(s) + 2Al3+ (aq)

For which:
Σ

Note that calculated from enthalpies of formation listed in table 2.2

represents the enthalpy change at 25oC and 1 atm.

2.7 Enthalpy of Phase Change

The amount of heat or the enthalpy associated with any phase change can be
experimentally quantified and tabulated. A particular phase change has an
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associated heat and is given a specific name. To melt a solid means to change it
from the solid-state to the liquid state. The process requires energy because the
molecules of the solid must be free from their rigid structure.

The enthalpy change associated with melting is the enthalpy change for
changing from a solid to a liquid at the melting temperature. For water, this would be

Fusion is the process of phase change from solid to liquid. The enthalpy for this
change is

The enthalpy for the opposite process, freezing, will be exactly equal but opposite in
sign.

The enthalpy of ice fusion is 6.01 kJ/mole; therefore, the enthalpy for freezing water
is -6.01 kJ/mole.

Table 2.3 shows the tabulation for the enthalpy change, which is typically for the
endothermic process. Thus, for solid/liquids, the fusion value is tabulated,
and for liquids/gases, you will find tabulated data for

Similarly, for the reverse process (gas to a liquid), the enthalpy is equal but opposite
in sign.
.
The same follows for the solid/gas phase transitions of sublimation (solid to gas) and
deposition (gas to solid).

Sample Problem 2.14. Calculate the total heat required to convert 500 grams of ice
from the freezer at -50.0oC, place it in a container with a thermometer, and surround
it with a heating coil that supplies heat at a constant rate until it completely converted
into steam at 200.0oC (see Figure 2.3).

The graph of temperature as a function of time is shown below. In the graph's

segment marked (1), the ice temperature rises until it reaches the melting point at
0oC. In region (2), ice melts at a constant temperature of 0 oC until it turns into a
liquid. In the segment (3) of the graph, only liquid water is present, and its
temperature rises until it reaches the boiling point at 1000C. In part (4), the water
boils at a constant temperature of 1000C until it becomes steam; another change of

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phase occurs, from liquid to the gaseous phase. And finally, in the segment (5), the
resulting vapor continues to absorb heat, and its temperature rises.

If all the water vapor had been trapped and not allowed to diffuse away, the
heating process continues; the temperature becomes 200 oC. The gas would now be
called "superheated steam." The table for phase change that happened in the
process is table 2.4

Figure 2.4. The figure shows how the temperature a sample of water varies as it absorbs heat.

Given:
Other data will be taken from tables 2.1 and 2.4

Required: Total heat needed to convert ice at -50.0oC into superheated

steam at 200.0oC.

Solution: We can use either the mass or the number of moles of water.
Molar mass of water = 2(H) + 1(O) = 2(1) + 1(16) = 18

= 52,214.5 J

= 166,477.0 J

= 208,581 J

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vaporizing
= 1,127,390 J
at

= 100,828 J

Total amount of heat absorbed to convert ice at to steam at 1655490.5 J or 1655 kJ

Discussion: The vast amount of energy needed for converting water from a liquid to a gas, as by the
series of processes shown in Figure 2.3, is exploited in converting chemical energy into electricity.
When the fuel (typically coal or natural gas) burns, chemical energy is released as heat. The goal of
the power plant is to convert as much of this energy as possible into electricity. The difficult step in
this process is to trap the heat given off in the combustion reaction. Water is the material of choice for
this process because it has a large heat of vaporization.

Sample Problem 2.15. What is the enthalpy of fusion of methanol if 25.23 grams of
methanol, CH3OH, froze, and 4.01kJ of heat were released?
Given:
Required: enthalpy of fusion for the reaction

25.23 g ΔH = -4.01 kJ

Note: the ratio can be used as a conversion factor and the

unit of

Molar mass of = 1(C) +4(H) +1(O) = 1(12)+4(1)+1(16) = 32

Solution:

(32 ) = -5.09
-5.09

Discussion: The enthalpy for freezing is the opposite process of fusion will be exactly equal but
opposite in sign.

