CMY 117 | General Chemistry

Presented at the University of Pretoria

First Semester

Course Notes developed

by Mr HJ van der Poll
 Preface

Welcome to the course! These lecture notes were constructed and developed by Mr HJ van der Poll and are best used with his
accompanying lectures and video material. Importantly, these notes do not aim to be a replacement for attending lectures or
to replace the textbook. It is assumed that you work through all the possible resources at your disposal.

I hope these notes will assist you in reaching your full potential!

Best’

Hendrik

Consultation
For consultation, kindly see my consultation times below. Always be sure to indicate that you intend to visit my office during
the consultation hours via email at [Link]@[Link].

Office | Natural Science 1 Room 3-44

Mondays Thursdays

09:30 – 11:30 09:30 – 11:30

Lecture Notes
For 2025, I will be teaching Themes 8 - 14. For full notes on Themes 1 through 7, kindly refer to Prof. Nombona’s Lecture notes
for 2025. I will provide a short review on Significant figures from Theme 1, but thereafter the notes start with Theme 8.

My YouTube Channel
I have a YouTube Channel called The van der Poll Method. You must use the video material provided to prepare for lectures
and do the additional examples. This will adequately prepare you for class, tutorials and assessments. You will typically see a
block that says ”Click Here to access this Theme’s YouTube Playlist”, which will directly take you to the playlist on YouTube
that contains all the videos (made by me) on the particular Theme. I make use of a so-called flip class room whereby the
theory videos cover the basics (”theory” and sometimes basic examples) and overall introduction in the video presented on
YouTube, and then we will discuss the more in-depth problem-solving aspects of the course in class (see the examples labelled
”Solution will be discussed during lecture period”).

Therefore, to get the most out of my lectures, you must prepare for each lecture and always be up to date. The section on
”Preparing for Lectures” gives a calendar that you can follow to prepare for the lectures of this section.

i
 CMY 117 | General Chemistry

Preparing for Lectures

For all your lectures, you must ensure that you have prepared the lectures outlined in the study calendar shown below. Of
special importance are those for the first lecture. We will start Theme 8 with Example 8.4, hence ensure that you use the video
content provided to adequately prepare for the lecture.

Ensure that you watch the videos of the sections that will be presented on the day in class because of the flip classroom style,
my focus will be on the examples labelled ”Solution will be discussed during lecture period”. The idea is to increase the time
we have to discuss the nuance of the problems rather than having to rush through all of the content.

University of Pretoria | Department of Chemistry ii

 Table of Contents

Theme 1 Matter and Measurement 1 8.10 Additional Practice Problems. . . . . . . . 28

1.1 Introduction . . . . . . . . . . . . . 1
Theme 9 Energy and Chemical Reactions 32
1.1.1 Determining Significant Figures . . . . . . . . . . 1

1.1.2 Significant Figures in Calculations . . . . . . . . 2 9.1 Introduction . . . . . . . . . . . . . 32

9.2 The Basic Principles of Energy . . . . . . . 32

Theme 8 Reaction Stoichiometry 3 9.2.1 How Do We Know What is the System and
What are the Surroundings? . . . . . . . . . . . . 33
8.1 Introduction . . . . . . . . . . . . . 3
9.2.2 The Direction and Amount of Heat
8.2 Mass Relationships in Chemical Reactions: Transferred – Thermal Equilibrium . . . . . . . . 33
Stoichiometry . . . . . . . . . . . . . 3
9.3 How Much Heat Can Something Absorb? –
8.3 Reactions Where One Reactant is in Limited Specific Heat Capacity . . . . . . . . . . 34
Supply: Limiting Reagents . . . . . . . . 5
9.4 What Happens When Energy is Absorbed and a
8.3.1 Stoichiometry Calculation with a Limiting Substance Changes State? . . . . . . . . . 36
Reactant. . . . . . . . . . . . . . . . . . . . . . . . . 5
9.5 The First Law of Thermodynamics . . . . . . 38
8.4 Percentage Yield . . . . . . . . . . . . 9
9.5.1 Enthalpy . . . . . . . . . . . . . . . . . . . . . . . . 40
8.5 Chemical Equations and Chemical Analysis . . 11
9.5.2 What is a State Function? . . . . . . . . . . . . . . 41
8.5.1 Quantitative Analysis of a Mixture . . . . . . . . 11
9.6 Enthalpy and Chemical Reactions . . . . . . 41
8.5.2 Determining the Formula of a Compound by
Combustion – Let’s Burn It! . . . . . . . . . . . . . 12 9.7 Calorimetry. . . . . . . . . . . . . . 42

8.6 Measuring Concentrations of Compounds in 9.7.1 Measuring Enthalpy Using Calorimetry . . . . . 42

Solution . . . . . . . . . . . . . . . 16 9.7.2 Measuring Internal Energy Using

Calorimetry . . . . . . . . . . . . . . . . . . . . . . 43
8.6.1 Solution Concentration: Molarity . . . . . . . . . 16
9.8 Enthalpy Calculations . . . . . . . . . . 45
8.6.2 Preparing Solutions of Known Concentration. . 17
9.8.1 Hess’s Law . . . . . . . . . . . . . . . . . . . . . . . 45
8.7 The Concept of pH – A Concentration Scale for
Acids and Bases . . . . . . . . . . . . 19 9.8.2 Energy Level Diagrams . . . . . . . . . . . . . . . 47

8.8 Stoichiometry of Reactions in Aqueous Solution 9.8.3 Standard Enthalpies of Formation. . . . . . . . . 47

– Fundamentals . . . . . . . . . . . . 20
9.8.4 Enthalpy Change of Reaction. . . . . . . . . . . . 48
8.9 Stoichiometry of Reactions in Aqueous Solution
9.9 What Can Thermodynamics Help Predict? . . . 50
– Titrations . . . . . . . . . . . . . . 23
9.10 Additional Practice Problems. . . . . . . . 51
8.9.1 Titration: A Method of Chemical Analysis . . . 23

8.9.2 Determining Molar Mass by Titration . . . . . . 26

Theme 10 The Properties of Gasses 54
8.9.3 Titrations Using Oxidation-Reduction
Reactions . . . . . . . . . . . . . . . . . . . . . . . . 27 10.1 Introduction . . . . . . . . . . . . . 54

iii
Table of Contents CMY 117 | General Chemistry

10.2 How Do We Model Gasses and Gas Pressure? . . 54 12.5 Boiling Point . . . . . . . . . . . . . 81

10.3 Gas Laws: The Experimental Basis . . . . . 55 12.6 Critical Temperature and Pressure . . . . . . 81

10.4 The Ideal Gas Law . . . . . . . . . . . 56 12.7 Surface Tension, Capillary Action, and Viscosity . 82
10.4.1 The Density of a Gas . . . . . . . . . . . . . . . . . 57 12.8 Additional Practice Problems. . . . . . . . 83
10.4.2 We can Calculate the Molar Mass of a Gas
from P, V, and T Data . . . . . . . . . . . . . . . . 57
Theme 13 The Properties of Solutions 85
10.5 Gas Laws and Chemical Reactions . . . . . . 59
13.1 Introduction . . . . . . . . . . . . . 85
10.6 What Happens When We Mix Ideal Gasses? –
Partial Pressures . . . . . . . . . . . . 61 13.2 Units of Concentration . . . . . . . . . . 85

10.7 Additional Practice Problems. . . . . . . . 63 13.3 How Are Solutions Made? . . . . . . . . . 87

13.3.1 We Can Dissolve One Liquid in Another

Theme 11 Intermolecular Forces 65 Liquid . . . . . . . . . . . . . . . . . . . . . . . . . . 87

13.3.2 We Can Also Dissolve Solids in Liquids . . . . . 88

11.1 Introduction . . . . . . . . . . . . . 65
13.3.3 The Enthalpy (Energy) Picture When
11.2 States of Matter and Intermolecular Forces . . . 65
Dissolving Solutes. . . . . . . . . . . . . . . . . . . 88
11.3 Interactions between Ions and Molecules with a
13.4 Pressure and Temperature Affect the Solubility
Permanent Dipole . . . . . . . . . . . 66
of Compounds . . . . . . . . . . . . . 88
11.4 Interactions between Molecules with a
Permanent Dipole . . . . . . . . . . . 67 13.4.1 Dissolving Gases in Liquids: Henry’s Law . . . . 89

11.4.1 Dipole-Dipole Forces . . . . . . . . . . . . . . . . . 67 13.4.2 Temperature Effects on Solubility: Le

Chatelier’s Principle . . . . . . . . . . . . . . . . . 90
11.4.2 Hydrogen Bonding . . . . . . . . . . . . . . . . . . 68
13.5 Colligative Properties . . . . . . . . . . 91
11.4.3 Hydrogen Bonding and the Unusual
Properties of Water . . . . . . . . . . . . . . . . . . 70 13.5.1 Raoult’s Law is About Changes in Vapour
Pressure . . . . . . . . . . . . . . . . . . . . . . . . . 91
11.5 Intermolecular Forces Involving Non-polar
Molecules . . . . . . . . . . . . . . 71 13.5.2 Boiling Points Increase When Solutes are
Dissolved In Solvents. . . . . . . . . . . . . . . . . 93
11.5.1 Dipole-Induced Dipole Forces: Debye Forces . 71
13.5.3 Freezing Points Decrease When Solutes are
11.5.2 Induced Dipole-Induced Dipole Forces:
Dissolved In Solvents. . . . . . . . . . . . . . . . . 94
London Dispersion Forces . . . . . . . . . . . . . 71
13.5.4 Osmotic Pressure: How Solution Equilibrate
11.6 A Summary of van der Waals Intermolecular
Their Concentrations . . . . . . . . . . . . . . . . 94
Forces. . . . . . . . . . . . . . . . 73
13.5.5 We Can Use Colligative Properties to
11.7 Additional Practice Problems. . . . . . . . 76 Determine Molar Mass of Substances. . . . . . . 96

13.5.6 Colligative Properties of Solutions Containing

Theme 12 The Properties of Liquids 77 Ions . . . . . . . . . . . . . . . . . . . . . . . . . . . 97

12.1 Introduction . . . . . . . . . . . . . 77 13.6 Colloids . . . . . . . . . . . . . . . 99

12.2 Vapourization and Condensation of Liquids . . 77 13.6.1 What Types of Colloids are There? . . . . . . . . 99

12.3 Vapour Pressure . . . . . . . . . . . . 78 13.6.2 What is a Surfactant? . . . . . . . . . . . . . . . . . 100

12.4 The Clausius-Clapeyron Equation . . . . . . 81 13.7 Additional Practice Problems. . . . . . . . 101

University of Pretoria | Department of Chemistry iv

CMY 117 | General Chemistry Table of Contents

Theme 14 Chemical Kinetics 103 14.5.3 The Integrated Rate Law for Zeroth-Order
Reactions . . . . . . . . . . . . . . . . . . . . . . . . 114
14.1 Introduction . . . . . . . . . . . . . 103
14.5.4 Graphical Methods for Determining Reaction
14.2 How Fast Does a Reaction Occur? – The Rates Order and the Rate Constant . . . . . . . . . . . . 115
of Reactions . . . . . . . . . . . . . 103
14.5.5 Half-Life and First-Order Reactions. . . . . . . . 115
14.2.1 How Do We Calculate the Rate of a Reaction? . 103
14.6 A Microscopic View of Reaction Rates . . . . 117
14.2.2 Relative Rates and Stoichiometry . . . . . . . . . 105
14.6.1 Collision Theory: Concentration and
14.3 How Does the Conditions of a Reaction Affect Reaction Rate . . . . . . . . . . . . . . . . . . . . . 117
the Rate?. . . . . . . . . . . . . . . 106 14.6.2 Collision Theory: Activation Energy . . . . . . . 118
14.4 How Will Changing Concentrations Affect The 14.6.3 Collision Theory: Activation Energy and
Reaction Rate?. . . . . . . . . . . . . 107 Temperature . . . . . . . . . . . . . . . . . . . . . 118

14.4.1 What is a Rate Equation? . . . . . . . . . . . . . . 107 14.6.4 Collision Theory: Effect of Molecular
Orientation on Reaction Rate . . . . . . . . . . . 119
14.4.2 The Idea of The Order of a Reaction . . . . . . . 108
14.6.5 The Arrhenius Equation. . . . . . . . . . . . . . . 119
14.4.3 More on This Rate Constant, k . . . . . . . . . . . 108

14.4.4 How do We Determine a Rate Equation?. . . . . 108

14.7 What are Catalysts? . . . . . . . . . . . 122

14.7.1 What Effect does Catalysts Have on Reaction

14.5 Concentration–Time Relationships: Integrated
Rates? . . . . . . . . . . . . . . . . . . . . . . . . . . 122
Rate Laws . . . . . . . . . . . . . . 111
14.7.2 Enzymes . . . . . . . . . . . . . . . . . . . . . . . . 123
14.5.1 The Integrated Rate Law for First-Order
Reactions . . . . . . . . . . . . . . . . . . . . . . . . 111 14.8 Additional Practice Problems. . . . . . . . 124
14.5.2 The Integrated Rate Law for Second-Order
Reactions . . . . . . . . . . . . . . . . . . . . . . . . 113

v University of Pretoria | Department of Chemistry

 Theme
Matter and Measurement
1 Click Here to access this Theme’s YouTube Playlist

1.1 Introduction

In most experiments, several kinds of measurements must be made, and some can be made more precisely than others. A
result calculated from experimental data cannot be more precise than the least precise piece of information used in
the calculation. This is where the rules for significant figures come in. Significant figures (also called significant digits) are
the digits in a measured quantity that are known exactly plus one inexact digit.

1.1.1 Determining Significant Figures

Suppose you want to calculate the density of a piece of metal. The mass and dimensions were determined by standard laboratory
techniques. Most of these data have two digits to the right of the decimal, but they have different numbers of significant figures:

Measurement Data Collected Number of Significant Figures

Mass of Metal 13.56 g

Length 6.45 cm

Width 2.50 cm

Thickness 3.1 mm = 0.31 cm

When you read a number in a problem or collect data in the laboratory, how do you determine which digits are significant?

1. Exact numbers have an infinite number of significant figures.

2. For measured numbers we must consider the number of significant figures.

What About Zeros?

The values 13.56 g and 6.45 cm contain only nonzero digits, which are always significant in a reported measurement. Thus,
13.56 g has four significant figures, and 6.45 mm has three. But how many significant figures are in the values: 0.31 cm and
2.50 cm? Are the zeroes significant?

We can set up the following ”rules” regarding zeros:

▷ Zeroes between two other significant digits are significant.

▷ Zeroes to the right of a nonzero number, and also to the right of a decimal place, are significant.

▷ Zeroes that are placeholders are not significant. There are two types of numbers that fall under this rule.

1
1.1 Introduction CMY 117 | General Chemistry

– The first are decimal numbers with zeroes that occur to the left of the first nonzero digit. For example, in 0.0013,
only the 1 and the 3 are significant; the zeroes are not.
– The second are numbers with trailing zeroes that must be there to indicate the magnitude of the number. The best
practice here is to use a ”dot” or ”dash” notation to assist here.

1.1.2 Significant Figures in Calculations

We can define a couple of ”rules” for significant figures in calculations:

1. When adding or subtracting numbers, the number of decimal places in the answer is equal to the number of decimal
places in the number with the fewest digits after the decimal.

2. In multiplication or division, the number of significant figures in the answer is determined by the value with the fewest
significant figures.

3. When a number is rounded off, the last digit retained is increased by one (rounded up) only if the following digit is 5 or
greater.

When working problems, you should do the calculation with all the digits allowed by your calculator and round off only at
the end of the calculation. Rounding off in the middle of a calculation can introduce errors.

Example 1.1
Using Significant Figures
An example of a calculation is:

(0.120)(0.08206)(273.15 + 5)
Volume of Gas (L) =
(230/760.0)

Calculate the final answer to the correct number of significant figures.

University of Pretoria | Department of Chemistry 2

 Theme
Reaction Stoichiometry
8 Click Here to access this Theme’s YouTube Playlist

8.1 Introduction

In Theme 7, you learned how to write balanced chemical equations to describe chemical reactions. Theme 8 shows how these
equations can be used to predict how much of a reactant is required to react with a given quantity of another reactant, or
how much of a product can be produced. These calculations form the basis of reaction stoichiometry, which deals with
the amounts of reactants and products in a chemical reaction. Chemists use these types of calculations to help them design
experiments and evaluate their results.

8.2 Mass Relationships in Chemical Reactions: Stoichiometry

Learning Outcomes for This Section: Mass Relationships in Chemical Reactions – Stoichiometry

What are our aims for this section?

▷ Understand the principle of conservation of matter, which forms the basis of chemical stoichiometry.

▷ Calculate the mass of one reactant or product in a reaction knowing the balanced equation and the mass of
another reactant or product in that reaction.

▷ Use amounts tables to organize chemical information.

The reaction of elemental phosphorus and chlorine produces the compound PCl3 , and the following balanced equation shows
the quantitative relationship between reactants and products in this reaction:

P4 (𝑠) + 6 Cl2 (𝑔) −−−→ 4 PCl3 (𝑙)

1 mol 6 mol 4 mol
124 g 425 g 549 g

At the molecular level, this balanced equation tells you that one molecule of phosphorus reacts with six molecules of chlorine
to produce four molecules of phosphorus trichloride. At the macroscopic level where reactions are observed, the coefficients
refer to the number of moles of each reactant and product.

So what the equation actually tells us is:

1 mol (124 g) of solid phosphorus (P4 )+6 mol (425 g) chlorine gas (Cl2 ) −−−→ 4 mol (549 g) of liquid phosphorus trichloride (PCl3 )

In the next example, we will look at how we can use an amounts table to aid us in the reaction stoichiometry calculations.

3
8.2 Mass Relationships in Chemical Reactions: Stoichiometry CMY 117 | General Chemistry

Example 8.1
Mass Relations in Chemical Reactions
Glucose, C6 H12 O6 , reacts with oxygen to give CO2 and H2 O. What mass of oxygen (in grams) is required to completely
react with 25.0 g of glucose? What masses of carbon dioxide and water (in grams) are formed?

Solution discussed in Video Lecture

University of Pretoria | Department of Chemistry 4

CMY 117 | General Chemistry 8.3 Reactions Where One Reactant is in Limited Supply: Limiting Reagents

Problem Solving Tip 8.1: Stoichiometry Calculations

When you are asked to determine what mass of product can be formed from a given mass of reactant. It is not possible
to calculate the mass of product in a single step. Instead, you must follow a route such as that illustrated in the strategy
map here for the reaction of reactant A to give the product B. Remember to follow these steps:

1. Write the balanced equation for the chemical

reaction, for example:

𝑥A −−−→ 𝑦B

2. Convert the mass (g) of reactant A to the amount (moles) of A using the molar mass of A.
3. Next, use the stoichiometric factor to find the amount (moles) of B.
4. Finally, obtain the mass (g) of B by multiplying the amount of B by its molar mass.

When solving a stoichiometry problem, remember that you will always use a stoichiometric factor at some point.

8.3 Reactions Where One Reactant is in Limited Supply: Limiting Reagents

Learning Outcomes for This Section: Limiting Reagents

What are our aims for this section?

▷ Determine which reactant is in limited supply in a reaction involving several reactants.

▷ Determine the yield of a product based on the limiting reactant.

Balanced chemical equations give the ideal stoichiometric relationship between reactants and products. However, reactions
are often conducted using more of one reactant than is called for by an exact stoichiometric ratio. This is usually done to make
sure that one of the reactants is consumed completely, even though some of another reactants remain unused. The reactant
that remains unused is the so-called limiting reagent.

Think of a limiting reagent as the ingredient that runs out first and stops production. For example, if a cake needs 4 eggs and
100g of flour, but you only have 2 eggs and 100g of flour, you can only make half a cake. The eggs limit how much you can
make, they are the limiting ingredient. Even though there is enough flour, it does not matter once the eggs are used up!

8.3.1 Stoichiometry Calculation with a Limiting Reactant

We can follow a short procedure to determine which reagent is in excess and which is limiting.

1. Calculate the amount (moles) of each reactant.

2. Calculate the expected mass of the product.

3. Determine the limiting reagent and the maximum product mass that can be obtained.

4. Calculate the mass of the excess reagent.

5. Summarise your information in an amounts table.

5 University of Pretoria | Department of Chemistry

8.3 Reactions Where One Reactant is in Limited Supply: Limiting Reagents CMY 117 | General Chemistry

Example 8.2
A Reaction with a Limiting Reactant
Methanol, CH3 OH, which can be used as a fuel in racing cars and in fuel cells, can be made by the reaction of carbon
monoxide and hydrogen.
CO(𝑔) + 2 H2 (𝑔) −−−→ CH3 OH(𝑙)

Suppose 356 g of CO and 65.0 g of H2 are mixed and allowed to react.