Table 2.3 Phase Change Processes

Phase change Process exothermic/ endothermic Enthalpy
liquid → solid freezing exothermic ΔH = -
solid → liquid melting/fusion endothermic ΔH = +
liquid → gas vaporization endothermic ΔH = +
gas → liquid condensation exothermic ΔH = -
solid → gas sublimation endothermic ΔH = +
gas → solid deposition exothermic ΔH = -

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Table 2.4. ΔH ( ) for Phase Changes

Substance Chemical Melting Boiling
formula point (oC) point (oC)
Benzene C6H6 5 9.84 80 30.8
Bromine Br2 -7 10.8 59 29.6
Mercury Hg -39 2.33 357 59.4
Naphthalene C10H8 80 19.3 218 43.3
Water H2O 0 6.01 100 40.7
*Values of are given at the melting point, values at the boiling point. The heat of vaporization of
0 0 0
water decreases from 44.9 kJ/mol at 0 C to 44.0 kJ/mol at 25 C to 40.7 kJ/mol at 100 C

Sample Problem 2.16. In the manufacture of plastics, the hydrocarbon Benzene,

C6H6, is usually used, and it a carcinogen affecting the bone marrow. According to
studies, long-term exposure to benzene has to cause leukemia and other blood
disorders. The following equation gives the thermochemical equation for the
combustion of benzene:
C6H6 (l) + O2 (g) → 6CO2 (g) + 3H2O (l) = -3267.4 kJ
a. Calculate the heat of formation of benzene.
b. Calculate for the reaction 12CO2 (g) + 6H2O (l) → 2C6H6 (l) + 15 O2 (g)
c. Calculate for the reaction C6H6 (g) + O2 (g) → 6CO2 (g) + 3H2O (g)

Solution:
a)
-3267.4 kJ = 6( CO2) + 3( H2O) - ( C6H6)
C6H6 = 3267.4 kJ + 6 mol (-393.5 kJ/mol) + 3 mol (-285.8 kJ/mol)
C6H6 = +49.0 kJ/mol
b) Rule 2 = - (-3267.4) kJ = 3267.4 kJ
Rule 1 = 2(3267.4 kJ) = 6534.8 kJ
c) In answering question c, the following steps will be applied:
1. Notice that the given equation is identical to the combustion equation
except for benzene and water's physical states.
2. a. Write the thermochemical equation for the vaporization of water.
b. Multiply the equation by three (3) since there are three moles of H2O in
the combustion reaction.
3. a. Write the thermochemical equation for the vaporization of benzene.
b. Note that C6H6(g) is a reactant in the equation where is needed.

c. Reverse the vaporization equation for benzene and change the sign of
its .
4. Apply Hess's Law by adding all the equations, so you come up with
for the overall given equation.

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Solution:
( )

( ) ( )

Apply Hess’s law in (1) + (2) + combustion equation

Overall reaction

Sample Problem 2.17. Calculate the enthalpy change for the reaction:
2C (graphite) + 3 H2 (g) ---> C2H6 (g)
From the data given below:
C(graphite) + O2(g) ---> CO2(g) ΔH = -393.5 kJ eq (1)
H2(g) + 1⁄2O2(g) ---> H2O(ℓ) ΔH = -285.8 kJ eq (2)
2C2H6(g) + 7O2(g) ---> 4CO2(g) + 6H2O(ℓ) ΔH = -3119.6 kJ eq (3)

Required: enthalpy change for the reaction ΔH: 2C (graphite) + 3 H2 (g) ---> C2H6 (g)

Solution:
(1)x2 2C(graphite) + 2O2(g) → 2CO2(g) ΔH = -787.0 kJ
(2)x3 3H2(g) + 3⁄2O2(g) → 3H2O(ℓ) ΔH = -857.4 kJ
R(3)/2 2CO2(g) + 3H2O(ℓ) → C2H6(g) + 7⁄2O2(g) ΔH = +1559.8 kJ