(a) What mass of methanol can be produced?

(b) What mass of the excess reactant remains after the limiting reactant has been consumed?

Solution discussed in Video Lecture

University of Pretoria | Department of Chemistry 6

CMY 117 | General Chemistry 8.3 Reactions Where One Reactant is in Limited Supply: Limiting Reagents

Problem Solving Tip 8.2: Moles of Reaction and Limiting Reactants

There is another method for solving stoichiometry problems that applies especially well to limiting reactant problems.
This involves the useful concept of moles of reaction. The definition of this can be quite strange at first but what this
means is:

One mole of reaction occurs when the reaction has taken place according to the number of moles given by the
coefficients in the balanced equation.

For example, for the reaction of CO and O2 ,

2CO(𝑔) + O2 (𝑔) −−−→ 2CO2 (𝑔)

1 mole of reaction occurs when 2 mol of CO and 1 mol of O2 produce 2 mol of CO2 . The unit moles of reaction
(mol-rxn) counts how many times the chemical reaction itself occurs.
Now, suppose 9.5 g of CO and excess O2 are combined. What amount of CO2 (moles) can be produced?

| 1 mol CO | 1 mol-rxn | 2 mol CO2 |

9.5 g CO | | | | = 0.34 mol CO2
| 28.0 g CO | 2 mol CO | 1 mol-rxn |

All reactants and products involved in a chemical reaction undergo the same number of moles of reaction
because the reaction can only occur a certain number of times before one or more of the reactants are consumed and
the reaction reaches completion.

If one of the reactants is in limited supply, the actual number of times a reaction can be carried out, the number of
moles of reaction, will be determined by the limiting reactant. Using an approach similar to Example 8.2, you first
calculate the amount of each reactant initially present and then calculate the moles of reaction that could occur with
each amount of reactant. [This is equivalent to dividing the amount (moles) of each reactant by its stoichiometric
coefficient.] The reactant producing the smaller number of moles of reaction is the limiting reactant. Once the limiting
reactant is known, you proceed as before.

As an example, consider the reaction of oxygen and ammonia

4NH3 (𝑔) + 5O2 (𝑔) −−−→ 4NO(𝑔) + 6H2 O(𝑙)

Suppose equal masses of NH3 and O2 are mixed (750. g of each). Are these reactants mixed in the correct stoichiometric
ratio or is one of them in short supply? That is, will one of them limit the quantity of NO that can be produced? How
much NO can be formed if the reaction using this reactant mixture goes to completion? And how much of the excess
reactant is left over when the maximum amount of NO has been formed? For the sake of this problem solving tip we
will look at how we can use the idea of ”mol-rxn” to solve the same limiting reagent problem.

Step 1. Calculate the moles of reaction predicted for each reactant and decide on the limiting reactant. In the case of the
NH3 /O2 reaction, 1 mole of reaction uses 4 mol of NH3 and 5 mol of O2 and produces 4 mol of NO and 6 mol of H2 O.
750. g NH3 is 44.04 mol of NH3 , so this would mean that 44.04/4 =11.01 mol of reaction is possible, you can verify this
by checking the units:
| 1 mol-rxn |
44.04 mol NH3 | | = 11.01 mol-rxn
| 4 mol NH3 |
Based on the amount (750. g, or 23.44 mol) of O2 available, 4.688 mol of reaction could occur, again you can verify the

7 University of Pretoria | Department of Chemistry

8.3 Reactions Where One Reactant is in Limited Supply: Limiting Reagents CMY 117 | General Chemistry

calculation by checking the units:

| 1 mol-rxn |
23.44 mol O2 | | = 4.688 mol-rxn
| 5 mol O2 |

Because fewer moles of reaction can occur with the amount of O2 available, so O2 is the limiting reactant.

Step 2. Calculate the change in amount and the amount upon completion of the reaction for each reactant and product.
The number of moles of reaction predicted by the limiting reactant corresponds to the number of moles of reaction
that can actually occur. Each reactant and product will undergo this number of moles of reaction, 4.688 mol-rxn in
this case. To calculate the change in amount for a given reactant or product, multiply this number of moles of reaction
by the stoichiometric coefficient of the reactant or product. To illustrate, for NH3 this corresponds to the following
calculation:
| 4 mol NH3 |
4.688 mol-rxn | | = 18.75 mol NH3
| 1 mol-rxn |
The amount of each reactant and product after reaction is calculated as usual. We can summarise this in an amounts
table as follows

Equation 4 NH3 (g) + 5 O2 (g) −−→ 4 NO(g) + 6 H2 O(g)

Initial Amount (mol) 44.04 23.44 0 0

Moles of Reaction (based on Limiting 4.688 4.688 4.688 4.688

Reagent)

Change in amount (mol)* −4.688(4) −4.688(5) +4.688(4) +4.688(6)

= −18.75 = −23.44 = +18.75 = +28.13

Amount after reaction (mol) 25.29 0 18.75 28.13

*Notice that the moles of reaction are multiplied by the stoichiometric coefficient for each reactant and product.

University of Pretoria | Department of Chemistry 8

CMY 117 | General Chemistry 8.4 Percentage Yield

8.4 Percentage Yield

Learning Outcomes for This Section: Percentage Yield

What is our aim for this section?

▷ Explain the differences among actual yield, theoretical yield, and percent yield, and calculate percent yield for
a reaction.

We can define a few terms:

▷ Theoretical Yield: The maximum mass of product that can be obtained from a chemical reaction is the theoretical yield.
The theoretical yield is obtained from a stoichiometry calculation.

▷ Experimental or Actual Yield: The actual yield of the product (the mass of material that is actually obtained in the
laboratory) is almost always less than the theoretical yield.

▷ Percentage Yield: This percentage specifies how much of the theoretical yield was obtained.

We can calculate Percentage Yield Using Equation (8.1):

Actual Yield
Percentage Yield = × 100 (8.1)
Theoretical Yield

Example 8.3
Calculating Percentage Yield
Aspirin can be made in the laboratory by the following reaction:

C4 H6 O3 (𝑙) + C7 H6 O3 (𝑠) −−−→ CH3 CO2 H(𝑙) + C9 H8 O4 (𝑠)

Acetic Anhydride Salicylic Acid Acetic Acid Aspirin

What is the percent yield of the reaction if 6.26 g of aspirin is obtained from 14.4 g of salicylic acid (C7 H6 O3 ) and an
excess of acetic anhydride?

Solution discussed in Video Lecture

9 University of Pretoria | Department of Chemistry

8.4 Percentage Yield CMY 117 | General Chemistry

Example 8.4
An All-Inclusive Stoichiometry Example
Bornite (Cu3 FeS3 ) is an ore of copper. When it is heated in air, the following reaction takes place:

2Cu3 FeS3 (𝑠) + 7O2 (𝑔) −−−→ 6Cu(𝑠) + 2FeO(𝑠) + 6SO2 (𝑔)

Suppose 600. g of bornite (with a 97.3% purity) is reacted with 500. g of oxygen. By taking into account the limiting
reagent, determine the amount of SO2 gas produced (64.07 g⋅mol−1 ) if the percentage yield of the reaction is 79.70%.

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 10

CMY 117 | General Chemistry 8.5 Chemical Equations and Chemical Analysis

8.5 Chemical Equations and Chemical Analysis

Learning Outcomes for This Section: Chemical Equations and Chemical Analysis

What are our aims for this section?

▷ Use stoichiometry principles to analyze a mixture of compounds.

▷ Find the empirical formula of an unknown compound using chemical stoichiometry.

8.5.1 Quantitative Analysis of a Mixture

Quantitative chemical analysis involves determining the amount or concentration of a substance in a sample. In such
analyses, the principles of chemical stoichiometry allow chemists to conduct chemical reactions and relate the quantities of
products obtained to the quantity of the material of interest.

Quantitative chemical analysis generally depends on one of the following basic ideas:

▷ A substance (A), present in an unknown amount, can be allowed to react with a known amount of another substance
(B). If the stoichiometric ratio for their reaction is known (A/B), the unknown amount (of A) can be determined (for
example, determining the amount of acetic acid in vinegar).

▷ A material of unknown composition can be converted to one or more substances of known composition. Those substances
can be identified, their amounts determined, and these amounts related to the amount of the original, unknown substance
(for example, gravimetric analysis, in which the mass of a precipitate is used to determine the composition of an
unknown sample).

Figure 8.1: The procedure for analyzing a solution for the sulfate ion content by precipitation. This procedure is an
example of a gravimetric analysis.

11 University of Pretoria | Department of Chemistry

8.5 Chemical Equations and Chemical Analysis CMY 117 | General Chemistry

Example 8.5
Analysis of a Mineral
Sodium sulfate, Na2 SO4 , occurs naturally as the mineral thenardite. To analyze an impure mineral sample for the
quantity of Na2 SO4 , the sample is crushed, then dissolved in water to form a solution of Na2 SO4 . Next, the aqueous
solution is treated with aqueous barium chloride, BaCl2 , to give solid BaSO4 (see Figure 8.1).

Na2 SO4 (𝑎𝑞) + BaCl2 (𝑎𝑞) −−−→ BaSO4 (𝑠) + 2 NaCl(𝑎𝑞)

Suppose a 0.498 g sample containing thenardite produces 0.541 g of solid BaSO4 . What is the mass percent of Na2 SO4
in the sample?

Solution discussed in Video Lecture

8.5.2 Determining the Formula of a Compound by Combustion – Let’s Burn It!

The empirical formula of a compound can be found using the percent composition. One method, combustion analysis,
involves burning the compound in oxygen to form oxides. This process allows the calculation of the compound’s percent
composition or empirical formula based on the oxides produced.

Problem Solving Tip 8.3: General Approach to Finding an Empirical Formula by Chemical Analysis

Step 1. A chemical reaction converts Step 2. The reaction products are Step 3. The amount (moles) of each
the unknown but pure compound into isolated, and the amount (moles) of product is related to the amount
known products. each product is determined. (moles) of each element in the
original compound.
Step 4. The percentage composition Step 5. The empirical formula is
of the compound is determined. determined from the relative amounts
(moles) of elements in the original
compound.

University of Pretoria | Department of Chemistry 12

CMY 117 | General Chemistry 8.5 Chemical Equations and Chemical Analysis

Example 8.6
Using Combustion Analysis to Determine the Empirical Formula of a Hydrocarbon
When 1.125 g of a liquid hydrocarbon, C𝑥 H𝑦 , is burned, 3.447 g of CO2 and 1.647 g of H2 O are produced. In a separate
experiment, the molar mass of the compound is found to be 86.2 g⋅mol−1 . Determine the empirical and molecular
formulas for the unknown hydrocarbon, C𝑥 H𝑦 .

Solution discussed in Video Lecture

13 University of Pretoria | Department of Chemistry

8.5 Chemical Equations and Chemical Analysis CMY 117 | General Chemistry

Example 8.7
Using Combustion Analysis to Determine the Empirical Formula of a Compound Containing C, H, and O
You have isolated an acid from clover leaves and know it contains only the elements C, H, and O. Burning 0.513 g of
the acid in oxygen produces 0.501 g of CO2 and 0.103 g of H2 O. What is the empirical formula of the acid, C𝑥 H𝑦 O𝑧 ?

Solution discussed in Video Lecture

University of Pretoria | Department of Chemistry 14

CMY 117 | General Chemistry 8.5 Chemical Equations and Chemical Analysis

Example 8.8
Determining the Molecular Formula of a Compound Through Combustion Analysis
Many compounds were investigated for allegedly assisting patients who had contracted Covid-19. One such compound
was Quovirin. This compound was analysed in a laboratory as follows:

▷ The compound contains C, H, N and O.

▷ Exactly 15 grams of the compound was combusted with excess oxygen gas at high temperatures to yield 36.3353
g CO2 and 6.3216 g H2 O.

▷ The compound contains 11.566% nitrogen by mass.

▷ Calculations from several experiments show that one molecule contains 3 atoms of nitrogen.

Determine by means of a full calculation the molecular formula of Quovirin.

Solution to be discussed during lecture period

15 University of Pretoria | Department of Chemistry

8.6 Measuring Concentrations of Compounds in Solution CMY 117 | General Chemistry

8.6 Measuring Concentrations of Compounds in Solution

Learning Outcomes for This Section: Measuring Concentrations of Compounds in Solution

What are our aims for this section?

▷ Calculate the concentration of a solute in a solution in units of moles per liter (molarity, mol⋅L−1 ) and use
solution concentrations in calculations.

▷ Describe how to prepare a solution of a given concentration from the solute and solvent or by dilution of a
more concentrated solution.

8.6.1 Solution Concentration: Molarity

Molarity, 𝑐, is the amount of solute per liter of solution:

amount of solute x (mol)

Molarity of 𝑥 (𝑐𝑥 ) = (8.2)
volume of solution (L)

For example, if 58.4 g (1.00 mol) of NaCl is dissolved in enough water to give a total solution volume of 1.00 L, the molarity, 𝑐
= 1.00 mol⋅L−1 . This is often abbreviated as 1.00 M, where capital M is the symbol for “moles per liter.” We sometimes also
write:

𝑐NaCl = [NaCl] = 1.00 mol⋅L−1 = 1.00 M

It is important to notice that molarity refers to the amount of solute per liter of solution and not per liter of solvent.

If one liter of water is added to one mole of a solid compound, the final volume will not be exactly one liter, and the final
concentration will not be exactly one mol⋅L−1 . Hence, read if a question adds the words: ”enough water was added to make
up a solution of 1 L ect.”

Example 8.9
Concentration
If 25.3 g of sodium carbonate, Na2 CO3 , is dissolved in enough water to make 250. mL of solution, what is the
concentration of Na2 CO3 ? What are the concentrations of the Na+ and CO2−
3 ions?

Solution discussed in Video Lecture

University of Pretoria | Department of Chemistry 16

CMY 117 | General Chemistry 8.6 Measuring Concentrations of Compounds in Solution

We can rewrite Equation (8.2) to give:

mol
Amount of solute x (mol) = 𝑐𝑥 ( ) × volume of solution (L) (8.3)
L

You will find this equation very useful in solving stoichiometry problems that involve solutions.

Example 8.10
Relating Amount and Molarity
You transfer 50.0 mL of a 0.250. M solution of sodium chloride into a graduated cylinder. What amount (mol) of sodium
chloride is in the cylinder?

Solution discussed in Video Lecture

8.6.2 Preparing Solutions of Known Concentration

Chemists often need to prepare a given volume of solution of known concentration. There are two commonly used methods
to do this.

Combining a Weighed Solute with the Solvent

Suppose you need to prepare 2.00 L of a 1.50 M solution of aqueous Na2 CO3 . You have some solid Na2 CO3 , distilled water, and
a 2.00. L volumetric flask.

So, how much (mass) Na2 CO3 is required to make this solution? How do we calculate that? Well, we use Equation (8.3), as
follows:

Thus, to prepare the desired solution, you should dissolve 318 g of Na2 CO3 in enough water to make 2.00 L of solution.

Diluting a More Concentrated Solution

Another method for making a solution of a given concentration is, to begin with a concentrated solution of known concentration
and add more solvent (usually water) until the desired, a lower concentration is reached.

17 University of Pretoria | Department of Chemistry

8.6 Measuring Concentrations of Compounds in Solution CMY 117 | General Chemistry

Example 8.11
Preparing a Solution by Dilution
What is the concentration of iron(III) ions in a solution prepared by diluting 1.00 mL of a 0.236 M solution of iron(III)
nitrate, Fe(NO3 )3 , to a volume of 100.0 mL?

Solution discussed in Video Lecture

A Closer Look 8.1: Serial Dilutions

You often will find that a solution you initially made in a laboratory is too concentrated for the analytical technique
you want to use. Suppose you have 100.0 mL of a seawater sample that has an NaCl concentration of 0.550
mol⋅L−1 . You transfer 10.00 mL of that sample to a 100.0-mL volumetric flask and fill to the mark with distilled
water. After thoroughly mixing the diluted sample, you then transfer 5.00 mL of that sample to another 100.0-mL
flask and fill to the mark with distilled water. What is the NaCl concentration in the final 100.0-mL sample? We do
the following step-wise dilution for this:

The original solution contains 0.550 mol⋅L−1 of NaCl. If you remove 10.00 mL, you have removed

 0.550 mol 
0.01000 L   = 5.500 × 10 mol NaCl
−3
1L

University of Pretoria | Department of Chemistry 18

CMY 117 | General Chemistry 8.7 The Concept of pH – A Concentration Scale for Acids and Bases

and the concentration in 100.0 mL of the diluted solution is

5.500 × 10−3 mol

𝑐NaCl = = 5.500 × 10−2 M
0.1000 L

or 1/10 of the concentration of the original solution. Now, take 5.00 mL of the diluted solution and dilute that
once again to 100.0 mL. The final concentration is

 5.500 × 10−2 mol  2.750 × 10−4 mol

0.00500 L   = 2.750 × 10−4 mol NaCl ⟹ 𝑐NaCl = = 2.750 × 10−3 M
 1L  0.1000 L

This is 1/200 of the concentration of the original solution. A fair question at this point is why not just take 1 mL
of the original solution and dilute to 200 mL? The answer is that there is less error introduced using larger pipets
such as 5.00- or 10.00-mL pipets rather than a 1.00-mL pipet. There is also a limitation in available glassware. A
200.00-mL volumetric flask is unlikely to be available.

8.7 The Concept of pH – A Concentration Scale for Acids and Bases

Learning Outcomes for This Section: The Concept of pH – a Concentration Scale for Acids and Bases

What are our Aims for this section?

▷ Understand the pH scale.

▷ Calculate the pH of a solution from the concentration of hydronium ions in the solution. Calculate the
hydronium ion concentration in a solution from its pH.

The pH of a solution is the negative of the base-10 logarithm of the hydronium ion concentration. We calculate it as follows:

+
pH = − log[H3 O ] (8.4)

These pH values are more convenient numbers to use than the numbers in scientific notation. You can see that something
you recognize as acidic has a relatively low pH, whereas ammonia, a common base, has a very low hydronium ion
concentration and a high pH.

To find the hydronium ion concentration of a solution you calculate the antilog, or inverse log, of the pH. That is,

+
[H3 O ] = 10−pH (8.5)

19 University of Pretoria | Department of Chemistry

8.8 Stoichiometry of Reactions in Aqueous Solution – Fundamentals CMY 117 | General Chemistry

Example 8.12
pH of Solutions
Consider the following questions:

(a) Lemon juice has [H3 O+ ] = 0.0032 M. What is its pH?

(b) Seawater has a pH of 8.07. What is the hydronium ion concentration of this solution?

(c) A solution of nitric acid has a concentration of 0.0056 mol⋅L−1 . What is the pH of this solution?

Solution discussed in Video Lecture

8.8 Stoichiometry of Reactions in Aqueous Solution – Fundamentals

Learning Outcomes for This Section: Stoichiometry of Reactions in Aqueous Solution – Fundamentals

What is our aim for this section?

▷ Use stoichiometry principles for reactions occurring in solution.

In the laboratory, chemists carry out most reactions in solutions, usually in water. Water is a common solvent even in nature.
For example, the reactions in our bodies occur in an aqueous environment.

The problems of this section differ from the previous stoichiometry problems in that the quantity of one reactant is given as the
volume of a solution with a known concentration instead of as a mass in grams. Because the balanced equation is written
in terms of amounts (moles), we will need to add some steps to get to that point.

University of Pretoria | Department of Chemistry 20

CMY 117 | General Chemistry 8.8 Stoichiometry of Reactions in Aqueous Solution – Fundamentals

Problem Solving Tip 8.4: Stoichiometry Calculations Involving Solutions

Example 8.13
Stoichiometry of a Reaction in Solution I
Metallic zinc reacts with aqueous HCl as follows:

Zn(𝑠) + 2 HCl(𝑎𝑞) −−−→ ZnCl2 (𝑎𝑞) + H2 (𝑔)

What volume of 2.50 M HCl, in millilitres, is required to completely consume 11.8 g of Zn?

Solution to be discussed during lecture period

21 University of Pretoria | Department of Chemistry

8.8 Stoichiometry of Reactions in Aqueous Solution – Fundamentals CMY 117 | General Chemistry

Example 8.14
Stoichiometry of a Reaction in Solution II
Nitric acid reacts with copper metal as follows

4HNO3 (𝑎𝑞) + Cu(𝑠) −−−→ Cu(NO3 )2 (𝑎𝑞) + 2NO2 (𝑔) + 2H2 O(𝑙)

The following information is known to you:

▷ 3.00 L of a 0.810 M HNO3 solution is available.

▷ A 150. mL portion of this solution was accurately diluted to 500. mL by adding distilled water.

▷ 4.000 g of powdered Cu was added to the final solution.