Add the equations, ΔH, and simplify:

2C (graphite) +3H2 (g) → C2H6 (g) ΔH= -84.6 kJ
Discussion: The enthalpy change computed is the enthalpy of formation of ethane C2H6 (g). Note that
equation (1) is multiplied by 2, equation (2) is multiplied by three (3), and equation (3) is reversed then
divided by 2 to come up with the thermochemical equation
2C (graphite) +3H2 (g) → C2H6 (g) ΔH= -84.6 kJ

Sample Problem 2.18. The standard enthalpy of formation for hydrogen chloride is
-92.3 kJ/mol. Given the following data:
N2(g) + 4H2(g) + Cl2(g) → 2NH4Cl(s) = -630.78 kJ eq (1)
N2(g) + 3H2(g) → 2NH3(g) = -296.4 kJ eq (2)

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Required: Determine the identity of the two missing products and calculate the
ΔHrxn for this reaction: NH4Cl(s) → _____ + _____

Solution: The thermochemical for the formation of hydrogen chloride (HCl) is

1
⁄2H2 (g) + 1⁄2Cl2 (g) → HCl (g)
R(1)/2 NH4Cl(s) → 1⁄2N2(g) + 2H2(g) + 1⁄2Cl2(g) = 315.39 kJ
1
(2)/2 ⁄2N2(g) + 3⁄2H2(g) → NH3(g) = -148.2 kJ

Add the equations and ΔH, and simplify:

NH4Cl(s) → HCl (g) + NH3 (g) ΔHrxn = 74.89 kJ

Discussion: Based on the enthalpy of formation of one mole of HCl, we set up the thermochemical
equation. Note that equation (1) is reversed and divided by two (2) because the resulting equation
must start with one mole NH4Cl(s), equation (2) is divided by 2 to cancel the N2 and H2 on both sides
of the equation.

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Course,Year&Section: Engineers MODULE 2

Instructor: Date:

Exercise 2.2
Check your learning: Answer the following questions and problems.
1. To calibrate a bomb calorimeter, the combustion of naphthalene (C 10H8),
which releases 5150.1 kJ/mol, is often used. A sample of naphthalene of
mass 1.05-g is burned in a calorimeter, producing a temperature increase of
3.86°C. Combustion of a 1.83-g sample of coal in the same calorimeter
causes a temperature change of 4.90°C. What is the energy density of coal?

2. Hydrogen gas, H2, reacts explosively with gaseous chlorine, Cl2, to form
hydrogen chloride, HCl (g). What is the enthalpy change for the reaction of 1
mole of H2 (g) with 1 mole of Cl2 (g) if both the reactants and products are at
standard state conditions? The standard enthalpy of formation of HCl (g) is -
92.3 kJ/mol.

3. When 1.34 g Zn(s) reacts with 60.0 mL of 0.750 M HCl(aq), 3.14 kJ of heat
are produced. Determine the enthalpy change per mole of zinc reacting for
the reaction:
Zn(s) +2HCl (aq) → ZnCl2 (aq) +H2 (g)

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4. Homes may be heated by pumping hot water through radiators. What mass of
water will provide the same amount of heat when cooled from 95.0 to 35.0 °C,
as the heat provided when 100 g of steam is cooled from 110 °C to 100 °C.

5. Write the heat of formation reaction equations for:

a) C2H5OC2H5(l) b) Na2CO3(s)

6. Explain why each of the following chemical equations is not a correct

formation reaction:
a) 4 Al(s) + 3 O2 (g) → 2 Al2O3(s)
b) N2 (g) + 3⁄2 H2 (g) → NH3 (g)
c) 2 Na (s) + O (g) → Na2O(s)

7. If 14.8 kJ of heat is given off when 1.6 g of HCl condenses from vapor to
liquid, what is ΔHcondensation for this substance?