Determine the [NO− 2+

3 ] and [Cu ] in the final solution after the reaction has been completed. (You may assume that no
volume change occurs when the metal is added to the solution.)

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 22

CMY 117 | General Chemistry 8.9 Stoichiometry of Reactions in Aqueous Solution – Titrations

8.9 Stoichiometry of Reactions in Aqueous Solution – Titrations

Learning Outcomes for This Section: Stoichiometry of Reactions in Aqueous Solution – Titrations

What is our aim for this section?

▷ Explain how a titration is conducted, explain the procedure for standardization of a solution, and calculate
concentrations or amounts of reactants from titration data.

8.9.1 Titration: A Method of Chemical Analysis

Suppose you are asked to determine the concentration of hydrochloric acid, HCl, in a solution. Because the compound is
an acid, it reacts with a base such as sodium hydroxide. Hence, we can use this reaction to determine the concentration of
hydrochloric acid present in a given volume of hydrochloric acid solution if the following conditions are met:

▷ You can determine when the amount of sodium hydroxide added is exactly the amount required to react with all the
hydrochloric acid present in solution.

▷ You know the concentration of the sodium hydroxide solution and volume added at exactly the point of complete reaction.

These conditions are fulfilled in a titration. Figure 8.2 illustrates the procedure of a titration.

Figure 8.2: Titration of an acid in aqueous solution with a base.

23 University of Pretoria | Department of Chemistry

8.9 Stoichiometry of Reactions in Aqueous Solution – Titrations CMY 117 | General Chemistry

The solution containing hydrochloric acid is placed in a flask along with an acid-base indicator, a dye that changes color
when the pH of the reaction solution reaches a certain value. An aqueous sodium hydroxide solution of accurately known
concentration is placed in a buret. The sodium hydroxide in the buret is added slowly to the acid solution in the flask.

As long as some acid is present in the solution, all the base supplied from the buret is consumed, the solution remains acidic,
and the indicator color is unchanged. At some point—the equivalence point—the amount of OH− supplied by the base exactly
equals the amount of H3 O+ supplied by the acid. In the vicinity of the equivalence point, the pH rises rapidly with each
additional drop of NaOH. The titration is finished when one final drop of NaOH raises the pH sufficiently to change the colour
of the acid–base indicator. If the indicator is chosen properly, its color will change at, or very near, the equivalence point (see
Figure 8.2).

Example 8.15
Acid-Base Titration
A 15.00. mL sample of an aqueous hydrochloric acid solution with an unknown concentration is transferred to a flask,
and an acid–base indicator is added. After adding 29.27 mL of 0.09977 M NaOH, the acid-base indicator changes colour,
indicating that the equivalence point has been reached. What is the concentration of hydrochloric acid in the original
solution?

Solution discussed in Video Lecture

University of Pretoria | Department of Chemistry 24

CMY 117 | General Chemistry 8.9 Stoichiometry of Reactions in Aqueous Solution – Titrations

Example 8.16
Determining Purity by Acid-Base Titration
A 1.034 g sample of impure oxalic acid, H2 C2 O4 (a diprotic acid), is dissolved in water and an acid–base indicator added.
The sample requires 34.47 mL of 0.485 M NaOH to titrate the acid. One mole of acid requires two moles of NaOH for
a complete reaction. What is the mass of oxalic acid in the sample, and what is its mass percent?

Solution to be discussed during lecture period

25 University of Pretoria | Department of Chemistry

8.9 Stoichiometry of Reactions in Aqueous Solution – Titrations CMY 117 | General Chemistry

8.9.2 Determining Molar Mass by Titration

We have used analytical data to determine the empirical formula of a compound. The molecular formula could then be derived
if the molar mass were known. If the unknown substance is an acid or a base, it is possible to determine the molar mass by
titration.

Example 8.17
Determining the Molar Mass of an Acid by Titration
A 1.056 g sample of an unknown organic acid, HA, is titrated with standardized NaOH (that is, with a NaOH solution
whose concentration is accurately known). Calculate the molar mass of HA knowing the acid sample reacts with 33.78
mL of 0.256 M NaOH according to the equation

HA(𝑎𝑞) + NaOH(𝑎𝑞) −−−→ NaA(𝑎𝑞) + H2 O(𝑙)

Solution discussed in Video Lecture

University of Pretoria | Department of Chemistry 26

CMY 117 | General Chemistry 8.9 Stoichiometry of Reactions in Aqueous Solution – Titrations

8.9.3 Titrations Using Oxidation-Reduction Reactions

Many oxidation-reduction reactions can be used in chemical analysis because the reactions go rapidly to completion in an
aqueous solution, and methods exist to determine their equivalence points.

Example 8.18
Using an Oxidation-Reduction Reaction in a Titration
The iron in a sample of iron ore can be converted quantitatively to the iron(II) ion, Fe2+ , in an aqueous solution, and
this solution can then be titrated with aqueous potassium permanganate, KMnO4 . The balanced, net ionic equation
for the reaction occurring in this titration is

− +
MnO4 (𝑎𝑞) + 5 Fe2+
(𝑎𝑞) + 8 H3 O(𝑎𝑞) −−−→ Mn2+
(𝑎𝑞) + 5 Fe3+
(𝑎𝑞) + 12 H2 O(𝑙)
Purple Colourless Colourless Pale Yellow

A 1.026 g sample of iron-containing ore requires 24.35 mL of 0.0195 M KMnO4 to reach the equivalence point. What is
the mass percent of iron in the ore?

Solution to be discussed during lecture period

27 University of Pretoria | Department of Chemistry

8.10 Additional Practice Problems CMY 117 | General Chemistry

8.10 Additional Practice Problems

Here I list some additional practice problems for you to do at home. The solutions to these problems are provided in the video
content on YouTube.

Basic Reaction Stoichiometry Calculations and Yield

Answer the following questions for the combustion reactions below, given that the only products of the combustion are the
gasses CO2 and H2 O.

(a) How many moles of O2 are required to fully combust with 2.191 kg of propane gas (C3 H8 ).

(b) What mass of propane is required to produce 6.560 kg of CO2 at a yield of 86.00%?

(c) What mass of water is produced by the combustion of 1.460 kg butane (C4 H10 )? Furthermore, how many hydrogen
atoms is represented by this mass of water?

(d) What mass of carbon dioxide is obtained when 3.867 L of air (23.3% O2 ) reacts with butane? Given that the air density
under the reaction conditions is 1.30 kg⋅L−1 .

Limiting Reagents

Consider the combustion of butane (C4 H10 ). Assume for this combustion reaction the only products are the gasses CO2 and
H2 O.

(a) What mass of CO2 can be produced by the reaction of 116.2 g of butane with 215.9 g O2 ?.

(b) What mass of excess reagent is left after the reaction has been completed?

Limiting Reagents and Reaction Addition

What mass of water (and carbon dioxide) is produced when 400 g C3 H8 and 116 g C4 H10 and 430 g O2 react?

Coupled Reactions and Limiting Reagent

What mass of Pd metal is theoretically deposited on the dosimeter when 10.0 g of propane reacts with oxygen gas if the reactions
given below occur subsequently? (Assume both reactions occur at a 100% yield)

2 C3 H8 (𝑔) + 9 O2 (𝑔) −−−→ 4 CO2 (𝑔) + 2 CO(𝑔) + 8 H2 O(𝑔)

CO(𝑔) + PdCl2 ⋅ 2 H2 O(𝑠) −−−→ CO2 (𝑔) + Pd(𝑠) + 2 HCl(𝑔) + H2 O(𝑔)

Using Gravimetry to Determine the %Purity of a Sample

A sample of ammonium nitrate to be used a fertilizer, is suspected of being contaminated with lead nitrate. A 1.500 g sample
is crushed, dissolved in water and treated with potassium chromate to give 0.569 g of a lead chromate precipitate. Determine
the %purity of the sample.

University of Pretoria | Department of Chemistry 28

CMY 117 | General Chemistry 8.10 Additional Practice Problems

Determining a Molecular Formula Through Combustion

Lysine is an amino acid containing C, H, N and oxygen. A 2.175 mg sample of the compound is combusted, yielding 3.929 mg
of CO2 and 1.876 mg of H2 O. In a separate experiment, 1.873 mg of lysine combusted to give 0.436 mg of NH3 . Given that the
molecular mass of lysine lies between 140 u and 160 u, determine the molecular formula of lysine.

Concentration Calculations

Consider the following questions regarding making a solution using copper(II) nitrate trihydrate (Cu(NO3 )2 ⋅3 H2 O):

(a) If 4.00 mol copper(II) nitrate trihydrate must be dissolved to make 500.00 mL of a solution, determine the concentration
(molarity) of the salt in solution.

(b) Consider 250.00 mL of a 1.50 M solution of copper(II) nitrate trihydrate. Determine the molarities of all the ions in
solution.

(c) Consider 250.00 mL of a solution that contains 59.60 g of copper(II) nitrate trihydrate. Determine the molarities of all
the ions in solution.

(d) A solution of 0.038 M copper(II) nitrate trihydrate is available. In an experiment 0.760 mmol of Cu(NO3 )2 is required.
What volume of the solution contains this amount of solute?

Solution Calculations

A solution of C2 H5 OH(𝑙) (ethanol) in water is prepared by adding 80.0 mL of ethanol to enough water to make a solution with
a final volume of 250.00 mL. What is the molarity of the ethanol in the final solution? (The density of ethanol is 0.79 g⋅cm−3 .)

Serial Dilutions

Consider 750. mL of a stock solution that is 1.00 M Cu(NO3 )2 . Two dilutions are made as follows:

(a) 50.00 mL of the stock solution is pipetted into a 250 mL volumetric flask and made up to the mark with distilled water.

(b) 10.00 mL of solution (a) is pipetted into a 200 mL volumetric flask and made up to the mark with distilled water.

Determine the concentration of NO−

3 in solution (b).

Dilutions by Mixing

Consider mixing 50.00 mL of a 0.100 M Cu(NO3 )2 solution with 100.00 mL of 1.00 M Cu(NO3 )2 solution. Determine the
concentration of all the species in the final solution (You may assume that the volumes are additive).

Reactions in Solutions

Suppose 150.0 mL of a 1.00 M Cu(NO3 )2 solution is allowed to react with 200.0 mL of a 0.500 M Na2 CO3 solution. Answer the
following questions for the given scenario:

(a) Determine the concentration of all the species after the reaction is completed.

29 University of Pretoria | Department of Chemistry

8.10 Additional Practice Problems CMY 117 | General Chemistry

(b) Suppose 11.87 g of carbonate precipitate is obtained in the reaction described. What is the % yield of this reaction?

(c) Suppose the solid sodium carbonate used to make the solution was only 92.3% pure. What mass of the solid would have
to be weighed out to give 12.36 g of the copper carbonate precipitate?

pH Calculations

Answer the following pH-related questions:

(a) Vinegar has a [H3 O+ ] = 1.55 × 10−3 M. Determine the pH of vinegar.

(b) Household ammonia has a pH = 11.28. Determine the [H3 O+ ] and [OH− ]

(c) A solution of H2 SO4 has a concentration of 0.0040 M. Determine the pH of this solution.

Reactions in Solution and pH

Determine the molarities of all the ions present in a solution made by adding 1.50 × 102 mL of 2.00 × 10−2 M Ba(OH)2 solution
to 1.00 × 102 mL of 5.00 × 10−2 M HCl. Subsequently determine the pH of the final solution after the reaction has taken place.
+
Hint: Think pH = − log[H3 O ], and that pOH = − log[OH− ].

Back (Indirect) Titration to Determine the Concentration of a Volatile Substance

A student was asked to determine the concentration of ammonia, a volatile substance, in a commercially available cloudy
ammonia solution used for cleaning. First the student pipetted 25.00mL of the cloudy ammonia solution into a 250.0mL conical
flask. 50.00mL of 0.100M HCl(𝑎𝑞) was immediately added to the conical flask which reacted with the ammonia in solution.
The excess (unreacted) HCl was then titrated with 0.050M Na2 CO3 (𝑎𝑞) . 21.50mL of Na2 CO3 (𝑎𝑞) was required. Calculate the
concentration of the ammonia in the cloudy ammonia solution.

Back (Indirect) Titration to Determine the Amount of an Insoluble Salt

A student was asked to determine the mass, in grams, of calcium carbonate present in a 0.125g sample of chalk. The student
placed the chalk sample in a 250mL conical flask and added 50.00mL 0.200M HCl using a pipette. The excess HCl was then
titrated with 0.250M NaOH. The average NaOH titre was 32.12mL Calculate the mass of calcium carbonate, in grams, present
in the chalk sample.

Back (Indirect) Titration to Determine Sample Purity

−1
A sample of Na2 CO3 (𝑀 = 105.99 g ⋅ mol ) is suspected of being contaminated with NaCl. The carbonate reacts with acid, but
not the NaCl. To ensure complete decomposition of the carbonate, excess HCl(𝑎𝑞) was added to 0.453 g of the impure sample,
namely 15.00 mL of 2.000 M HCl. The reaction taking place is

Na2 CO3 (𝑎𝑞) + 2 HCl(𝑎𝑞) −−−→ 2 NaCl(𝑎𝑞) + CO2 (𝑔) + H2 O(𝑙)

After all the ’fizzing’ stopped, enough water was added to the reaction mixture to make a solution, call this Solution A, of
250.00 mL.

University of Pretoria | Department of Chemistry 30

CMY 117 | General Chemistry 8.10 Additional Practice Problems

A 20.00 mL aliquot (a fixed portion of the larger amount) of Solution A was then neutralised by titration with 15.03 mL of
0.116 M NaOH, given by the reaction equation:

NaOH(𝑎𝑞) + HCl(𝑎𝑞) −−−→ NaCl(𝑎𝑞) + H2 O(𝑙)

Determine the % of NaCl impurity in the original sample.

Redox Titrations

A 0.370 g sample of molybdenum ore was crushed and dissolved in acid, resulting in a solution of molybdate ions, MoO2−
4 .
This was subsequently converted to Mo3+ by a reduction process.

A 25.00 mL sample of the Mo3+ solution was titrated against a 0.0955 M KMnO4 solution. The average titre was measured to
be 20.85 mL. The products of the titration are a solution of manganese (II) ions and MoO2+
2 (𝑎𝑞) . Assume 100% conversion in all
steps.

For this titration answer the following:

(a) Write a fully balanced ionic equation for the redox reaction taking place during the titration.

(b) Determine the concentration of the original MoO2−

4 solution.

(c) Determine the mass percentage of molybdenum in the ore sample.

31 University of Pretoria | Department of Chemistry

 Theme
Energy and
9 Chemical Reactions
Click Here to access this Theme’s YouTube Playlist

9.1 Introduction

The importance of energy is evident in everyday life – in heating and cooling homes, in powering appliances, and in propelling
vehicles, among other things. Most of the energy used for these purposes is obtained by conducting chemical reactions, largely
by burning fossil fuels (natural gas, coal, and petroleum). Natural gas is used for heating, coal and natural gas are burned to
provide electrical power, and fuels derived from petroleum are used in automobiles, trucks, and aircraft. In addition, energy is
required for living things: Chemical reactions in our bodies provide energy for bodily functions, for movement, and to maintain
body temperature.

Thermodynamics is the area of science that deals with energy and its relationship to quantities such as heat and work.
Determining the energy changes that occur when chemical processes take place is an important factor in the study of chemical
systems. In this chapter, you will learn how to measure energy changes for chemical processes, particularly those that result
in heating and cooling, and how these can be used to explore chemical reactions more thoroughly.

9.2 The Basic Principles of Energy

Learning Outcomes for This Section: The Basic Principles of Energy

What are our aims for this section?

▷ Recognize and use the language of thermodynamics: the system and its surroundings; exothermic and
endothermic reactions.

▷ Describe the nature of energy transfers as heat.

▷ Understand the sign conventions of thermodynamics.

Energy is the capacity to perform work, categorized into kinetic energy related to motion and potential energy derived from an
object’s position or state, with thermal energy referring to the molecular kinetic energy in chemistry.

Though energy can be converted from one type into another, the total amount of energy is conserved. This is formally stated
in the law of conservation of energy:

Energy can neither be created nor destroyed. Or, stated differently, the total energy of the universe is constant.

In the next section we will look at how we define the concepts of system and surroundings.

32
CMY 117 | General Chemistry 9.2 The Basic Principles of Energy

9.2.1 How Do We Know What is the System and What are the Surroundings?

In thermodynamics, the terms system and surroundings have precise and important meanings:

▷ A system is defined as an object, or collection of objects, being studied.

▷ The surroundings include everything outside the system that can exchange energy and/or matter with the system.

We define the system and surroundings as needed. As long as the two are in contact, they are able to exchange energy, which is
the most important criteria.

9.2.2 The Direction and Amount of Heat Transferred – Thermal Equilibrium

One way that energy can be transferred is as heat; this occurs when two objects at different temperatures are brought into
contact. Eventually, the two objects reach the same temperature, and the system has reached thermal equilibrium.

We can note two principle points here:

1. Energy transfer as heat occurs spontaneously from an object at a higher temperature to an object at a lower temperature;
the object whose temperature increases gains thermal energy, and the object whose temperature decreases loses
thermal

2. Transfer of energy as heat continues until both objects are at the same temperature and thermal equilibrium is achieved.

Hence, if we close off the system from the surroundings. The only thing that can happen is that objects in the system can
exchange their own heats. This case is called an isolated system.

When energy can only be transferred as heat between a system and its surroundings (see Figure 9.1), we define this as a closed
system since there may be heat transfer between system and surroundings, but not matter.

The directionality (meaning system → surroundings or system ← surroundings) of this transfer is described as exothermic or
endothermic:

▷ In an exothermic process, energy is transferred as heat from a system to its surroundings. The energy of the system
decreases and the energy of the surroundings increases. The energy transferred as heat is designated by the symbol 𝑞.
Because the system ends up with less energy than it started with, 𝑞sys < 0 (where the subscript sys refers to the system).

▷ An endothermic process is the opposite of an exothermic process. Energy is transferred as heat from the surroundings to
the system, increasing the energy of the system and decreasing the energy of the surroundings. For an endothermic
process, 𝑞sys > 0 because the system ends up with more energy than it started with.

33 University of Pretoria | Department of Chemistry

9.3 How Much Heat Can Something Absorb? – Specific Heat Capacity CMY 117 | General Chemistry

Figure 9.1: Exothermic and endothermic processes. The symbol q represents the energy transferred as heat, and the subscript
sys refers to the system.

9.3 How Much Heat Can Something Absorb? – Specific Heat Capacity

Learning Outcomes for This Section: How Much Heat Can Something Absorb? – Specific Heat Capacity

What is our aim for this section?

▷ Use specific heat capacity in calculations of energy transfers as heat involving temperature changes.

When an object is heated or cooled without a change in its physical state (solid to liquid etc.), its temperature change is
proportional to the quantity of thermal energy gained or lost by the object. The energy gained or lost as heat (𝑞, in joules)
is described by Equation (9.1)
𝑞 = 𝐶Δ𝑇 (9.1)

The constant, 𝐶, is called the heat capacity. This constant, usually reported in units of J⋅K−1 , has a unique value for every
object. The change in temperature, Δ𝑇, is calculated as the final temperature minus the initial temperature

Δ𝑇 = 𝑇final − 𝑇intial (9.2)

For many calculations, the specific heat capacity (𝑐) is used. This is defined as the energy transferred as heat that is required to
raise the temperature of one gram of a substance or a mixture by one kelvin. It is often reported in units of joules per gram per
kelvin (J⋅g−1 ⋅K−1 ). The energy gained or lost as heat when a given mass of a substance is warmed or cooled can be calculated
using Equation (9.3)
𝑞 = 𝑐𝑚Δ𝑇 (9.3)

Heat capacity can also be expressed on a per-mole basis. The amount of energy that is transferred as heat in raising the
temperature of one mole of a substance by one kelvin is the molar heat capacity.

In each of these equations, a positive 𝑞 indicates that the system’s energy increases, while a negative 𝑞 indicates that the
system’s energy decreases.

Interesting Information: The relationship between energy, mass, and specific heat capacity has numerous implications.
The high specific heat capacity of liquid water, 4.184 J⋅g−1 ⋅K−1 , is a major reason that large bodies of water have a profound
influence on climate. In spring, lakes warm up more slowly than the air. In autumn, the energy transferred by a large lake as it
cools moderates the drop in air temperature. The relevance of specific heat capacity is also illustrated when food is wrapped in

University of Pretoria | Department of Chemistry 34

CMY 117 | General Chemistry 9.3 How Much Heat Can Something Absorb? – Specific Heat Capacity

aluminum foil (specific heat capacity 0.897 J⋅g−1 ⋅K−1 ) and heated in an oven. You can remove the foil with your fingers after
taking the food from the oven. The small mass of aluminum foil used and its low specific heat capacity result in only a small
quantity of energy being transferred to your fingers (which have a larger mass and a higher specific heat capacity).

Example 9.1
Specific Heat Capacity
How much energy must be transferred to raise the temperature of a cup of coffee (250 mL) from 20.5 °C (293.7 K) to
95.6 °C (368.8 K)? Assume that water and coffee have the same density (1.00 g⋅mL−1 ) and specific heat capacity (4.184
J⋅g−1 ⋅K−1 ).

Solution to be discussed during lecture period

Figure 9.2: Transfer of energy as heat. When energy is transferred as heat from a hot metal to cool water, the thermal energy
of the metal decreases and that of the water increases. The value of 𝑞metal is thus negative and the value of 𝑞water is positive

35 University of Pretoria | Department of Chemistry

9.4 What Happens When Energy is Absorbed and a Substance Changes State? CMY 117 | General Chemistry

Example 9.2
Using Specific Heat Capacity
In an experiment like that shown in Figure 9.2, an 88.5-g piece of iron whose temperature is 78.8 °C (352.0 K) is placed
in a beaker containing 244 g of water at 18.8 °C (292.0 K). When thermal equilibrium is reached, what is the final
temperature?

Solution to be discussed during lecture period

9.4 What Happens When Energy is Absorbed and a Substance Changes

State?

Learning Outcomes for This Section: What Happens When Energy is Absorbed and a Substance Changes State?

What is the aim for this section?

▷ Use the heat of fusion and heat of vaporization to calculate the energy transferred as heat in changes of state.

A change of state refers to changes (such as melting or boiling) between the three states of matter: solid, liquid, and gas. We
can define a few terms to describe when which change of state occurs:

▷ The energy transferred as heat required to convert a substance from a solid to a liquid is called the heat of fusion.

▷ The energy transferred as heat to convert a liquid to a vapor is called the heat of vaporization.

Importantly, the temperature remains constant during a change of state. This is because during a change of state, the added
energy is used to overcome the forces holding one molecule to another, not to increase the temperature. This can be shown
graphically as follows:

University of Pretoria | Department of Chemistry 36

CMY 117 | General Chemistry 9.4 What Happens When Energy is Absorbed and a Substance Changes State?

Example 9.3
Energy and Changes of State
Calculate the energy needed to convert 500. g of ice at −50.0 °C (223.2 K) to steam at 200.0 °C (473.2 K). The heat of
fusion of water at 0 °C is 333 J⋅g−1 , and the heat of vaporization at 100 °C is 2256 J⋅g−1 . Look up the values you need.

Solution to be discussed during lecture period

37 University of Pretoria | Department of Chemistry

9.5 The First Law of Thermodynamics CMY 117 | General Chemistry

Example 9.4
Change of State
What is the minimum mass of ice at 0 °C that must be added to the contents of a can of diet cola (340. mL) to cool the
cola from 20.5 °C to 0.0 °C? Assume that the specific heat capacity and density of diet cola are the same as for water.

Solution to be discussed during lecture period

9.5 The First Law of Thermodynamics

Learning Outcomes for This Section: The First Law of Thermodynamics

What are our aims for this section?

▷ Recognize how energy transferred as heat and work contribute to changes in the internal energy of a system.

▷ Calculate the work done by a system when a gas expands against a constant pressure.

▷ Calculate changes in enthalpy and internal energy.

▷ Recognize state functions whose values are determined only by the state of the system and not by the pathway
by which the state was achieved.

Recall that thermodynamics is the science of heat and work. Up to this point in the chapter, heat has been discussed, but not
work. Work (𝑤) done by a system or on a system also affects the energy in the system.

If a system does work on its surroundings, the system must expend energy, and the system’s energy will decrease; 𝑤 is
therefore negative, 𝑤 < 0. Conversely, if work is done by the surroundings on a system, the energy of the system will
increase; 𝑤 > 0.

University of Pretoria | Department of Chemistry 38

CMY 117 | General Chemistry 9.5 The First Law of Thermodynamics

For any system, you can identify energy transfers both as heat and as work between the system and surroundings. This change
in energy for a system is called the internal energy, and is given explicitly by Equation (9.4),

Δ𝑈 = 𝑤 + 𝑞 (9.4)

This is the mathematical statement of the first law of thermodynamics: The energy change for a system (Δ𝑈) is the sum of
the energy transferred as heat (𝑞) between the system and its surroundings and the energy transferred as work (𝑤) between
the system and its surroundings.

Actual values of internal energy are rarely determined or needed. Instead, changes in internal energy (Δ𝑈) are determined. In
fact, Equation (9.4) provides a means for determining Δ𝑈: Measure the energy transferred as heat and work to or from the
system. We can summarise the sign combinations as follows:

Sign Conventions for q and w of the System

Energy transferred as . . . Sign Convention Effect on Usystem
Heat to the system (endothermic) q>0 (+) U increases
Heat from the system (exothermic) q<0 (−) U decreases
Work done on the system w >0 (+) U increases
Work done by the system w <0 (−) U decreases

In this module we will specifically look at 𝑝–𝑉 work (pressure-volume work). Which means we look at the work of systems in
terms of pressure and volume changes.

For example, if a gas expands against a constant external pressure, we can calculate the work as follows:

𝑤 = −𝑝Δ𝑉 (9.5)

A Closer Look 9.1: p–V Work

The example of a gas sealed in a cylinder with a movable piston can be used to understand the work done by
a system on its surroundings (or vice versa) when the volume of a system changes. If the gas in the cylinder is
heated, it expands, pushing the piston upward until the internal gas pressure equals the (constant) downward
external pressure applied by the piston and the atmosphere (see figure). Ideally, the piston moves without friction,
so that none of the work done by an expanding gas is lost to heating the cylinder walls. When the gas is heated, it
expands and pushes the piston upward. This shows the gas doing work on its surroundings. If the piston moves
smoothly (without friction), no energy is wasted. The work required to move the piston is found using the formula
:
work = force × distance

Pressure is force ÷ area, so we can also write that work = pressure × change in volume
(Δ𝑉 = 𝑉final − 𝑉initial ), or what you should recognise as:

𝑤 = −𝑝Δ𝑉

The minus sign means the system loses energy when it does work on the
surroundings (like pushing the piston up). This formula works when the pressure
stays the same. If the pressure changes, the calculation is more complex.

39 University of Pretoria | Department of Chemistry

9.5 The First Law of Thermodynamics CMY 117 | General Chemistry

Equation (9.5) implies a few important facts. The first is that in a constant-volume process, Δ𝑉 = 0. This means the energy
transferred as work will also be zero. Thus, the change in internal energy of the system under constant-volume conditions is
equal only to the energy transferred as heat (𝑞𝑉 ). The subscript 𝑉 indicates conditions of constant volume:

Example 9.5
Energy and Work
Nitrogen gas (1.50 L) is confined in a cylinder under constant atmospheric pressure (1.01×105 pascals). The gas expands
to a volume of 2.18 L when 882 J of energy is transferred as heat from the surroundings to the gas. What is the change
in the internal energy of the gas?

Solution to be discussed during lecture period

9.5.1 Enthalpy

Most experiments in a chemical laboratory are carried out in beakers or flasks open to the atmosphere, where the external
pressure is constant. Hence it could be handy to have some parameter that describes processes in these terms.

Under conditions of constant pressure,

University of Pretoria | Department of Chemistry 40

CMY 117 | General Chemistry 9.6 Enthalpy and Chemical Reactions

For a system where the only type of work possible is p–V work, the change in enthalpy is Δ𝐻, which is equal to the energy
transferred as heat at constant pressure, 𝑞𝑝 . The sign of Δ𝐻 indicates the directionality of energy transfer as heat (under
conditions of constant pressure). We can summarise the meaning of the sign as follows:

▷ Negative values of Δ𝐻: energy is transferred as heat from the system to the surroundings (exothermic process).

▷ Positive values of Δ𝐻: energy is transferred as heat from the surroundings to the system (endothermic process).

9.5.2 What is a State Function?

Internal energy and enthalpy share a significant characteristic – namely, changes in these quantities depend only on the initial
and final states. They do not depend on the path taken going from the initial state to the final state. No matter how a reaction
proceeds from reactants to products, the values of Δ𝐻 and Δ𝑈 are always the same. A quantity that has this property is called
a state function.

Functions that depend on the path taken, for example, work and heat. Depending on how the heat is added or how the work
is done, these values change. However, interestingly, their sum is a state function again, Δ𝑈 = 𝑤 + 𝑞.

9.6 Enthalpy and Chemical Reactions

Learning Outcomes for This Section: Enthalpy and Chemical Reactions

What is our aim for this section?

▷ Understand and use the enthalpy change for the conversion of reactants to products in their standard states,
Δr 𝐻 −∘ .

A chemical reaction leads to a change in enthalpy. We call this the standard reaction enthalpy, Δr 𝐻 −∘ .

There are two important things to know about Δr 𝐻 −∘ .

1. The standard enthalpy change, Δr 𝐻 −∘ , refers to the heat change when pure, unmixed reactants in their standard states
form pure, unmixed products, also in their standard states. A substance’s standard state is its most stable form at 1 bar
pressure (1 × 105 Pa) and a specified temperature.

2. The “per mol-rxn” designation in the units for Δr 𝐻 −∘ means that this is the enthalpy change for a mole of reaction (where
rxn is an abbreviation for reaction). One mole of reaction takes place when a chemical reaction occurs in exactly the
amounts specified by the coefficients of the balanced chemical equation.

Furthermore, for the enthalpy change of reaction:

▷ Enthalpy changes are specific to the reaction being carried out. The identities of reactants and products, and their states
(s, l, g), are important, as are the amounts of reactants and products.

▷ The enthalpy change depends on the number of moles of reaction, that is, the number of times the reaction as written is
carried out.

▷ Δr 𝐻 −∘ has a negative value for an exothermic reaction; it has a positive value for an endothermic reaction.

▷ Values of Δr 𝐻 −∘ are numerically the same, but opposite in sign, for chemical reactions that are the reverse of each other.

41 University of Pretoria | Department of Chemistry

9.7 Calorimetry CMY 117 | General Chemistry

Example 9.6
Calculating the Enthalpy Change for a Reaction
Sucrose (table sugar, C12 H22 O11 ) can be oxidized to CO2 and H2 O, and the enthalpy change for the reaction can be
measured.
−1
C12 H22 O11 (𝑠) + 12 O2 (𝑔) −−−→ 12 CO2 (𝑔) + 11 H2 O(𝑙) Δr 𝐻 −∘ = −5645kJ ⋅ mol-rxn

What is the enthalpy change when 5.00 g of sugar is burned under conditions of constant pressure?

Solution to be discussed during lecture period

9.7 Calorimetry

Learning Outcomes for This Section: Calorimetry

What is our aim for this section?

▷ Describe how to measure and calculate the quantity of energy transferred as heat in a reaction by calorimetry.

The energy evolved or absorbed as heat in a chemical or physical process can be

measured by calorimetry. The apparatus used in this kind of experiment is a
calorimeter.

9.7.1 Measuring Enthalpy Using Calorimetry

A constant-pressure calorimeter can be used to measure the quantity of energy

transferred as heat under constant-pressure conditions, that is, the enthalpy change
for a chemical reaction.
Figure 9.3: Coffee-cup calorimeter
In this situation, we define the chemicals and the solution as the system. The cup and everything beyond the cup are assumed
that there is no energy transfer to the cup or beyond, the energy is transferred only as heat within the system.

University of Pretoria | Department of Chemistry 42

CMY 117 | General Chemistry 9.7 Calorimetry

Two energy changes occur within the system. One is the energy released or gained as heat by the chemical reaction (𝑞r ) itself
(any energy absorbed or released by the reaction). The other energy change is the corresponding energy gained or lost as heat
by the solution. Hence, by the law of conservation of energy: We will normally solve for 𝑞r in this equation.

Example 9.7
Using a Coffee-Cup Calorimeter
You place 0.0500 g of magnesium chips in a coffee-cup calorimeter and then add 100.0 mL of 1.00 M HCl. The reaction
that occurs is
Mg(𝑠) + 2 HCl(𝑎𝑞) −−−→ H2 (𝑔) + MgCl2 (𝑎𝑞)

The solution’s temperature increases from 22.21 °C (295.36 K) to 24.46 °C (297.61 K). What is the enthalpy change for
the reaction per mole of Mg? Assume that the solution’s specific heat capacity is 4.20 J ⋅ g−1 ⋅ K−1 , the density of the
HCl solution is 1.00 g⋅mL−1 , and no energy as heat is lost to the surroundings.

Solution to be discussed during lecture period

9.7.2 Measuring Internal Energy Using Calorimetry

Constant-volume calorimetry is often used to evaluate the energy released by the

combustion of fuels and the caloric value of foods. A weighed sample of a combustible
solid or liquid is placed inside a bomb, often a cylinder about the size of a large fruit
juice can with thick steel walls and ends (Figure 9.4).

The heat generated by the combustion reaction warms the system, which is the bomb,
its contents, and the water. Assessment of energy transfers as heat within the system
shows that
𝑞r + 𝑞bomb + 𝑞water = 0 Figure 9.4: Bomb caliometer

where 𝑞r is the energy released as heat by the reaction, 𝑞bomb is the energy involved in heating the calorimeter bomb, and 𝑞water
is the energy involved in heating the water in the calorimeter.

43 University of Pretoria | Department of Chemistry

9.7 Calorimetry CMY 117 | General Chemistry

Because the volume does not change in a constant-volume calorimeter, energy transfer as work does not occur. Therefore, the
energy transferred as heat at constant volume (𝑞𝑉 ) is equal to the change in internal energy, Δ𝑈.

Example 9.8
Constant-Volume Calorimetry
Octane, C8 H18 , a primary constituent of gasoline, burns in air

25
C8 H18 (𝑙) + O −−−→ 8 CO2 (𝑔) + 9 H2 O(𝑙)
2 2 (𝑔)

A 1.15-g sample of octane is burned in a constant-volume calorimeter similar to that shown in Figure 9.4. The
calorimeter is in an insulated container with 1.20 kg of water. The temperature of the water and the bomb rises from
25.00 °C (298.15 K) to 34.43 °C (307.58 K). The heat required to raise the bomb’s temperature (its heat capacity), 𝐶bomb ,
is 837 J⋅K−1 . (a) What is the heat of combustion per gram of octane? (b) What is the heat of combustion per mole of
octane?

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 44

CMY 117 | General Chemistry 9.8 Enthalpy Calculations

9.8 Enthalpy Calculations

Learning Outcomes for This Section: Enthalpy Calculations

What are our aims for this section?

▷ Apply Hess’s law to find the enthalpy change for a reaction.

▷ Know how to draw and interpret energy level diagrams.

▷ Use standard molar enthalpies of formation, Δf 𝐻 −∘ , to calculate the standard enthalpy change for a reaction,
Δr 𝐻 −∘ .

Chemists and chemical engineers often want to know if a reaction is expected to be exothermic or endothermic and to what
extent. We can do this using data on other reactions and combining them.

9.8.1 Hess’s Law

The calculations in this section is based on Hess’s law, which states that if a reaction is the sum of two or more other reactions,
Δr 𝐻 −∘ for the overall process is the sum of the Δr 𝐻 −∘ values of those reactions.

Example 9.9
Using Hess’s Law
Suppose you want to know the enthalpy change for the formation of methane, CH4 , from solid carbon (as graphite)
and hydrogen gas:
C(𝑠) + 2 H2 (𝑔) −−−→ CH4 (𝑔) Δr 𝐻 −∘ = ?

The enthalpy change for this reaction cannot be measured in the laboratory because the reaction is very slow. However,
the enthalpy changes can be measured for the combustion of carbon, hydrogen, and methane.

−1
Equation 1: C(𝑠) + O2 (𝑔) −−−→ CO2 (𝑔) Δr 𝐻1−∘ = −393.5 kJ ⋅ mol-rxn
1 −1
Equation 2: H2 (𝑔) + O2 (𝑔) −−−→ H2 O(𝑙) Δr 𝐻2−∘ = −285.8 kJ ⋅ mol-rxn
2
−1
Equation 3: CH4 (𝑔) + 2 O2 (𝑔) −−−→ CO2 (𝑔) + 2 H2 O(𝑙) Δr 𝐻3−∘ = −890.3 kJ ⋅ mol-rxn

Solution to be discussed during lecture period

Lorem ipsum dolor sit amet, consectetuer adipiscing elit. Ut purus elit, vestibulum ut, placerat ac, adipiscing vitae,
felis. Curabitur dictum gravida mauris. Nam arcu libero, nonummy eget, consectetuer id, vulputate a, magna. Donec
vehicula augue eu neque. Pellentesque habitant morbi tristique senectus et netus et malesuada fames ac turpis egestas.
Mauris ut leo. Cras viverra metus rhoncus sem. Nulla et lectus vestibulum urna fringilla ultrices. Phasellus eu tellus
sit amet tortor gravida placerat. Integer sapien est, iaculis in, pretium quis, viverra ac, nunc. Praesent eget sem vel leo
ultrices bibendum. Aenean faucibus. Morbi dolor nulla, malesuada eu, pulvinar at, mollis ac, nulla. Curabitur auctor
semper nulla. Donec varius orci eget risus. Duis nibh mi, congue eu, accumsan eleifend, sagittis quis, diam. Duis eget
orci sit amet orci dignissim rutrum. Nam dui ligula, fringilla a, euismod sodales, sollicitudin vel, wisi. Morbi auctor
lorem non justo. Nam lacus libero, pretium at, lobortis vitae, ultricies et, tellus. Donec aliquet, tortor sed accumsan
bibendum, erat ligula aliquet magna, vitae ornare odio metus a mi. Morbi ac orci et nisl hendrerit mollis. Suspendisse
ut massa. Cras

45 University of Pretoria | Department of Chemistry

9.8 Enthalpy Calculations CMY 117 | General Chemistry

Lorem ipsum dolor sit amet, consectetuer adipiscing elit. Ut purus elit, vestibulum ut, placerat ac, adipiscing vitae,
felis. Curabitur dictum gravida mauris. Nam arcu libero, nonummy eget, consectetuer id, vulputate a, magna. Donec
vehicula augue eu neque. Pellentesque habitant morbi tristique senectus et netus et malesuada fames ac turpis egestas.
Mauris ut leo. Cras viverra metus rhoncus sem. Nulla et lectus vestibulum urna fringilla ultrices. Phasellus eu tellus
sit amet tortor gravida placerat. Integer sapien est, iaculis in, pretium quis, viverra ac, nunc. Praesent eget sem vel leo
ultrices bibendum. Aenean faucibus. Morbi dolor nulla, malesuada eu, pulvinar at, mollis ac, nulla. Curabitur auctor
semper nulla. Donec varius orci eget risus. Duis nibh mi, congue eu, accumsan eleifend, sagittis quis, diam. Duis eget
orci sit amet orci dignissim rutrum. Nam dui ligula, fringilla a, euismod sodales, sollicitudin vel, wisi. Morbi auctor
lorem non justo. Nam lacus libero, pretium at, lobortis vitae, ultricies et, tellus. Donec aliquet, tortor sed accumsan
bibendum, erat ligula aliquet magna, vitae ornare odio metus a mi. Morbi ac orci et nisl hendrerit mollis. Suspendisse
ut massa. Cras

University of Pretoria | Department of Chemistry 46

CMY 117 | General Chemistry 9.8 Enthalpy Calculations

Figure 9.5: Energy level diagrams. (a) Relating enthalpy changes in the formation of CO2 (g) . (b) Relating enthalpy changes
in the formation of H2 O(l) . Enthalpy changes associated with changes between energy levels are given alongside the vertical
arrows.

9.8.2 Energy Level Diagrams

When using Hess’s law, it is often helpful to represent enthalpy data schematically in an energy level diagram. In such drawings,
the various substances being studied, the reactants and products in a chemical reaction, for example, are placed on an arbitrary
energy scale. Examples are shown in Figure 9.5.

The relative enthalpy of each is given by its position on the vertical axis, and numerical differences in enthalpy between them
are shown by vertical arrows. Such diagrams can give you a visual perspective of the magnitude and direction of enthalpy
changes and show how the enthalpies of the substances are related.

The enthalpy change for a reaction is a state function; that is, the enthalpy change from reactants to products does not
depend on the path taken. Energy diagrams illustrate this point. Chemists often want to know the enthalpy change for one
step of a reaction. If the overall enthalpy change and the enthalpy changes for all the steps but one are known, then the
unknown change can be calculated.

9.8.3 Standard Enthalpies of Formation

The standard molar enthalpy of formation, Δf 𝐻 −∘ , is the enthalpy change for the formation of 1 mol of a compound directly
from its component elements in their standard states.

47 University of Pretoria | Department of Chemistry

9.8 Enthalpy Calculations CMY 117 | General Chemistry

Hence the reaction equations used here must be in terms of one mole of the product to be applicable. Furthermore, the enthalpy
of formation of a compound does not necessarily correspond to a reaction that can be carried out.