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8. Determine the heat of reaction for the oxidation of iron:

2Fe(s) + 3⁄2O2 (g) ---> Fe2O3(s)

Given the thermochemical equations:
2Fe(s) + 6H2O(ℓ) ---> 2Fe(OH)3(s) + 3H2(g) ΔH = +322 kJ
Fe2O3(s) + 3H2O(ℓ) ---> 2Fe(OH)3(s) ΔH = +289 kJ
2H2(g) + O2(g) ---> 2H2O(ℓ) ΔH = +572 kJ

9. Some heats of combustion are given below:

C12H22O11(s) + 12O2 (g) ---> 12CO2 (g) + 11H2O (ℓ) ΔH = -1349.6 kcal
H2 (g) + 1⁄2O2 (g) ---> H2O (ℓ) ΔH = -68.3 kcal
C(s) + O2 (g) ---> CO2 (g) ΔH = -94 kcal
Determine the heat of formation for sucrose.
12C(s) + 11H2(g) + 11⁄2O2 (g) ---> C12H22O11(s)

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10. Given the following data:

SrO(s) + CO2(g) ---> SrCO3(s) ΔH = -234 kJ
2SrO(s) ---> 2Sr(s) + O2(g) ΔH = +1184 kJ
2SrCO3(s) ---> 2Sr(s) + 2C(s, gr) + 3O2(g) ΔH = +2440 kJ
Find the ΔH of formation for CO2 the following reaction:
C(s, gr) + O2 (g) ---> CO2 (g)

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2.8 FIRST LAW OF THERMODYNAMICS

Thermodynamics deals with the study of systems involving energy in the

form of heat and work. An example of an excellent thermodynamic system is gas
confined by a piston in a cylinder. Once the gas is heated, it will expand, doing work
on the piston; this is one example of how a thermodynamic system can do work.

The First Law of thermodynamics states that an increase of a system's

internal energy is equal to the sum of the heat added to the system plus the
work done on the system.

Heat (q) and work (w) are the only possible forms of energy transfer. We can
relate the overall change in energy, ΔU, of a system to these two components. Heat
is commonly designated as q and work as w so that we can write.

The symbol Δ (delta) is introduced here as a notation meaning "the change in." This
symbol, which will be used frequently in our thermodynamics study, is always
defined as the difference between the final state and the initial state.

The internal energy of a system ( U) may be increased/ decreased when you

add/remove heat to the system or do work on it. For example, if the system is a gas,
the internal energy includes the translational, vibrational, and rotational kinetic
energies of the molecules. It also includes potential energy terms arising from the
forces between the molecules. It may also have excitation energy if the atoms are
excited to energy levels above the ground state. It may be challenging to determine
the total internal energy, depending on which forms of energy you consider.
Similarly, the potential energy terms are always dependent on what state you
define to have zero potential energy. Therefore it is impossible to describe the total
internal energy of a system uniquely. The First Law tells us that the increase in a
system's internal energy is when the heat is added to it, and work is done on it.

The SYSTEM is what we wish to focus our attention on. In our present study
in chemistry, the system is the chemical reaction.

For example: 2H2 + O2 → 2H2O. The system consists of those substances

which are reacting.

The SURROUNDINGS are everything not on the system. If the above

reaction is happening in the gas phase, we can consider the container walls as part
of the surroundings.

Our focus of study will be on the change in the amount of energy, not the
absolute amount of energy in the system or the surroundings.
When energy (heat or work) is liberated or goes out of the system, the system
decreases. It is assigned a negative sign and is called exothermic. A negative q
means that heat is removed from the system, and negative W means work is done

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by the system or system does the work. In an exothermic process, heat is liberated,
causing the temperature of the immediate surroundings to increase.