If we review some common formation enthalpy values like in Appendix L of the textbook, we can make a few observations:

▷ The standard enthalpy of formation for an element in its standard state is zero.

▷ Most Δf 𝐻 −∘ values are negative, indicating that the formation of most com-pounds from their elements is exothermic.
Very few values are positive, and these represent compounds that are unstable with respect to decomposition to the
elements.

▷ Values of Δf 𝐻 −∘ can often be used to compare the stabilities of related compounds.

9.8.4 Enthalpy Change of Reaction

Using standard molar enthalpies of formation and Equation (9.6), it is possible to calculate the enthalpy change for a reaction
under standard conditions.
Δr 𝐻 −∘ = ∑ 𝑛𝑖 Δf 𝐻 −∘ (products) − ∑ 𝑛𝑖 Δf 𝐻 −∘ (reactants) (9.6)
𝑖 𝑖

Example 9.10
Using Enthalpies of Formation
Nitroglycerin, C3 H5 (NO3 )3 , is a powerful explosive that forms four different gases when detonated:

1
2 C3 H5 (NO3 )3 (𝑙) −−−→ 3 N2 (𝑔) + O + 6 CO2 (𝑔) + 5 H2 O(𝑔)
2 2 (𝑔)

Calculate the enthalpy change that occurs when 10.0 g of nitroglycerin is detonated. The standard enthalpy of formation
−1
of nitroglycerin, Δf 𝐻 −∘ , is −364 kJ ⋅ mol . Use Appendix L in your textbook to find other Δf 𝐻 −∘ values that are needed.

Solution to be discussed during lecture period

Lorem ipsum dolor sit amet, consectetuer adipiscing elit. Ut purus elit, vestibulum ut, placerat ac, adipiscing vitae,
felis. Curabitur dictum gravida mauris. Nam arcu libero, nonummy eget, consectetuer id, vulputate a, magna. Donec
vehicula augue eu neque. Pellentesque habitant morbi tristique senectus et netus et malesuada fames ac turpis egestas.
Mauris ut leo. Cras viverra metus rhoncus sem. Nulla et lectus vestibulum urna fringilla ultrices. Phasellus eu tellus
sit amet tortor gravida placerat. Integer sapien est, iaculis in, pretium quis, viverra ac, nunc. Praesent eget sem vel leo
ultrices bibendum. Aenean faucibus. Morbi dolor nulla, malesuada eu, pulvinar at, mollis ac, nulla. Curabitur auctor
semper nulla. Donec varius orci eget risus. Duis nibh mi, congue eu, accumsan eleifend, sagittis quis, diam. Duis eget
orci sit amet orci dignissim rutrum. Nam dui ligula, fringilla a, euismod sodales, sollicitudin vel, wisi. Morbi auctor
lorem non justo. Nam lacus libero, pretium at, lobortis vitae, ultricies et, tellus. Donec aliquet, tortor sed accumsan
bibendum, erat ligula aliquet magna, vitae ornare odio metus a mi. Morbi ac orci et nisl hendrerit mollis. Suspendisse
ut massa. Cras

University of Pretoria | Department of Chemistry 48

CMY 117 | General Chemistry 9.8 Enthalpy Calculations

Lorem ipsum dolor sit amet, consectetuer adipiscing elit. Ut purus elit, vestibulum ut, placerat ac, adipiscing vitae,
felis. Curabitur dictum gravida mauris. Nam arcu libero, nonummy eget, consectetuer id, vulputate a, magna. Donec
vehicula augue eu neque. Pellentesque habitant morbi tristique senectus et netus et malesuada fames ac turpis egestas.
Mauris ut leo. Cras viverra metus rhoncus sem. Nulla et lectus vestibulum urna fringilla ultrices. Phasellus eu tellus
sit amet tortor gravida placerat. Integer sapien est, iaculis in, pretium quis, viverra ac, nunc. Praesent eget sem vel leo
ultrices bibendum. Aenean faucibus. Morbi dolor nulla, malesuada eu, pulvinar at, mollis ac, nulla. Curabitur auctor
semper nulla. Donec varius orci eget risus. Duis nibh mi, congue eu, accumsan eleifend, sagittis quis, diam. Duis eget
orci sit amet orci dignissim rutrum. Nam dui ligula, fringilla a, euismod sodales, sollicitudin vel, wisi. Morbi auctor
lorem non justo. Nam lacus libero, pretium at, lobortis vitae, ultricies et, tellus. Donec aliquet, tortor sed accumsan
bibendum, erat ligula aliquet magna, vitae ornare odio metus a mi. Morbi ac orci et nisl hendrerit mollis. Suspendisse
ut massa. Cras

49 University of Pretoria | Department of Chemistry

9.9 What Can Thermodynamics Help Predict? CMY 117 | General Chemistry

9.9 What Can Thermodynamics Help Predict?

Learning Outcomes for This Section: What Can Thermodynamics Help Predict?

What is our aim for this section?

▷ To understand what thermodynamic quantities can predict regarding reactions.

An extensive study of thermodynamics will ultimately provide answers to four questions:

1. How do you measure and calculate the energy changes associated with physical changes and chemical reactions?

2. What is the relationship between energy changes, heat, and work?

3. How can you determine whether a chemical reaction is product-favored or reactant-favored at equilibrium?

4. How can you determine whether a chemical reaction or physical process will occur spontaneously, that is, without
outside intervention?

Reactions in which reactants are largely converted to products when equilibrium is reached are called product-favored at
equilibrium. Reactions in which only small amounts of products are present at equilibrium are called reactant-favored at
equilibrium.

A common misconception is that all exothermic reactions are product-favored at equilibrium and all endothermic reactions
are reactant-favored at equilibrium. From all our examples, you might formulate that idea as a hypothesis that can be tested
by experiment and by examination of other examples.

You would find that in most cases, product-favored reactions have negative values of Δr 𝐻 −∘ , and reactant-favored reactions have
positive values of Δr 𝐻 −∘ . But this is not always true; there are exceptions! The reasons behind these observations is left for
Theme 4 in CMY 127.

University of Pretoria | Department of Chemistry 50

CMY 117 | General Chemistry 9.10 Additional Practice Problems

9.10 Additional Practice Problems

Here I list some additional practice problems for you to do at home. The solutions to these problems are provided in the video
content on YouTube.

Heat Transfer Processes

An architect evaluates different materials to act as heat-absorbing panels for the design of a solar-heated home. To do this, they
must evaluate the temperature change of several materials subjected to the same amount of solar energy.

(a) Calculate the minimum quantity of thermal energy transfer that is required to increase the temperature of 45.0 kg of
granite by 15.0 °C. (The specific heat capacity of granite is 0.810 J ⋅ g−1 ⋅ K−1 )

(b) Calculate the temperature change of 45.0 kg of iron if it stores the same amount of energy as the granite. (The specific
heat capacity of iron is 0.449 J ⋅ g−1 ⋅ K−1 )

(c) Calculate the temperature change of 45.0 kg of water if it stores the same amount of energy as the granite. (The specific
heat capacity of water is 4.184 J ⋅ g−1 ⋅ K−1 )

Heat Transfer In a Closed System

An insulated container holds 100.0 mL of H2 O at 20.0 °C. Suppose a 55.0 g cube of copper is heated to 425 °C. The metal is
added to the water and the temperature of the ’combination’ is recorded until thermal equilibrium is reached. What is the
temperature of the water and the copper at this point? The specific heat of water is 4.184 J ⋅ g−1 ⋅ K−1 and the molar heat
−1
capacity of the copper is 24.46 J ⋅ mol ⋅ K−1 . You may assume that the density of water is exactly 1 g ⋅ mL−1 .

Phase Changes and Energy

An athlete has just finished running a marathon. Compare the cooling effect on the body when (i) 100.0 mL of water evaporates
during perspiration (sweating) versus (ii) drinking 100.0 mL cold water at 5.00 °C (the water is assumed to warm up to body
temperature, 37.5 °C). The specific heat of water is 4.184 J ⋅ g−1 ⋅ K−1 and the heat of vaporisation is 2256 J ⋅ g−1 . Assume that
the density of water is exactly 1 g ⋅ mL−1 .

Energy Needed in Phase Changes

Calculate the energy needed to convert 72.0 g of ice at −10.0 °C to steam at 120.0 °C. You may assume that ‘heating’ is the only
cause of energy transfer between the water and the surroundings. Assume that the density of water is exactly 1 g⋅mL−1 .

The First Law

A certain gas confined to a cylinder with a moving piston, expands in volume from 2.0 L to 6.0 L at constant pressure. This
occurs because the gas is heated with the addition of 128 J. Determine the change in internal energy (Δ𝑈) for this process if

(i) The gas expands against a pressure of 1.2 atm.

(ii) The gas expands against a vacuum.

51 University of Pretoria | Department of Chemistry

9.10 Additional Practice Problems CMY 117 | General Chemistry

Heating a Substance

The dimensions of a swimming pool are 43.3 m by 13.3 m by 4.39 m. The water in the pool is equal to 92.0% of this volume.
The owner of the pool wishes to heat the water from 26.4 °C to 33.3 °C. This can be done by using the heat transfer from the
combustion of propane gas. How many grams of propane will be required to heat the water in this manner? Assume that no
other energy transfer occurs and that the transfer process is 100% efficient.

Given:
−1
C3 H8 (𝑔) + 5 O2 (𝑔) −−−→ 3 CO2 (𝑔) + 4 H2 O(𝑙) Δr 𝐻 −∘ = −2220 kJ ⋅ mol-rxn

The specific heat and density of water is 4.184 J⋅g−1 ⋅K−1 and 1 g⋅mL−1 .

Heat of Reaction

The reaction of iron metal with oxygen in air leads to the production of iron(III) oxide. This forms the basis of a ‘hot pack’
used by an athlete to warm tired muscles after exercise. How much ‘heating’ can be provided by a hot pack that contains 0.100
pounds of iron metal? Assume no other energy transfer occurs.
−1
Given: Δr 𝐻 −∘ = −824.2 kJ ⋅ mol-rxn , 1 lb = 454 g.

Constant Pressure Caliometry – Coffee-Cup Caliometry

30.0 mL of 0.700 M NaOH is placed in a coffee-cup calorimeter. To this is added 25.0 mL of 0.600 M HCl. The reaction that
occurs is:
NaOH(𝑎𝑞) + HCl(𝑎𝑞) −−−→ NaCl(𝑎𝑞) + H2 O(𝑙)

The temperature of the reaction mixture was measured and found to have changed from 23.4 °C to 30.4 °C. What is the (molar)
enthalpy change for the reaction in kJ⋅mol−1 ? Assume that the specific heat and density of the solution is the same as that of
water, namely 4.184 J ⋅ g−1 ⋅ K−1 and 1.00 g ⋅ mL−1 , respectively.

Constant Volume Caliometry – Bomb Caliometry

−1
A 3.30 g sample of glucose, C6 H12 O6 , (molar mass = 180.16 g ⋅ mol ) was combusted in a bomb calorimeter to form carbon
dioxide and water. The temperature of the bomb and the water changed from 22.4 °C to 34.1 °C. If the calorimeter contained
850. g of water and the bomb had a heat capacity of 874 J ⋅ °𝐶 −1 , determine the internal energy change for 1 mol of glucose.
The specific heat of water is 4.184 J ⋅ g−1 ⋅ K−1 .

Hess’s Law and Enthalpy of Reaction

Determine the standard enthalpy of reaction for the production of propane gas:

3 C(𝑠) + 4 H2 (𝑔) −−−→ C3 H8 (𝑔)

Given

C3 H8 (𝑔) + 5 O2 (𝑔) −−−→ 3 CO2 (𝑔) + 4 H2 O(𝑙) Δr 𝐻 −∘ = −2220 kJ

C(𝑠) + O2 (𝑔) −−−→ CO2 (𝑔) Δr 𝐻 −∘ = −393.5 kJ
1
H2 (𝑔) + O −−−→ H2 O(𝑙) Δr 𝐻 −∘ = −285.5 kJ
2 2 (𝑔)

University of Pretoria | Department of Chemistry 52

CMY 117 | General Chemistry 9.10 Additional Practice Problems

Enthalpy Change of Reaction

Determine the enthalpy change that occurs when 65.14 g of ethyne (C2 H2 , Molar Mass = 26.04 g⋅mol−1 ) reacts with oxygen in
a welding torch. Use the relevant data from the Tables in your textbook.

Enthalpy of Formation

Calculate the enthalpy of reaction for

2 N2 (𝑔) + 5 O2 (𝑔) −−−→ 2 N2 O5 (𝑔)
−1 −1
Given Δf 𝐻 −∘ (H2 O(𝑙) ) = −285.8 kJ ⋅ mol , Δf 𝐻 −∘ (HNO3 (𝑙) ) = −174.1 kJ ⋅ mol , and that

−1
N2 O5 (𝑔) + H2 O(𝑙) −−−→ 2 HNO3 (𝑙) Δr 𝐻 −∘ = −76.6 kJ ⋅ mol

53 University of Pretoria | Department of Chemistry

 Theme
The Properties of Gasses
10 Click Here to access this Theme’s YouTube Playlist

10.1 Introduction

Of the three states of matter, gas behaviour is the easiest to understand when viewed at the molecular level, and as a result, gases
are well understood. It is possible to describe the properties of gases qualitatively in terms of the behaviour of the molecules
that make up the gas. It is also possible to describe the properties of gases quantitatively using fairly simple mathematical
models. One objective of scientists is to develop models of natural phenomena, and a study of gas behaviour will introduce
you to this approach.

10.2 How Do We Model Gasses and Gas Pressure?

Learning Outcomes for This Section: How Do We Model Gasses and Gas Pressure?

What is our aim for this section?

▷ Describe how pressure measurements are made and the units of pressure, especially atmospheres (atm) and
millimetres of mercury (mm Hg).

A remarkably accurate description of most gases requires knowing only four quantities: the pressure (𝑃), volume (𝑉 ), temperature
(𝑇, kelvins), and amount (𝑛) of the gas. Pressure is the force exerted on an object divided by the area over which it is exerted.

Pressure is often reported in units of millimetres of mercury (mm Hg), the height (in mm) of the mercury column in a
mercury barometer above the surface of the mercury in the dish. At sea level, this height is about 760 mm. Pressures are also
reported as standard atmospheres (atm), a unit defined as follows:

1 standard atmosphere (1 atm) = 760 mm Hg (exactly)

The SI unit of pressure is the pascal (Pa). However, the pascal is quite small relative to normal measured pressures, hence
kilopascal is more often used, kPa. Another unit is the bar, where 1 bar = 100000 Pa = 100 kPa.

We can summarise all the units for pressure as follows:

1 atm = 760 mm Hg (exactly) = 101.325 kilopascals (kPa) = 1.01325 bar

and

1 bar = 1 × 105 Pa (exactly) = 1 × 102 kPa = 0.98692 atm

54
CMY 117 | General Chemistry 10.3 Gas Laws: The Experimental Basis

A Closer Look 10.1: Measuring Gas Pressure

In the laboratory, the pressure of a gas is often measured with a U-tube manometer (see figure). The closed side
of the tube has been evacuated so that no gas remains to exert pressure on the mercury on that side. The other
side is open to the gas whose pressure you want to measure. When the gas presses on the mercury in the open
side, the gas pressure is read directly (in mm Hg) as the difference in mercury levels on the closed and open sides.

Outside the laboratory, you may have used a tire gauge to

check the pressure in your car or bike tires. In the United
States, such gauges usually indicate the pressure in pounds
per square inch (psi) where 1 atm = 14.7 psi. Some gauges give
the pressure in kilopascals as well. Be sure to recognize that
the reading on the scale of a tire gauge refers to the pressure
in excess of atmospheric pressure. (A flat tire is not a vacuum;
it contains air at atmospheric pressure.) For example, if the
gauge reads 35 psi (2.4 atm), the pressure in the tire is actually
about 50 psi or 3.4 atm.

Example 10.1
Pressure Unit Conversions
Convert a pressure of 635 mm Hg into its corresponding value in units of atmospheres (atm), bars, and kilopascals
(kPa).

Solution discussed in Video Lecture

10.3 Gas Laws: The Experimental Basis

This section is seen as self-study since it formed part of the Grade 12 curriculum. Kindly see your textbook Section 10.2 for the full
details and information on this section. Ensure that you understand the basis of the gas laws (Boyle’s law, Charles’s law, Avogadro’s
hypothesis) and know how to use those laws.

55 University of Pretoria | Department of Chemistry

10.4 The Ideal Gas Law CMY 117 | General Chemistry

10.4 The Ideal Gas Law

Learning Outcomes for This Section: The Ideal Gas Law

What are our aims for this section?

▷ Understand the origin of the ideal gas law and how to use the equation.

▷ Relate gas density to molar mass, pressure, and temperature.

▷ Calculate the molar mass of a compound from the pressure of a known quantity of a gas in a given volume at
a known temperature.

From your self-study, you should know that four interrelated quantities can be used to describe a gas: pressure, volume,
temperature, and amount (moles), i.e.:

Boyle’s Law Charles’s Law Avogadro’s Hypothesis

𝑉 ∝ 1/𝑝 𝑉∝𝑇 𝑉∝𝑛
constant T, n constant p, n constant T, p

If we combine all three laws we see that:

𝑛𝑇
𝑉∝
𝑝

Typically what we do in mathematics at this point is if things are proportional to each other, we can write the = sign if we
introduce some proportionality constant, let’s call this 𝑅. This constant, which is called the gas constant, is a number used to
interrelate the properties of any gas:
𝑛𝑇
𝑉 = 𝑅( ) ⇒ 𝑝𝑉 = 𝑛𝑅𝑇 (10.1)
𝑝
The equation 𝑃𝑉 = 𝑛𝑅𝑇 is called the ideal gas law. It describes the behaviour of a so-called ideal gas. There are no ideal
gasses, but the law holds under certain conditions for most gasses.

The value of 𝑅 is determined experimentally and can be confirmed by doing a calculation at STP (standard temperature and
pressure).

Example 10.2
Ideal Gas Law
The nitrogen gas in an automobile airbag, with a volume of 65 L, exerts a pressure of 829 mm Hg at 25 °C. What amount
of N2 gas (in moles) is in the airbag?

Solution discussed in Video Lecture

University of Pretoria | Department of Chemistry 56

CMY 117 | General Chemistry 10.4 The Ideal Gas Law

10.4.1 The Density of a Gas

𝑚
We know to calculate the moles of a substance we use 𝑛 = , where 𝑚 is the mass and 𝑀 is the substance’s molar mass. If we
𝑀
use this for 𝑛 in Equation (10.1), we can write

𝑚 𝑚 𝑝𝑀
𝑝𝑉 = ( ) 𝑅𝑇 ⇒ =
𝑀 𝑉 𝑅𝑇

What is 𝑚/𝑉 ? It is of course the density of the gas! So, we call 𝑚/𝑉 = 𝑑, as so

𝑝𝑀
𝑑= (10.2)
𝑅𝑇

Example 10.3
Density and Molar Mass
Calculate the density (in units of g⋅L−1 ) of CO2 at STP.

Solution discussed in Video Lecture

10.4.2 We can Calculate the Molar Mass of a Gas from P, V, and T Data

When a new compound is isolated in the laboratory, one of the first things chemists often do is determine its molar mass. If
the compound is easily volatilized, a classical method of determining the molar mass is to measure the pressure and volume
exerted by a given mass of the gas at a given temperature.

Example 10.4
Calculating the Molar Mass of a Gas from P, V, and T Data
By experiment, you are trying to determine the formula of a gaseous compound you made to replace
chlorofluorocarbons in air conditioners. You have determined that the empirical formula is CHF2 , but you need to
know the molar mass to determine the molecular formula. You find that a 0.100-g sample of the compound exerts
a pressure of 70.5 mm Hg in a 256-mL container at 22.3 °C. What is the molar mass of the compound? What is its
molecular formula?

Solution to be discussed during lecture period Lorem ipsum dolor sit amet, consectetuer adipiscing elit. Ut purus elit,
vestibulum ut, placerat ac, adipiscing vitae, felis. Curabitur dictum gravida mauris. Nam arcu libero, nonummy eget,
consectetuer id, vulputate a, magna. Donec vehicula augue eu neque. Pellentesque habitant morbi tristique senectus et
netus et malesuada fames ac turpis egestas. Mauris ut leo. Cras viverra metus rhoncus sem. Nulla et lectus vestibulum
urna fringilla ultrices. Phasellus eu tellus sit amet tortor gravida placerat. Integer sapien est, iaculis in, pretium quis,
viverra ac, nunc. Praesent eget sem vel leo ultrices bibendum. Aenean faucibus. Morbi dolor nulla, malesuada eu,
pulvinar at, mollis ac, nulla. Curabitur auctor semper nulla. Donec varius orci eget risus. Duis nibh mi, congue eu,
accumsan eleifend, sagittis quis, diam. Duis eget orci sit amet orci dignissim rutrum.