When energy (heat or work) is added or flows into the system, it increases its
energy. A positive sign is assigned and is called endothermic. A positive q means
that heat is added to the system, and positive W means work is done to the system
or surrounding does the work. An endothermic absorbs heat and cools the
surrounding.

Convention: +W - work is done to the system or surrounding does the work

-W - work is done on the system or system does the work
+q - heat is added to the system
-q - heat is removed from the system
+ – internal energy increases
- – internal energy decreases

Sample Problem 2.19. If 555 J of heat is added to a gas that does 218 J of work,
what is the change in the system's energy?
Given: q = +555 J (added to the gas)
w = -218 J (done by the gas)
Required: =?
Solution:
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Sample Problem 2.20. The gas starts with 300 J of internal energy while adding
180 J of heat to the gas; the gas does 70 J of work. Calculate the final internal
energy of the gas?
Given:
q = +180 J (added to the gas (system))
w = -70 J (done by the gas (system))
Required:
Solution: and

Sample Problem 2.21. What is the change in the system's internal energy if the
surrounding gain 275 J of heat energy and if the surroundings perform 470 J of
work?
Given: q = -275 J (removed from the system)
w = +470 J (done on the system)
Required: =?
Solution:

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Exercise 2.3
Solve the problems by showing the given, required, and complete solution.
1. Determine in which case is heat added to the system?
(a) ΔU = –43 J, w = 40 J; or (b) ΔU = 31 J, w = 34 J?

2. In a particular process, 500 J of work is done on the system, which gives off
200 J of heat. What is the value of for the process?

3. Which system does more work?

(a) U = -436 J, q= 400 J or (b) U = 317 J, q= 347 J ( U = q + W)

4. Calculate
(a) q when a system does 44 J of work and its energy decreases by 62 J
(b) U for a gas that releases 48 J of heat and has 112 J of work done on it.

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5. Calculate the internal energy, U of gas in the following process in which the
gas
(a) Does 12 J of work by expanding and absorbs 20 J of heat.
(b) Give off 30 J of heat and has 52 J of work done on it as it contracts.

6. Consider the following reaction in the vessel with a movable piston.

X (g) + Y (g) → Z (s)
For this reaction, ΔU = 286 J, the piston moves up, and the system absorbs
388 J of heat from its surroundings.
(a) Does the system do work? (b) How much work?

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Reflection/Insights:

Name: Chemistry for Score

Course,Year&Section: Engineers MODULE 2

Instructor: Date:

The Philippines rely on fossil fuels (about two thirds) as one of the sources of
energy. The combustion of fossil fuel is an exothermic process and releases an
enormous amount of heat. Identify its effect on our environment and give
suggestions to address its impact on our environment. Write your answer in not more
than ten sentences.

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Post Test:

Name: Chemistry for Score

Course,Year&Section: Engineers MODULE 2

Instructor: Date:

Multiple Choice: Shade the letter corresponding to the best answer.

1. In an equation, the positive sign (+ΔH) indicates that the reaction is
[A] Endothermic [B] exothermic [C] ectothermic [D] hypothermic
2. Which of the following changes is not exothermic?
[A] Condensing steam. [B] Combustion of butane.
[C] Melting copper. [D] Freezing water.

3. Enthalpy (H) is
[A] The heat content of a system at constant pressure.
[B] A chemical equation that includes the amount of heat released or absorbed
during the reaction.
[C] The heat released or absorbed during a chemical reaction.
[D] The heat released after burning 1 mole of a substance.

4. Thermochemical equation refers to

[A] A chemical equation that includes the amount of heat released or absorbed
during the reaction.
[B] The heat released or absorbed during a chemical reaction.
[C] The heat released after burning 1 mole of a substance.
[D] The amount of heat needed to melt 1 mole of a solid.

5. When calcium oxide is added to water, an egg can be cooked on top. What
explains this?
[A] The reaction absorbs heat and cooks the egg [B] The egg warms when it is
cracked and begins to cook
[C] Energy is removed from the air and cooks the egg
[D] The reaction releases heat and cooks the egg

6. The combustion of methane can be written as CH4 + 2O2 → CO2 + 2H2O + heat.
Which of the following statement best describe this process?
[A] It is endothermic because it absorbs heat.
[B] It is endothermic because it releases heat
[C] It is exothermic because it absorbs heat.
[D] it is exothermic because it releases heat

7. The freezing point of water is 00C. Its melting point is

[A] Slightly less than 00C [B] 00C [C] slightly more than 00C [D] 320C
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8. Hess's Law states that a chemical reaction is independent of the route by which
chemical reactions takes place while keeping the same
[A] Initial conditions [B] final conditions [C] both A and B [D] mid-conditions

9. Sulfur tetrafluoride (SF4) hydrolyses as follows:

SF4 (g) + 2H2O (l) → SO2 (g) + 4HF (g)
Given the following information: Standard enthalpy of formation: (298 K) for
SF4 (g), H2O (l), SO2 (g), and HF (g) are –763, –286, –297, and –273 ,
respectively. What is the value of (298 K) for the hydrolysis shown
above?
[A] -479 [B] –54 [C] 54 [D] 479

10. Which statement is correct about the fusion of copper?

[A] A solid is formed. [B] Heat is released.
[C] Heat is required. [D] The process is exothermic.

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Final Requirement
1. Submit the following
 Pre-Test
 Exercises 2.1, 2.2, 2.3
 Experiment 2
 Answer to Reflection/Learning Insight
 Post Test
2. Take the Quiz 2

SUGGESTED READINGS, VIDEOS AND WEBSITES

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Glossary

A bomb calorimeter is a device used to measure the energy change for processes
occurring under conditions of constant volume; commonly used for reactions
involving solids and gaseous reactants or products

Calorie (cal): unit of heat or other energy; the amount of energy required to raise 1
gram of water by 1 degree Celsius; 1 cal is equal to 4.184 J

A calorimeter is a device designed to measure the amount of heat absorbed or

released in a chemical or physical process

Calorimetry is a process of measuring the amount of heat involved in a chemical or

physical process.
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The endothermic process is a chemical reaction or physical change that absorbs

heat

Energy pertains to the capacity to do work or supply heat

Enthalpy (H) is the sum of a system’s internal energy and the mathematical product
of its pressure and volume

Enthalpy change (ΔH) is the heat released or absorbed by a system under constant
pressure during a chemical or physical process

Expansion work (pressure-volume work): work was done as a system expands or

contracts against external pressure

The exothermic process is a chemical reaction or physical change that releases

heat

The First Law of thermodynamics: the internal energy of a system changes due to
heat flow in or out of the system or work done on or by the system

Heat (q) refers to the transfer of thermal energy between two bodies

Heat capacity (C) is an extensive property of a body of matter that represents the
quantity of heat required to increase its temperature by 1 degree Celsius (or 1 kelvin)

Hess's Law states is the sum of several steps, the enthalpy change of the process
equals the sum of the enthalpy changes of the steps

Hydrocarbons are compounds composed only of hydrogen and carbon, and they
are the major component of fossil fuels

Internal energy (U) of a system is the total of all possible kinds of energy present in
a substance or substances

joule (J) is an SI unit of energy; 1 joule is the kinetic energy of an object with a mass
of 2 kilograms moving with a velocity of 1 meter per second, 1 Joule = 1 kg m 2/s and
4.184 J = 1 cal

Kinetic energy: energy of a moving body, in joules, equal ½ mv2 (where m = mass
and v = velocity)

Nutritional Calorie (Calorie) is the unit used for quantifying energy provided by the
digestion of foods, defined as 1000 cal or 1 kcal

Potential energy is the energy possessed of a particle or system of particles derived

from the relative position, composition, or condition

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Specific heat capacity (c) is an intensive property of a substance that represents

the quantity of heat required to raise the temperature of 1 gram of the substance by
1 degree Celsius (or 1 kelvin)