57 University of Pretoria | Department of Chemistry

10.4 The Ideal Gas Law CMY 117 | General Chemistry

Noom

University of Pretoria | Department of Chemistry 58

CMY 117 | General Chemistry 10.5 Gas Laws and Chemical Reactions

10.5 Gas Laws and Chemical Reactions

Learning Outcomes for This Section: Gas Laws and Chemical Reactions

What is our aim for this section?

▷ Apply the gas laws to study the stoichiometry of reactions.

Many industrially important reactions involve gases. If you want to understand the quantitative aspects of such reactions, you
need to carry out stoichiometry calculations. The scheme in Figure 10.1 connects these calculations for gas reactions with
the stoichiometry calculations in Theme 8.

Figure 10.1: A scheme for stoichiometry calculations. Here, A and B may be either reactants or products. The amount of A
(mol) can be calculated from its mass in grams and its molar mass, from the concentration and volume of a solution, or from
p, V, and T data using the ideal gas law. Once the amount of B is determined, this value can be converted to a mass, solution
concentration, solution volume, or property of a gas.

Example 10.5
Gas Laws and Stoichiometry I
Hydrogen gas is produced from the reaction of lithium and water. What mass of lithium is required to produce 23.5 L
of H2 (𝑔) at 17.0 °C and a pressure of 743 mm Hg? The gas-producing reaction is

2 Li(𝑠) + 2 H2 O(𝑙) −−−→ 2 LiOH(𝑎𝑞) + H2 (𝑔)

Solution discussed in Video Lecture

59 University of Pretoria | Department of Chemistry

10.5 Gas Laws and Chemical Reactions CMY 117 | General Chemistry

Example 10.6
Gas Laws and Stoichiometry II
Hydrogen gas is generated when hydrochloric acid solution is added to solid zinc as follows:

2HCl(𝑎𝑞) + Zn(𝑠) −−−→ ZnCl2 (𝑎𝑞) + H2 (𝑔)

(a) How many grams of zinc is required to form 12.00 L of hydrogen gas at exactly 18 ∘ C and a pressure of 790 mmHg?

(b) How many litres of hydrogen gas will be formed (at 98.4 kPa and 300. K) when 25 mL of 0.112 M hydrochloric
acid is pipetted into a flask containing 15.6 g zinc?

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 60

CMY 117 | General Chemistry 10.6 What Happens When We Mix Ideal Gasses? – Partial Pressures

10.6 What Happens When We Mix Ideal Gasses? – Partial Pressures

Learning Outcomes for This Section: What Happens When We Mix Ideal Gasses? – Partial Pressures

What is our aim for this section?

▷ Master the use of Dalton’s law of partial pressures.

The air we all breathe is a mixture of nitrogen, oxygen, argon, carbon dioxide, water vapor, and small amounts of other gases.
Each of these gases exerts its own pressure, and atmospheric pressure is the sum of the pressures exerted by each gas. The
pressure of each gas in the mixture is called its partial pressure.

Dalton was the first to notice that if you sum the individual pressures of each gas you obtain the total pressure, hence why the
observation is called Dalton’s Law of Partial Pressures. Mathematically it states that

𝑝total = 𝑝A + 𝑝B + 𝑝C + … (10.3)

where 𝑝A , 𝑝B , and 𝑝C are the pressures of the different gases in a mixture, and 𝑝total is the total pressure.

Additionally, for a mixture of three ideal gases in a given volume (𝑉) and at a given temperature (𝑇), you can calculate the total
pressure if you know the total number of moles of gas in the system:

For mixtures of gases, it is convenient to introduce a quantity called the mole fraction, 𝑋, which is defined as the number of
moles of a particular substance in a mixture divided by the total number of moles of all substances present. Mathematically,
the mole fraction of a substance A in a mixture with B and C is expressed as

𝑛A 𝑛 𝑛A
𝑋A = = A ⇒ 𝑛total =
𝑛A + 𝑛 B + 𝑛 C 𝑛total 𝑋A

And so, combining our results, we find: Thus, the pressure of a gas in a mixture of gases is the product of its mole fraction

and the total pressure of the mixture. In other words, the partial pressure of a gas is directly related to the fraction of particles
of that gas in the mixture.

61 University of Pretoria | Department of Chemistry

10.6 What Happens When We Mix Ideal Gasses? – Partial Pressures CMY 117 | General Chemistry

Example 10.7
Partial Pressures of Gases
Halothane, C2 HBrClF3 , is a nonflammable, nonexplosive, and nonirritating gas that was widely used as an inhalation
anaesthetic. The total pressure of a mixture of 15.0 g of halothane vapour and 23.5 g of oxygen gas is 855 mm Hg. What
is the partial pressure of each gas?

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 62

CMY 117 | General Chemistry 10.7 Additional Practice Problems

10.7 Additional Practice Problems

Here I list some additional practice problems for you to do at home. The solutions to these problems are provided in the video
content on YouTube.

Charles’ Law

Using Charles’ Law answer the following questions:

(a) A certain gas occupies a volume of 35.5 L at 0 °C. Calculate the new volume at 63.78 °C.

(b) A certain gas has a temperature of 153.32 °F, occupying a volume of 864 L. Calculate the temperature when the volume
is reduced to 10.0 × 109 nL.

Gay-Lussac’s Law

The gas in an aerosol can is under a pressure of 3.00 atm at a temperature of 25.00 °C. The can will burst at a pressure of 11.3
atm. When the can is thrown into a fire, at what temperature ( in °C) will it burst?

Avogadro’s Law

An important reaction in the industrial manufacture of nitric acid is the following:

Pt, 850 ∘ C
4NH3 (𝑔) + 5 O2 (𝑔) −−−−−−→ 4 NO(𝑔) + 6 H2 O(𝑔)

(a) What volume of oxygen is required for complete reaction with 16.4 L of ammonia?

(b) What is the total volume of products formed?

Standard Temperature and Pressure (STP)

Determine the mass of gas present in 2.00 L of hydrogen at STP?

The Universal Gas Constant R

−1
Starting with 𝑅 = 0.082057 L ⋅ ⋅mol ⋅ K−1 , determine each of the other values of 𝑅 given in the data sheet.

Gas Stoichiometry

A 50.00 g sample of a mixture of NaCl and MgCO3 was heated and 10.0 L of CO2 was collected at a pressure of 755 torr and at
20.0 °C. How many grams of NaCl was present in the original sample?

Partial Pressure of Gasses

Diborane reacts with O2 to give boric oxide and water vapor:

B2 H6 (𝑔) + 3 O2 (𝑔) −−−→ B2 O3 (𝑠) + 3 H2 O(𝑔)

63 University of Pretoria | Department of Chemistry

10.7 Additional Practice Problems CMY 117 | General Chemistry

If you mix B2 H6 and O2 in the correct stoichiometric ratio, and if the total pressure of the mixture is 200.0 mm Hg, what are
the partial pressures of the gases?

Mixing Gasses

A 3.00 L flask containing nitrogen gas at 1.80 atm, and a 2.00 L flask containing hydrogen gas at 3.50 atm are connected via
glass tubing and a valve. The valve is then opened. Assuming no change in temperature, determine the total pressure of the
final mixture.

Gas Mixtures – Dry & Wet Gasses

A certain experiment generates 2.58 L of hydrogen gas, which is collected over water. Assume the temperature stays constant
at 20 °C. This occurs on a day when the atmospheric pressure is 98.60 kPa. Determine the volume of the ’dry’ collected gas
when it is at STP?

Gas Mixtures

A sample of solid KClO3 was heated in a test tube and the following complete decomposition occurred:

KClO3 (𝑠) −−−→ 2 KCl(𝑠) + 3 O2 (𝑔)

0.650 L of oxygen was collected under water at 22.0°°C and a total pressure of 754 torr. Under these conditions the vapour
pressure of water is 21 torr. Calculate the partial pressure of the gas and the mass of salt originally present.

University of Pretoria | Department of Chemistry 64

 Theme
Intermolecular Forces
11 Click Here to access this Theme’s YouTube Playlist

11.1 Introduction

The objective of this Theme is to help you understand the interactions between atoms, ions, and molecules at the particulate
level. Many properties of liquids and solids depend on the strength of these forces. You will find this Theme useful because
it explains many interesting properties of matter. Take water, for example. We will look to find an explanation for why water
both melts and boils at temperatures far greater than other molecules of similar size, why it dissolves many ionic compounds,
and why small drops of water form spheres. You will also learn why water is among the few materials for which the solid (in
the case of water: ice) has a lower density than the liquid.

11.2 States of Matter and Intermolecular Forces

Learning Outcomes for This Section: States of Matter and Intermolecular Forces

What is our aim for this section?

▷ Know what types of intermolecular forces exist and what molecular properties they can influence.

One reason we can use the ideal gas equation (𝑝𝑉 = 𝑛𝑅𝑇) is that it makes the assumption that there are no intermolecular
forces between the gas molecules. However, for liquids and solids this is not the case. The reason being is that in these more
condensed states the molecules are packed more closely together and hence their inter-attractive and repulsive forces start
playing a role.

Collectively, intermolecular attractive forces are called van der Waals forces; they include the attractive and repulsive forces
between

▷ molecules with permanent dipoles (dipole-dipole forces).

▷ polar molecules and non-polar ones (dipole–induced dipole forces, sometimes called Debye forces).

▷ non-polar molecules (induced dipole–induced dipole forces, also called London dispersion forces).

Though intermolecular forces are quite weak they have a surprisingly large impact on the molecular properties of a compound,
for example:

▷ directly related to melting point, boiling point, and the energy needed to convert a solid to a liquid or a liquid to a vapor.

▷ important in determining the solubility of gases, liquids, and solids in solvents.

▷ crucial in determining the structures of biologically important molecules such as DNA and proteins.

65
11.3 Interactions between Ions and Molecules with a Permanent Dipole CMY 117 | General Chemistry

11.3 Interactions between Ions and Molecules with a Permanent Dipole

Learning Outcomes for This Section: Interactions between Ions and Molecules with a Permanent Dipole

What is our aim for this section?

▷ Know what determines the strength of the interaction between ions and molecules with permanent dipoles and
the effect of that interaction.

Many molecules are polar and conceptually we can see polar molecules as having a ”positive” end and a ”negative” end. Hence
if we dissolve an ionic compound in a polar compound (e.g. NaCl in water), the result is that the cation is attracted to the
”negative” side of the water and the anion to the ”positive” side. The forces that result here are called ion-dipole forces.

When a polar molecule encounters an ion, the attractive forces depend on three factors:

▷ The distance between the ion and the dipole. The closer they are, the stronger the attraction.

▷ The charge on the ion. The higher the ion charge, the stronger the attraction.

▷ The magnitude of the dipole. The greater the magnitude of the dipole, the stronger the attraction.

When dissolving species, heat is involved in some manner. This heat is called the enthalpy of solvation, Δhydration 𝐻 −∘ . This
energy depends on two factors

▷ As the size of an ion increases the magnitude of the enthalpy decreases; and

▷ As the charge of an ion increases the magnitude of the enthalpy increases.

Example 11.1
Hydration Energy
−1 −1
Explain why the enthalpy of hydration of Na+ (−405 kJ ⋅ mol ) is more negative than that of Cs+ (−263 kJ ⋅ mol ),
−1
whereas that of Mg2+ is much more negative (−1922 kJ ⋅ mol ) than that of either Na+ or Cs+ .

University of Pretoria | Department of Chemistry 66

CMY 117 | General Chemistry 11.4 Interactions between Molecules with a Permanent Dipole

11.4 Interactions between Molecules with a Permanent Dipole

Learning Outcomes for This Section: Interactions between Molecules with a Permanent Dipole

What are our aims for this section?

▷ Recognize that two polar molecules can interact through dipole-dipole forces.

▷ Understand how hydrogen bonding can occur and can affect the properties of water.

11.4.1 Dipole-Dipole Forces

When a polar molecule encounters another polar molecule, of the same or a different kind, the positive end of one molecule
is attracted to the negative end of the other polar molecule. This is called a dipole-dipole interaction:

Intermolecular forces, such as dipole-dipole attractions, influence the evaporation of a liquid and the condensation of a gas,
−
∘
among other things. In the case of evaporation, we know that energy is required (Δ𝐻vap ) for the process to take place (endothermic
process). It is rational that the stronger the dipole-dipole forces (attractive forces) present in a molecule, the more energy it
will take to cause evaporation of a compound consisting of these molecules.

The boiling point of a liquid depends on intermolecular forces of attraction. As the temperature of a substance is raised, its
molecules gain kinetic energy. Eventually, when the boiling point is reached, the molecules have sufficient kinetic energy to
escape the forces of attraction with their neighbours. For molecules of similar molar mass, the greater the polarity, the higher
the temperature required for the liquid to boil. For example:

67 University of Pretoria | Department of Chemistry

11.4 Interactions between Molecules with a Permanent Dipole CMY 117 | General Chemistry

Intermolecular forces also influence solubility. A qualitative observation is that like dissolves like. That is, polar molecules
are likely to dissolve in a polar solvent, and nonpolar molecules are likely to dissolve in a nonpolar solvent. The converse is
also true: it is unlikely that polar molecules will dissolve in nonpolar solvents or that nonpolar molecules will dissolve in polar
solvents.

11.4.2 Hydrogen Bonding

Hydrogen fluoride, water, ammonia, and many other compounds with O–H and N–H bonds have exceptional properties. For
example, consider the boiling points for hydrogen compounds of elements in Groups 4A through 7A

Figure 11.1: The boiling points of some simple hydrogen compounds. The effect of hydrogen bonding is apparent in the
unusually high boiling points of H2 O, HF, and NH3 . (Also, notice that the boiling point of HCl is somewhat higher than
expected based on the data for HBr and HI, suggesting that some degree of hydrogen bonding also occurs in liquid HCl.)

Generally, the boiling points of related compounds increase with molar mass, and this trend is seen in the boiling points of
most hydrogen-containing compounds. However, H2 O, NH3 and HF deviate significantly from this trend.

In bonds between H and N, O, or F, the more electronegative element takes on a significant negative charge, and the hydrogen
atom acquires a significant positive charge. Because the H atom bonded to N, O, or F can be so highly positively charged, there
is an exceptionally strong electrostatic interaction with another electronegative atom in a neighbouring molecule to form a
hydrogen bond.

University of Pretoria | Department of Chemistry 68

CMY 117 | General Chemistry 11.4 Interactions between Molecules with a Permanent Dipole

Hydrogen bonding has important implications for any property of a compound that is influenced by intermolecular forces
of attraction. It is responsible for the unique properties of water (described in the next section) and plays a central role in
biochemistry.

Example 11.2
The Effect of Hydrogen Bonding
Ethanol, CH3 CH2 OH, and dimethyl ether, CH3 OCH3 , have the same molecular formula but a different arrangement
of atoms. Predict which of these compounds has the higher boiling point.

69 University of Pretoria | Department of Chemistry

11.4 Interactions between Molecules with a Permanent Dipole CMY 117 | General Chemistry

11.4.3 Hydrogen Bonding and the Unusual Properties of Water

You might not consider the properties of water as unique, but almost no other substance behaves in a similar manner. Water’s
unique features are a consequence of the ability of H2 O molecules to cling tenaciously to one another by hydrogen bonding.

The strong intermolecular forces of attraction between water molecules are a result of the fact that each water molecule can
participate in four hydrogen bonds. An individual water molecule has two polar OOH bonds and two lone pairs. Both hydrogen
atoms are available to hydrogen bond with oxygen atoms in adjacent water molecules. In addition, the oxygen lone pairs can
participate in hydrogen bonding to the hydrogen atoms in two other water molecules. The result, seen particularly in ice, is a
tetrahedral arrangement for the hydrogen atoms around each oxygen, involving two covalently bonded hydrogen atoms and
two hydrogen-bonded hydrogen atoms.

One consequence of the fact that each water molecule can be involved in four hydrogen bonds is that ice has an open-cage
structure with lots of empty space. The result is that ice has a density about 10% less than that of liquid water, which explains
why ice floats on water. (In contrast, the vast majority of other solids sink in their liquid phase.) Another feature of the ice
structure is that the oxygen atoms are arranged at the corners of puckered, hexagonal rings. Snowflakes are always based on
six-sided figures, a reflection of this internal molecular structure of ice.

When ice melts at 0 °C, the regular structure imposed on the solid state by hydrogen bonding breaks down, and a relatively
large increase in density occurs. Another surprising thing occurs when the temperature of liquid water is raised from 0 °C to
4 °C : The density of water increases.

For almost every other substance known, density decreases as the temperature is raised. Once again, hydrogen bonding is the
reason for this seemingly odd behavior. At a temperature just above the melting point, some of the water molecules continue
to cluster in ice-like arrangements, which require extra space. As the temperature is raised from 0 °C to 4 °C, the final vestiges
of the ice structure disappear, and the volume contracts further, giving rise to the increase in density. Water’s density reaches
a maximum at about 4 °C. From this point, the density declines with increasing temperature as observed for most substances.
Because of the way that water’s density changes as the temperature approaches the freezing point, lakes do not freeze from the
bottom up in the winter. When lake water cools with the approach of winter, its density increases, the cooler water sinks, and
the warmer water rises. This turn over process continues until all the water reaches 4 °C, the maximum density. (This is how
oxygenrich water moves to the lake bottom to restore the oxygen used during the summer and bring nutrients to the top of the
lake.) As the temperature decreases further, the colder water stays at the top of the lake, because water cooler than 4 °C is less
dense than water at 4 °C. With further heat loss, ice begins to form on the surface, floating there and protecting the underlying
water and aquatic life from further heat loss.

Extensive hydrogen bonding is also the origin of the extraordinarily high specific heat capacity of liquid water (4.184 J⋅g−1 ⋅K−1 ).
Although liquid water does not have the regular structure of ice, hydrogen bonding still occurs. There must be a significant
input of energy to disrupt the intermolecular forces and raise the temperature even a small amount.

University of Pretoria | Department of Chemistry 70

CMY 117 | General Chemistry 11.5 Intermolecular Forces Involving Non-polar Molecules

The high specific heat capacity of water is, in large part, why oceans and lakes can have a large effect on local weather. In
autumn, when the temperature of the air is lower than the temperature of the ocean or lake, water transfers energy as heat to
the atmosphere, moderating the drop in air temperature. Furthermore, so much energy is available to be transferred for each
degree drop in temperature that the decline in water temperature is gradual. For this reason, the temperature of the ocean or
a large lake is generally higher than the average air temperature until late in the autumn.

11.5 Intermolecular Forces Involving Non-polar Molecules

Learning Outcomes for This Section: Intermolecular Forces Involving Nonpolar Molecules

What are our aims for this section?

▷ Identify instances where a dipole can be induced by interaction with a polar molecule (Debye forces).

▷ Identify instances where molecules interact by London dispersion forces (induced dipole–induced dipole forces).

Many important molecules such as O2 , N2 , and the halogens are not polar. Why, then, does O2 dissolve in polar water? Why
can the N2 of the atmosphere be liquefied? Some intermolecular forces must be acting between O2 and water and between N2
molecules, but what is their nature?

11.5.1 Dipole-Induced Dipole Forces: Debye Forces

Polar molecules such as water can induce, or create, a dipole in molecules that do not have a permanent dipole. To see how
this can happen, picture a polar water molecule approaching a non-polar molecule such as O2 .

Chemists refer to these as dipole-induced dipole interactions or as Debye forces. The process of inducing a dipole is called
polarization, and the degree to which the electron cloud of an atom or a molecule can be distorted depends on the polarizability
of that atom or molecule. The electron cloud of an atom or molecule with a large, extended electron cloud such as I2 can be
polarized more readily than the electron cloud in a much smaller atom or molecule, such as He or H2 , in which the valence
electrons are close to the nucleus and more tightly held. In general, the higher the molar mass, the greater the polarizability of
the molecule.

11.5.2 Induced Dipole-Induced Dipole Forces: London Dispersion Forces

Non-polar compounds can be liquids or solids if the intermolecular forces are sufficient to bind the molecules together. Non-polar
iodine, I2 , is a solid and not a gas around room temperature and pressure for this reason. The enthalpy of vaporization of a
substance at its boiling point is a good indicator of the magnitude of intermolecular forces.