Standard enthalpy of combustion ( ) is the heat released when one mole of a

compound undergoes complete combustion under standard conditions

Standard enthalpy of formation ( ): enthalpy change of a chemical reaction in

which 1 mole of a pure substance is formed from its elements in their most stable
states under standard state conditions

the standard state is a set of physical conditions as accepted as common reference

conditions for reporting thermodynamic properties; 1 bar of pressure, and solutions
at one molar concentrations, usually at a temperature of 298.15 K

State function is the property depending only on the state of a system, and not the
taken path to reach that state

Surroundings refer to all matter other than the system

System refers to the portion of matter undergoing a chemical or physical change

Temperature: intensive property of matter that is a quantitative measure of

“hotness” and “coldness;” it is related to the average kinetic energy of the atoms or
molecules that make up the object

Thermal energy pertains to the kinetic energy associated with the random motion of
atoms and molecules

Thermochemistry is the study of measuring the amount of heat absorbed or

released during a chemical reaction or a physical change

Work (w) refers to energy transfer due to changes in external, macroscopic

variables such as pressure and volume; or causing matter to move against an
opposing force

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Answer Keys:
 Pretest

1. C 6. B
2. B 7. D
3. C 8. B
4. A 9. D
5. D 10. A

 Exercise 2.1
1. The temperature of 1 gram of burning wood is approximately the same for
both a match and a bonfire. It is an intensive property and depends on the
material (wood). However, the overall amount of produced heat depends on
the amount of material; this is an extensive property. The amount of wood in a
bonfire is much greater than that in a match; the total amount of produced
heat is also much greater, which is why we can sit around a bonfire to stay
warm, but a match stick would not provide enough heat to keep us from
getting cold.

2.

3. Heat capacity refers to the heat required to raise the temperature of the mass
of substance 1 degree; specific heat refers to the heat needed to raise the
temperature of 1 gram of the substance 1 degree. Thus, heat capacity is an
extensive property, and specific heat is an intensive one.
Problems. 1.

2. C =

3. c = 0.451 J/g °C; the metal is likely to be iron

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4. q = 43,312.5 Joules = 4.33x104 Joules

5. c = , Aluminum

 Exercise 2.2
1. 29.3 kJ/g
2. Answer: H2 (g) +Cl2 (g) →2HCl (g) =−184.6kJ
3. Answer: ΔH = –153 kJ
4. mwater=1864J251.01J/g = 7.43g
5. Answer: a) 4C(s, graphite) +5H2 (g) +½O2 (g) → C2H5OC2H5 (l)
b) 2Na(s) +C(s, graphite) + 3⁄2O2 (g) → Na2CO3(s)
6. Answer: a) two moles of the compound are formed.
b) The equation is not balanced.
c) The standard state of oxygen is O2
7. ΔHcondensation = -3.4 x 102 kJ/mol
8. ΔH = 891 kJ
9. ΔH = -529.7 kcal
10. ΔH = -394 kJ

 Exercise 2.3
1. (a) q = - 83 J (b) w = -3 J. None, heat is evolved in both cases.
2.
3. (a) w = - 836 J (b) w = -30 J. So more work is done in the system in (a).
4. a) 106 J b) 64 J
5. a) U = 8 J b) U = 22 J
6. a) yes b) W = 102 J

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References:
Brown, Lawrence S., and Holme Thomas A.; Chemistry for Engineering Students,
Second Edition, Brooks/Cole, Cengage Learning, 2011

Chang, Raymond. (2010). Chemistry 10th edition, International Edition. New York: McGraw
Hill Companies.

Masterton, William S., Hurley, Cecile N. and Neth, Edward J.; Chemistry Principles
and Reactions, 7th Edition, Brooks/Cole, Cengage Learning, 2012

Munyaki, Onesmus, M. (2017). Physical chemistry 1, African Virtual University.

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