71 University of Pretoria | Department of Chemistry

11.5 Intermolecular Forces Involving Non-polar Molecules CMY 117 | General Chemistry

To understand how two nonpolar molecules can attract each other, recall that the electron cloud surrounding atoms or molecules
can be distorted. Thus, when two atoms or non-polar molecules approach each other, attractions or repulsions between
their electrons and nuclei can lead to distortions in their electron clouds. That is, dipoles can be induced momentarily in
neighbouring atoms or molecules, and these induced dipoles lead to intermolecular attractions. These forces are called London
dispersion forces, or induced dipole–induced dipole forces:

It is important to understand that London dispersion forces:

▷ occur between all molecules, both non-polar and polar, but they are the only intermolecular forces between non-polar
molecules.

▷ can account for a major part of the net intermolecular force, even for polar molecules.

▷ increase with molar mass in a related series of compounds (such as the series CH4 … SnH4 ).

Example 11.3
Intermolecular Forces
Suppose you have a mixture of solid iodine, I2 , and the liquids water and carbon tetrachloride (CCl4 ). What
intermolecular forces exist between each possible pair of molecules?

University of Pretoria | Department of Chemistry 72

CMY 117 | General Chemistry 11.6 A Summary of van der Waals Intermolecular Forces

11.6 A Summary of van der Waals Intermolecular Forces

Learning Outcomes for This Section: A Summary of van der Waals Intermolecular Forces

What is our aim for this section?

▷ Describe the various kinds of intermolecular forces in liquids and solids.

Van der Waals intermolecular forces involve molecules that are polar or those in which polarity can be induced (see Table
11.5). It is important to recognize that

▷ several types of intermolecular forces may contribute to the overall ability of a molecule to interact with another of the
same or different kind (see Figure 11.2).

▷ induced dipole-induced dipole (London dispersion) forces can be quite substantial, even in a polar molecule like HCl
(see Figure 11.2).

▷ among the various types of van der Waals forces, hydrogen bonding can be a particularly important factor that influences
molecular properties.

Figure 11.2: Energies associated with intermolecular forces in several common molecules. For H2 O, it is estimated that the net
intermolecular force consists of 85% dipole-dipole (including H-bonding), 5% dipole-induced dipole, and 10% London force.

73 University of Pretoria | Department of Chemistry

11.6 A Summary of van der Waals Intermolecular Forces CMY 117 | General Chemistry

University of Pretoria | Department of Chemistry 74

CMY 117 | General Chemistry 11.6 A Summary of van der Waals Intermolecular Forces

Example 11.4
Intermolecular Forces
Identify the types of intermolecular forces that exist between each of the following:

(a) molecules in liquid methane, CH4 ;

(b) molecules of water and methanol (CH3 OH); and

(c) molecules of bromine and water.

75 University of Pretoria | Department of Chemistry

11.7 Additional Practice Problems CMY 117 | General Chemistry

11.7 Additional Practice Problems

Here I list some additional practice problems for you to do at home. The solutions to these problems are provided in the video
content on YouTube.

Identifying Intermolecular Forces

What type of intermolecular forces must be overcome in converting each of the following from a liquid to a gas?

(a) CH3 CO2 H (acetic acid)

(b) N2 H4 (hydrazine)

(c) SF6 (sulfur hexafluoride)

(d) Cl2 (chlorine)

Intermolecular Forces and Substance Phase

Consider the substances CH3 CH2 CH2 CH3 (butane), methanol CH3 OH and Ar (Argon). Which of these substances exist as a
gas at 25 °C and 1 atm?

Hydrogen Bonding

Which of the following compounds would be expected to form intermolecular hydrogen bonds in the liquid state (look up any
structures you may require)?

H2 Se, HCO2 H (formic acid), HI, (CH3 )2 CO (acetone)

More Intermolecular Forces

What types of intermolecular forces exist in the liquid phase of

(a) H2 O2

(b) CH2 Cl2

(c) H2 CO

(d) C2 H6

(e) (CH3 )2 CHOH

University of Pretoria | Department of Chemistry 76

 Theme
The Properties of Liquids
12 Click Here to access this Theme’s YouTube Playlist

12.1 Introduction

The objective of this Theme is to help you understand the interactions between atoms, ions, and molecules at the particulate
level. Many properties of liquids and solids depend on the strength of these forces; liquids will be discussed here. This Theme
is useful because it explains many interesting properties of matter.

Take water, for example. Water both melts and boils at temperatures far greater than other molecules of similar size, it dissolves
many ionic compounds, and small drops of water form spheres. You will also learn why water is among the few materials for
which the solid (in the case of water: ice) has a lower density than the liquid.

Learning Outcomes for This Section: The Properties of Liquids

This Theme covers the idea of the Physical Properties of Liquids and we will use each learning outcome as a section
in this Theme. Hence, what are our aims for this Theme?

▷ Define the equilibrium vapour pressure of a liquid, and explain the relationship between the vapour pressure and
boiling point of a liquid.

▷ Describe how intermolecular forces affect the surface tension, capillary action, and viscosity of liquids.

▷ Describe the phenomena of the critical temperature, 𝑇𝑐 , and critical pressure, 𝑝𝑐 , of a substance.

▷ Calculate enthalpy changes for changes of state.

▷ Represent the connection between vapour pressure and temperature graphically.

▷ Use the Clausius-Clapeyron equation to relate vapour pressure and enthalpy of vapourization.

Liquids are the most difficult to describe precisely of the three states of matter. The molecules in a gas under normal conditions
are far apart and may be considered more or less independent of one another. The structures of solids can be described because
the particles that makeup solids are usually in an orderly arrangement. The particles of a liquid interact with their neighbors,
like the particles in a solid, but, unlike solids, there is little long range order. In spite of the fact that liquids do not have a simple
or regular structure, their properties can be explained qualitatively by viewing them at the particulate level.

12.2 Vapourization and Condensation of Liquids

Vapourization or evapouration is the process in which a substance in the liquid state becomes a gas. Molecules in a liquid
have a range of energies; by increasing the temperature, we increase the average kinetic energy of the molecules.

Once a molecule close to a liquid’s surface has more kinetic energy than potential energy, it leads to evaporation.

77
12.3 Vapour Pressure CMY 117 | General Chemistry

Therefore, we can deduce that vaporization is an endothermic process because energy is required to overcome the intermolecular
forces (potential energy) of attraction holding the molecules together.

The energy required to vaporize 1 mole of a liquid is the standard molar enthalpy of vaporization, Δvap 𝐻 −∘ :

Vaporisation
Liquid −−−−−−−−−−−−−−−−→ Vapour Δvap 𝐻 −∘ = molar enthalpy of vapourization
Energy Absorbed By Liquid

Condensation is of course the opposite process. This happens when a molecule hits other molecules in the gas phase and
loses some of its kinetic energy. This leads to it reentering the liquid:

Condensation
Vapour −−−−−−−−−−−−−−−−→ Liquid − Δvap 𝐻 −∘ = molar enthalpy of condensation
Energy Released By Vapour

Condensation is the reverse of vapourization and so is an exothermic process. Energy is transferred to the surroundings. The
enthalpy change for condensation is equal but opposite in sign to the enthalpy of vapourization.

We can see from the data presented in tables (in your textbook) that there must be some correlation between the boiling
point of a liquid and its Δvap 𝐻 −∘ . We know that intermolecular forces become increasingly important with increasing mass, the
enthalpies of vapourization and the boiling points for halogen-containing acids is, for example, HCl < HBr < HI. Exceptions
can occur when hydrogen bonding is present in a liquid (e.g. Water, HF etc.)!

Example 12.1
Enthalpy of vapourization
You put 925 mL of water (about 4 cupfuls) in a pan at 100 °C, and the water slowly evapourates. How much energy is
transferred as heat to vapourize all the water? (Density of water at 100 °C = 0.958 g⋅cm3 .)

Solution discussed in Video Lecture

12.3 Vapour Pressure

Water completely evapourates (due to diffusion) in an open beaker, but not in a sealed one. What happens in the sealed case?
In this case a dynamic equilibrium results, where the water evapourates and then condenses, until both remain constant (not
equal!). At equilibrium, molecules still move continuously between the liquid phase and the vapour phase.

When we have this situation, we can measure a property called the equilibrium vapour pressure (or just, vapour pressure).
This is the pressure exerted by the vapour in equilibrium with the liquid phase. The process is illustrated in Figure 12.1.

University of Pretoria | Department of Chemistry 78

CMY 117 | General Chemistry 12.3 Vapour Pressure

-
Figure 12.1: An illustration of how vapour pressure is measured.

One thing we can do is plot vapour pressure as a function of temperature, which can provide a great deal of information. All
points along the vapour pressure - temperature curves represent conditions of pressure and temperature at which liquid
and vapour are in equilibrium. Some examples are shown in Figure 12.2. We can use these curves to deduce relative strength
of intermolecular forces in different substances.

-
Figure 12.2: vapour pressure curves for diethyl ether [(C2 H5 )2O ], ethanol (C2 H5 OH), and water. Each curve represents
conditions of T and P at which the two phases, liquid and vapour, are in equilibrium. These compounds exist as liquids
for temperatures and pressures to the left of the curve and as gases under conditions to the right of the curve.

79 University of Pretoria | Department of Chemistry

12.3 Vapour Pressure CMY 117 | General Chemistry

Example 12.2
Using vapour Pressure
You place 2.00 L of water in an open container in your dormitory room; the room has a volume of 4.25 × 104 L. You seal
the room and wait for the water to evapourate. Will all of the water evapourate at 25 °C? Although it is not realistic,
assume for simplicity there is zero humidity to start. (At 25 °C, the density of water is 0.997 g⋅mL−1 , and its equilibrium
vapour pressure is 23.8 mm Hg.)

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 80

CMY 117 | General Chemistry 12.4 The Clausius-Clapeyron Equation

12.4 The Clausius-Clapeyron Equation

We saw in Figure 12.2 that the plots were all curves, hence if
we plot the inverse function, 1/𝑇 and ln(𝑝), we get a straight
line which we can fit! The equation to plot is

Δvap 𝐻 −∘
ln(𝑝) = − ( ) + Constant (12.1)
𝑅𝑇

Equation (12.1) is called the Clausius-Clapeyron Equation.

An alternative equation allows you to estimate Δvap 𝐻 −∘ if you

know the vapour pressure of a liquid at two temperatures
−
∘
𝑝2 Δvap 𝐻 1 1
ln ( )=− ( − ) (12.2)
𝑝1 𝑅 𝑇2 𝑇1

We can then solve this equation for Δvap 𝐻 −∘ to estimate its

value. We start the rearrangement as follows

𝑝2 1 1
−𝑅 ln ( ) = Δvap 𝐻 −∘ ( − ) Figure 12.3: Plot of the Clausius–Clapeyron equation. The
𝑝1 𝑇2 𝑇1
values used are that of water.
Now we combine the 𝑇 term on the right
𝑝2 𝑇 − 𝑇2
−𝑅 ln ( ) = Δvap 𝐻 −∘ ( 1 )
𝑝1 𝑇2 𝑇1
and so
𝑝2 𝑇𝑇
∴Δvap 𝐻 −∘ = −𝑅 ln ( )[ 2 1 ]
𝑝1 𝑇1 − 𝑇2

12.5 Boiling Point

The boiling point of a liquid is the temperature at which its vapour pressure is equal to the external pressure. If the external
pressure is 760 mm Hg, this temperature is the normal boiling point.

The normal boiling point of water is 100 °C, and hence, at higher altitudes (lower atmospheric pressure), it boils at lower
temperatures.

12.6 Critical Temperature and Pressure

If we continue increasing the temperature and pressure of a substance, we will reach some 𝑇 and 𝑝 where the distinction
between gas and liquid is no longer possible. This is called the critical point. At this point we have the critical temperature,
𝑇𝑐 , and the critical pressure, 𝑝𝑐 . he substance that exists under these conditions is called a supercritical fluid.

A supercritical fluid is like a gas under such a high pressure that its density resembles that of a liquid, while its viscosity
(resistance to flow) remains close to that of a gas. However, for most substances, these values of 𝑇𝑐 and 𝑝𝑐 are quite high and
not easily obtainable. The only notable exception is CO2 , as shown in Figure 12.4.

81 University of Pretoria | Department of Chemistry

12.7 Surface Tension, Capillary Action, and Viscosity CMY 117 | General Chemistry

Figure 12.4: Critical temperature and pressure for CO2 . The pressure versus temperature curve representing equilibrium
conditions for liquid and gaseous carbon dioxide ends at the critical point; above that temperature and pressure, CO2 becomes
a supercritical fluid.

12.7 Surface Tension, Capillary Action, and Viscosity

Molecules in a liquid has no net force acting on them. However, molecules at the surface of liquid experiences a net attractively
inward force. This makes the liquid behave as if it had skin. The toughness of this skin is called the surface tension.

Capillary action (the movement of a liquid up a thin tube) and the observation of a curved meniscus when liquids are in
various containers are other consequences of intermolecular forces.

Another important property of liquids that intermolecular forces play a role in is viscosity, the resistance of liquids to flow.
For example, emptying a breaker with oil or honey will take much longer than one with water. Stronger intermolecular forces
lead to a more viscous liquid.

University of Pretoria | Department of Chemistry 82

CMY 117 | General Chemistry 12.8 Additional Practice Problems

12.8 Additional Practice Problems

Here I list some additional practice problems for you to do at home. The solutions to these problems are provided in the video
content on YouTube.

Vapor Pressure

Answer the following questions using Figure 12.2 in the notes:

(a) What is the equilibrium vapor pressure of diethyl ether at room temperature (approximately 20 °C)?

(b) Place the three compounds in Figure 12.2 in order of increasing intermolecular forces.

(c) If the pressure in a flask is 400 mm Hg and if the temperature is 40 °C, which of the three compounds (diethyl ether,
ethanol, and water) are liquids, and which are gases?

(d) You heat some water to 60 °C in a lightweight plastic bottle and seal the top very tightly so gas cannot enter or leave the
bottle. What happens when the water cools?

(e) A cylinder with a movable piston is partially filled with diethyl ether at a temperature of 30 °C and a pressure of 400
mm Hg. What phase(s) of diethyl ether exist under these conditions? The piston is pushed inward, compressing the gas.
After some time, the pressure stabilizes at 800 mm Hg. What phase(s) of diethyl ether exist under these conditions?

More on Vapor Pressure

Vapor pressure curves for CS2 (carbon disulfide) and CH3 NO2 (nitromethane) are drawn here:

Answer the following questions:

(a) What are the approximate vapor pressures of CS2 and CH3 NO2 at 40 °C?

(b) What type(s) of intermolecular forces exist in the liquid phase of each compound?

83 University of Pretoria | Department of Chemistry

12.8 Additional Practice Problems CMY 117 | General Chemistry

(c) What is the normal boiling point of CS2 ? Of CH3 NO2 ?

(d) At what temperature does CS2 have a vapor pressure of 600 mm Hg?

(e) At what temperature does CH3 NO2 have a vapor pressure of 600 mm Hg?

Supercritical Fluids

Methane (CH4 ) cannot be liquefied at room temperature, no matter how high the pressure. Propane (C3 H8 ), another simple
hydrocarbon, has a critical pressure of 42 atm and a critical temperature of 96.7 °C. Can this compound be liquefied at room
temperature? Explain briefly.

Surface Tension

Give an example illustrating the phenomenon of surface tension. Explain why surface tension is the consequence of intermolecular
forces.

Viscosity

What factors affect the viscosity of a substance? Which of the following substances, water (H2 O), ethanol (CH3 CH2 OH),
ethylene glycol (HOCH2 CH2 OH), and glycerol (HOCH2 CH(OH)CH2 OH), is expected to have the highest viscosity? Should
viscosity of a substance be affected by temperature? Explain your answers.

Capillary Action

When water is placed in a buret it forms a concave meniscus at the surface. In contrast, mercury (in a manometer for example)
forms a convex meniscus. Explain why this phenomenon occurs, and why the two liquids give different results. Predict the
meniscus shape if the buret is filled with ethylene glycol (HOCH2 CH2 OH).

Boiling Points of Substances

Select the substance in each of the following pairs that should have the higher boiling point: (a) Br2 or ICl; (b) neon or krypton.

University of Pretoria | Department of Chemistry 84

 Theme
The Properties
13 of Solutions
Click Here to access this Theme’s YouTube Playlist

13.1 Introduction

We have covered the properties of liquids in the previous Theme. Hence, we can now look at the idea of solutions (liquids with
some solute in it). This Theme explores factors that affect the solubility of solutes in liquid solvents. You will learn why large
quantities of sodium chloride dissolve in water, but a mixture of oil and water, perhaps in a salad dressing, readily separates
into two phases. For solutions of gases in water, such as dissolved oxygen in a lake, you will learn why the solubility of a gas
depends on temperature.

Adding a solute to a pure liquid changes the properties of the liquid. In fact, this is why some solutions are made. For instance,
a mixture of antifreeze and water in a car’s radiator prevents the coolant from boiling in the summer and freezing in the
winter. Adding or removing solutes from your blood affects the rate at which water moves in and out of your cells. For this
reason, intravenous fluids must have exact concentrations of solutes such as NaCl and glucose. The freezing point, boiling
point, osmotic pressure, and solvent vapour pressure for solutions are examples of colligative properties, which depend on
the number of solute particles per solvent molecule, not the identity of the solute.

13.2 Units of Concentration

Learning Outcomes for This Section: Units of Concentration

What are our aims for this section?

▷ Calculate and use the concentration units: molality, mole fraction, weight percent, and parts per million (ppm).

▷ Recognize the difference between molarity and molality.

The molality, 𝑚, of a solution is defined as the amount of solute (mol) per kilogram of solvent:

−1 amount of solute (mol)

Concentration (𝑐, mol ⋅ kg ) = molality of solute =
mass of solvent (kg)

The mole fraction, 𝑋, of a solution component is defined as the amount of that component (𝑛A ) divided by the total amount
of all of the components of the mixture (𝑛A + 𝑛B + 𝑛C + …). Mathematically it is represented as

𝑛A
Mole fraction of A, 𝑋A = (13.1)
𝑛A + 𝑛B + 𝑛C + …

Notice that the sum of the mole fractions of the components in the solution must always equal 1, because of how we define
mole fractions.

85
13.2 Units of Concentration CMY 117 | General Chemistry

Weight percent is the mass of one component divided by the total mass of the mixture, multiplied by 100%:

Mass of A
Weight Percent A = × 100% (13.2)
Mass of A + Mass of B + Mass of C + …

Finally, the unit ppm (parts per million) also refers to relative quantities of solute and solvent by mass; 1.0 ppm represents a
solution containing 1.0 g of a substance in a sample with a total mass of 1.0 million g (equivalent to 1 mg in 1000 g). This unit is
typically used to identify concentrations of solutes in very dilute solutions. It is useful in chemistry (especially in environmental
chemistry) and in disciplines such as biology, geology, and oceanography.

Example 13.1
Calculating Mole Fraction, Molality, Molarity, and Weight Percent
Suppose you add 1.2 kg of ethylene glycol, HOCH2 CH2 OH, as an antifreeze to 4.0 kg of water in the radiator of your
car. What are the mole fraction, molality, and weight percent of the ethylene glycol? The density of water is 1 L⋅kg−1 .

Solution to be discussed during lecture period

Example 13.2
Parts Per Billion
Silver ion has an average concentration of 28 ppb (parts per billion) in our water supply.

(a) What is the molality of the silver ion in the water supply?

(b) If you wanted 1.0 × 102 g of silver and could recover it chemically from water supplies, what volume of water in
liters would you have to treat? (Assume the density of water is 1.0 g⋅cm−3 .)

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 86

CMY 117 | General Chemistry 13.3 How Are Solutions Made?

13.3 How Are Solutions Made?

Learning Outcomes for This Section: How Are Solutions Made?

What are our aims for this section?

▷ Understand the process of dissolving a solute in a solvent and recognize the terminology used (saturated,
unsaturated, supersaturated, solubility, miscible).

▷ Understand the thermodynamics associated with the solution process and calculate the enthalpy of solution from
thermodynamic data.

A solution is saturated once the solute (e.g. NaCl, CuCl2 etc.) has reached its maximum concentration in the solution. Hence,
the liquid will no longer dissolve whatever solute you have.

The solubility of a solute is the concentration of solute in a saturated solution in equilibrium with undissolved solute. Hence,
when you have added exactly the amount that will dissolve fully in the liquid.

13.3.1 We Can Dissolve One Liquid in Another Liquid

If two liquids can be mixed in any proportion to form a homogeneous mixture, they are said to be miscible (water and bleach).
In contrast, immiscible liquids do not fully mix in all proportions; they exist in contact with each other as separate layers (oil
and water).

87 University of Pretoria | Department of Chemistry

13.4 Pressure and Temperature Affect the Solubility of Compounds CMY 117 | General Chemistry

13.3.2 We Can Also Dissolve Solids in Liquids

The like-dissolves-like guideline is also often followed when molecular solids dis-solve in liquids. Polar Solids dissolve in polar
liquids, whereas Non-Polar Solids dissolve in non-polar liquids.

13.3.3 The Enthalpy (Energy) Picture When Dissolving Solutes

What is the basis for the like-dissolves-like guideline? There are two factors that determine whether any process will occur.
One factor is the process’s enthalpy change, here the solution’s enthalpy. The second factor is the entropy change for the process.
Entropy is a topic for CMY 127, however, it essentially gives an idea of how likely a process is to occur by looking at the sign of
the value. Though enthalpy is not as useful, we can interpret a lot of information from it regarding the energy, and hence the
intermolecular forces present.

We can logically deduce our first fact regarding solvation energies. The first being that if we dissolve two ’like’ substances, for
example polar solute and polar solvent with hydrogen bonding intermolecular forces, the change in energy should be small,
because there is no change in the type of intermolecular force either possess before and after mixing.

A good indication if a solvent will dissolve the solute, is if the enthalpy of solution, Δsoln 𝐻 −∘ , is negative, however, this is not
always the case, sometimes endothermic solution processes also occur (this is because of that entropy factor).

When we dissolve an ionic substance, say NaCl, we must think of the process happening in two steps, that is

→ K+
1. KF(𝑠) − −
(𝑠) + F(𝑠) , where the energy required to do this is −Δlattice 𝐻

2. K+ −
→ K+
(𝑠) + F(𝑠) −
−
(𝑎𝑞) + F(𝑎𝑞) , where the energy here is called Δhydration 𝐻

The enthalpy of the overall reaction, called the enthalpy of solution (Δsoln 𝐻), is the sum of the two enthalpy changes:

Δsoln 𝐻 = −Δlattice 𝐻 + Δhydration 𝐻

As a general rule, to be water-soluble, an ionic compound will have an enthalpy of solution that is exothermic or only slightly
endothermic.

13.4 Pressure and Temperature Affect the Solubility of Compounds

Learning Outcomes for This Section: Pressure and Temperature Affect the Solubility of Compounds

What are our aims for this section?

▷ Describe the effects of pressure and temperature on the solubility of a solute.

▷ Use Henry’s law to calculate the solubility of a gas in a solvent.

▷ Apply Le Chatelier’s principle to predict the change in solubility of gases with temperature changes.

Pressure and temperature are two external factors that influence solubility. Both affect the solubility of gases in liquids, whereas
only temperature is a factor in the solubility of solids in liquids.

University of Pretoria | Department of Chemistry 88

CMY 117 | General Chemistry 13.4 Pressure and Temperature Affect the Solubility of Compounds

13.4.1 Dissolving Gases in Liquids: Henry’s Law

Henry’s law states that the solubility of a gas in a liquid is directly proportional to the
Henry’s Law Constants for
gas pressure. Mathematically, this can be represented as
Gases in Water (25 °C)
𝑆g = 𝑘H 𝑝g (13.3)
Gas k H (mol⋅kg−1 ⋅bar−1 )

He 3.8 × 10−4 where 𝑆g is the gas solubility (in mol⋅kg−1 ), Pg is the partial pressure of the gaseous
solute, and 𝑘H is Henry’s law constant (Table 13.2), a constant characteristic of the
H2 7.8 × 10−4
solute and solvent. A good example of Henry’s law in action is that of carbonated soft
N2 6.0 × 10 −4 drinks.

O2 1.3 × 10−3 You can better understand the effect of pressure on solubility by examining the system
at the particulate level. The solubility of a gas is defined as the concentration of the
CO2 0.034
dissolved gas in equilibrium with the substance in the gaseous state. At equilibrium,
CH4 1.4 × 10 −3 the rate at which solute gas molecules escape the solution and enter the gaseous state
equals the rate at which gas molecules re-enter the solution. An increase in pressure
C2 H6 1.9 × 10−3
results in more molecules of gas striking the surface of the liquid and entering the
solution in a given time. The solution eventually reaches a new equilibrium when the concentration of gas dissolved in the
solvent is high enough that the rate of gas molecules escaping the solution again equals the rate of gas molecules entering the
solution.

Example 13.3
Using Henry’s Law (Effect of Pressure)
What is the concentration of O2 in a freshwater stream in equilibrium with air at 25 °C and at a pressure of 1.0 bar?
Express the answer in grams of O2 per kg of water. The mole fraction of O2 in air is 0.21.

Solution to be discussed during lecture period

89 University of Pretoria | Department of Chemistry

13.4 Pressure and Temperature Affect the Solubility of Compounds CMY 117 | General Chemistry

13.4.2 Temperature Effects on Solubility: Le Chatelier’s Principle

The solubility of all gases in water decreases with increasing temperature. You may realize this from everyday observations
such as the appearance of air bubbles as water is heated below the boiling point. As you will see, it is possible to predict
temperature’s effect on a gas’s solubility from the sign of its enthalpy of solution.

When gases dissolve in water, they usually do so in an exothermic process. That is, energy is released as heat, and the value of
Δsoln 𝐻 is negative. The reverse process, loss of dissolved gas molecules from a solution, requires energy as heat. At equilibrium,
the rates of the two processes are the same

The effect of temperature on the solubility of a gas in a liquid can be predicted using Le Chatelier’s principle, which states
that a change in any of the factors determining an equilibrium causes the system to adjust by shifting in the direction that
reduces or counteracts the effect of the change.

The solubility of solids in water is also affected by temperature, but, unlike the situation involving solutions of gases, no
general pattern of behavior is observed. In Figure 13.1, the solubilities of several salts are plotted versus temperature. The
solubility of many salts increases with increasing temperature, but there are notable exceptions. Predictions based on whether
the enthalpy of solution is positive or negative are valid most of the time, but exceptions do occur.

Chemists can take advantage of the variation of solubility with temperature to purify compounds. An impure sample of a
compound that is more soluble at higher temperatures is dissolved by heating the solution. The solution is then cooled to
decrease the solubility (look at the photos in Figure 13.1). When the limit of solubility is reached at the lower temperature,
crystals of the pure compound form.

Figure 13.1: The temperature dependence of the solubility of some ionic compounds in water. The solubility of most ionic
compounds increases with increasing temperature. This is illustrated using NH4 Cl in the images.

University of Pretoria | Department of Chemistry 90

CMY 117 | General Chemistry 13.5 Colligative Properties

13.5 Colligative Properties

Learning Outcomes for This Section: Colligative Properties

What are our aims for this section?

▷ Using Raoult’s law, calculate the effect of dissolved solutes on solvent vapour pressure (𝑝solvent ).

▷ Calculate the effect of a solute on the boiling point and freezing point of a solvent.

▷ Calculate the osmotic pressure (Π) for solutions.

▷ Use colligative properties to determine the molar mass of a solute.

▷ Use the van’t Hoff factor in colligative property calculations involving ionic solutes.

13.5.1 Raoult’s Law is About Changes in Vapour Pressure

When a non-volatile solute dissolves in a liquid, the vapour pressure of the solvent is lowered. Experiments show that the
vapour pressure of the solvent over the solution, 𝑝solution , is proportional to the mole fraction (𝑋) of the solvent. Raoult’s law
expresses this relationship:
𝑝solvent = 𝑋solvent 𝑝−
∘
solvent (13.4)

Raoult’s law tells you that the vapour pressure of solvent over a solution (𝑝solvent ) is lower than that of the pure solvent
(𝑝−
∘
solvent ); it depends on the fraction of molecules in the solution that are solvent molecules.

An ideal solution is defined as one that obeys Raoult’s law precisely. However, just as no gas is truly ideal, no solution is
truly ideal. Nonetheless, Raoult’s law is a good approximation of solution behaviour in most instances, especially at low solute
concentrations.

For Raoult’s law to apply, the forces of attraction between solute and solvent molecules must be the same as those between
solvent molecules in the pure solvent. Hence, if solvent–solute interactions are stronger than solvent–solvent interactions,
the measured vapour pressure will be lower than the value calculated by Raoult’s law. If the solvent–solute interactions
are weaker than solvent–solvent interactions, the vapour pressure will be higher than calculated.

We can calculate the change in vapour pressure of the solvent as follows:

Δ𝑝solvent = −𝑋solute 𝑝−
∘
solvent (13.5)

91 University of Pretoria | Department of Chemistry

13.5 Colligative Properties CMY 117 | General Chemistry

Example 13.4
Using Raoult’s Law
You dissolve 651 g of ethylene glycol, HOCH2 CH2 OH, in 1.50 kg of water. What is the vapor pressure of the water
over the solution at 90 °C? Assume ideal behavior for the solution. Appendix G in your textbook lists 𝑝−
∘
water at various
temperatures.

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 92

CMY 117 | General Chemistry 13.5 Colligative Properties

13.5.2 Boiling Points Increase When Solutes are Dissolved In Solvents

When a solute is added to a solvent, according to Raoult’s law, the vapour pressure will lower, leading to a higher boiling point.
An important question is how the boiling point of the solution varies with solute concentration. The boiling point elevation,
Δ𝑇bp , is directly proportional to the molality of the solute:

Elevation in boiling point = Δ𝑇bp = 𝐾bp 𝑚solute (13.6)

In this equation, 𝐾bp is a proportionality constant called the molal boiling point elevation constant. It has the units of degrees
Celsius per molal (°C⋅m−1 ). Values for 𝐾bp are determined experimentally, and different solvents have different values. The
value of 𝐾bp corresponds to the elevation in boiling point for a 1 𝑚 solution.

Example 13.5
Boiling Point Elevation
Eugenol, a compound found in nutmeg and cloves, has the formula C10 H12 O2 . What is the boiling point of a solution
containing 0.144 g of this compound dissolved in 10.0 g of benzene?

Solution to be discussed during lecture period

93 University of Pretoria | Department of Chemistry

13.5 Colligative Properties CMY 117 | General Chemistry

13.5.3 Freezing Points Decrease When Solutes are Dissolved In Solvents

Another consequence of dissolving a solute in a solvent is that the freezing point of the solution is lower than that of the pure
solvent. For an ideal solution, the depression of the freezing point is given by an equation similar to that for the elevation of
the boiling point:
Freezing point depression = Δ𝑇fp = 𝐾fp 𝑚solute (13.7)

where 𝐾fp is the molal freezing point depression constant in degrees Celsius per molal (°C⋅m−1 ). The values are negative
quantities, so the result of the calculation is a negative value for Δ𝑇fp , signifying a decrease in temperature.

Example 13.6
Freezing Point Depression
What mass of ethylene glycol, HOCH2 CH2 OH, must be added to 5.50 kg of water to lower the freezing point of the
water from 0.0 °C to −10.0 °C?

Solution to be discussed during lecture period

13.5.4 Osmotic Pressure: How Solution Equilibrate Their Concentrations

Osmosis is the movement of solvent molecules through a semipermeable membrane from a region of lower solute concentration
to a region of higher solute concentration. The process continues until an equilibrium is reached and hence the concentration
remains constant on both sides of this membrane. Figure 13.2 illustrates the process of osmosis.

In order for the particles to move accros the membrane, we can think of the driving force like being a pressure of sorts. If you
apply pressure on one side of a system, you force the particles on that side to move in the opposite direction. Hence why this
is called osmotic pressure, Π, because it illustrates how much pressure is placed on the molecules to lead to an equilibrium
situation.

University of Pretoria | Department of Chemistry 94

CMY 117 | General Chemistry 13.5 Colligative Properties

Figure 13.2: Osmosis at the particulate level. Osmotic flow through a membrane that is selectively permeable
(semipermeable) to water. Dissolved substances such as hydrated ions or large sugar molecules cannot diffuse through the
membrane.

From experimental measurements on dilute solutions, it is known that osmotic pressure and concentration (𝑐) are related by
and equation similar to the ideal gas equation:
Π = 𝑐𝑅𝑇 (13.8)

In this equation, 𝑐 is the molar concentration (in moles per liter); 𝑅 is the gas constant; and 𝑇 is the absolute temperature (in
kelvins).

Example 13.7
Determining the Osmotic Pressure of a Solution of a Polymer
−1
Polyvinyl alcohol is a water-soluble polymer with an average molar mass of 28,000 g ⋅ mol . You dissolve 1.844 g of
this polymer in water to give 150. mL of solution. What is the osmotic pressure, measured at 27 °C?

Solution to be discussed during lecture period

95 University of Pretoria | Department of Chemistry

13.5 Colligative Properties CMY 117 | General Chemistry

13.5.5 We Can Use Colligative Properties to Determine Molar Mass of Substances

How can we determine the molar mass of an unknown compound? An experiment must be conducted to find this crucial
piece of information, and one way to do so is to use a colligative property of a solution of the compound.

Example 13.8
Determining Molar Mass from Boiling Point Elevation
A solution prepared from 1.25 g of oil of wintergreen (methyl salicylate) in 99.0 g of benzene has a boiling point of 80.31
°C. Determine the molar mass of methyl salicylate.

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 96

CMY 117 | General Chemistry 13.5 Colligative Properties

Example 13.9
Osmotic Pressure and Molar Mass
Beta-carotene is the most important of the A vitamins. Calculate the molar mass of 𝛽-carotene if 10.0 mL of a solution
in chloroform containing 7.68 mg of 𝛽-carotene has an osmotic pressure of 26.57 mm Hg at 25.0 °C.

Solution to be discussed during lecture period

13.5.6 Colligative Properties of Solutions Containing Ions

Salt (NaCl) if often times added to snow or ice that are on roads to decrease the melting temperature of the ice or snow and so
assisting in removing it from the road. Now recall that the effect of a solute on the properties of a solvent does not depend on
what is dissolved, but rather how much. Hence for example if we add the same amount of NaCl to a solution versus sugar, we
get twice the number of ions in the NaCl case than the sugar case.

So to estimate the freezing point depression for an ionic compound, first find the molality of solute from the mass and molar
mass of the compound and the mass of the solvent. Then, multiply the molality by the number of ions in the formula, for
example, two for NaCl.

However, experimental results have shown that though we theoretically expect two ions for NaCl, and three for NaSO4 , etc.,
there is never an exact doubling, or tripling of the measured depresiation in temperature, see Table 13.1. This is only the case
for electrolytes.

97 University of Pretoria | Department of Chemistry

13.5 Colligative Properties CMY 117 | General Chemistry

Table 13.1: Freezing Point Depressions of Some Ionic Solutions

Δ𝑇fp, measured
Mass % m (mol⋅kg−1 ) ΔT fp (measured, °C) ΔT fp (calculated, °C)
Δ𝑇fp, calculated
NaCl

0.00700 0.0120 −0.0433 −0.0223 1.94

0.500 0.0860 −0.299 −0.160 1.87
1.00 0.173 −0.593 −0.322 1.84
2.00 0.349 −1.186 −0.649 1.83

Na2 SO4

0.00700 0.00493 −0.0257 −0.00917 2.80

0.500 0.0354 −0.165 −0.0658 2.51
1.00 0.0711 −0.320 −0.132 2.42
2.00 0.144 −0.606 −0.268 2.26

So now what is going on? One person who suggested a way of adapting the theoretical value was Jacobus Henricus van’t Hoff,
who introduced the van’t Hoff Factor. The van’t Hoff factor is represented by i and is calculated as follows:

Δ𝑇 𝑓𝑝,𝑚𝑒𝑎𝑠𝑢𝑟𝑒𝑑 Δ𝑇 𝑓𝑝,𝑚𝑒𝑎𝑠𝑢𝑟𝑒𝑑
𝑖= = (13.9)
Δ𝑇 𝑓𝑝,𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝐾fp 𝑚

or then rewritten so that we can calculate the actual (measured) values:

Δ𝑇 𝑓𝑝,𝑚𝑒𝑎𝑠𝑢𝑟𝑒𝑑 = 𝑖𝐾fp 𝑚 (13.10)

The van’t Hoff factors can be used in calculations of any colligative property. Vapor pressure lowering, boiling point elevation,
freezing point depression, and osmotic pressure are all larger for electrolytes than for nonelectrolytes of the same morality.

Example 13.10
Freezing Point and Ionic Solutions
A 0.0200 𝑚 aqueous solution of an ionic compound, Co(NH3 )4 Cl3 , freezes at −0.0640 °C. How many ions does each
formula unit of Co(NH3 )4 Cl3 produce upon being dissolved in water?

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 98

CMY 117 | General Chemistry 13.6 Colloids

13.6 Colloids

Learning Outcomes for This Section: Colloids

What is our aim for this section?

▷ Recognize the properties and importance of colloids.

We defined a solution to be a homogeneous mixture of two or more substances in a single phase. However, we can make it
more precise in adding in a true solution, no settling of the solute should be observed and the solute particles should be in the form
of ions or relatively small molecules.

Colloidal dispersions, also called colloids, represent a state intermediate between a solution and a suspension. Some examples
include, milk, fog and porcelain. Some examples are listed below:

Types of Colloids

Type Dispersing Medium Dispersing Phase Examples

Aerosol Gas Liquid Fog, clouds, aerosol sprays

Aerosol Gas Solid Smoke, airborne viruses, automobile exhaust

Foam Liquid Gas Shaving cream, whipped cream

Foam Solid Gas Styrofoam, marshmallow

Emulsion Liquid Liquid Mayonnaise, milk, face cream

Gel Solid Liquid Jelly, JELL-O, cheese, butter

Sol Liquid Solid Gold in water, milk of magnesia, mud

Solid sol Solid Solid Milkglass

Chemists have been able to deduce a few properties of colloids. First, many of the substances that form colloids have high
molar masses; this is true of proteins such as hemoglobin that have molar masses in the thousands. Second, the particles of a
colloid are relatively large (several hundred nanometers in diameter). As a consequence, they exhibit the Tyndall effect; they
scatter visible light when dispersed in a solvent, making the mixture appear cloudy. Third, even though colloidal particles are
large, they are not so large that they settle out.

13.6.1 What Types of Colloids are There?

Colloids are classified according to the state of the dispersed phase and the dispersing medium. The table above lists several
types of colloids and gives examples of each.

Colloids with water as the dispersing medium can be classified as hydrophobic (from the Greek, meaning “water-fearing”) or
hydrophilic (“water-loving”). A hydrophobic colloid is one in which only weak attractive forces exist between the water and the
surfaces of the colloidal particles.

Emulsions are colloidal dispersions of one liquid in another, such as oil or fat in water. Familiar examples include salad
dressing, mayonnaise, and milk. So why are milk and mayonnaise apparently homogeneous mixtures that do not separate into

99 University of Pretoria | Department of Chemistry

13.6 Colloids CMY 117 | General Chemistry

layers? The answer is that they contain an emulsifying agent such as soap or a protein. Lecithin, found in egg yolks, can act
as an emulsifying agent, so mixing egg yolks with oil and vinegar stabilizes the colloidal dispersion known as mayonnaise. To
understand this process further, con-sider how soaps and detergents, substances known as surfactants, function.

13.6.2 What is a Surfactant?

Soaps and detergents are emulsifying agents. Soap is made by heating a fat with sodium or potassium hydroxide, which
produces anions of long-chain carboxylic acids, sometimes referred to as fatty acids. The fatty-acid anion has both a nonpolar,
hydrophobic hydrocarbon tail that is soluble in similar hydrocarbons and a polar, hydrophilic head that is soluble in water.
Oil cannot be readily washed away from dishes or clothing with water because oil is nonpolar and thus insoluble in water. To
clean away the oil, soap is added to the water. The nonpolar molecules of the oil interact with the nonpolar hydrocarbon tails
of the soap molecules, leaving the polar heads of the soap to interact with surrounding water molecules. The oil and water
then mix (Figure 13.3), and the oil can be washed away.

Figure 13.3: The cleaning action of soap. Soap molecules interact with water through the charged, hydrophilic end of
the molecule. The long, hydrocarbon end of the molecule is hydrophobic, but it can bind through dispersion forces with
hydrocarbons and other nonpolar substances.

Substances such as soaps that affect the properties of surfaces, and therefore affect the interaction between two phases, are
called surface-active agents, or surfactants, for short. A surfactant used for cleaning is a detergent. One function of a surfactant
is to lower the surface tension of water, which enhances the cleansing action of the detergent.

University of Pretoria | Department of Chemistry 100

CMY 117 | General Chemistry 13.7 Additional Practice Problems

13.7 Additional Practice Problems

Here I list some additional practice problems for you to do at home. The solutions to these problems are provided in the video
content on YouTube.

Molality, Mole Fraction and Weight%

”Concentrated” hydrochloric acid is an aqueous solution of 37.2% HCl that is commonly used as a laboratory reagent. The
density of this solution is 1.19 g⋅mL−1 .

(a) What mass of HCl is contained in 0.500 L of this solution?

(b) Calculate the mole fraction and molality of the ”concentrated” acid.

Parts Per Million

0.145 g KMnO4 is dissolved in a 500 mL volumetric flask.

(a) Determine the concentration of the KMnO4 in ppm.

(b) Determine the concentration of the K+ in ppm.

Other Concentration Units

When the concentration of lead in tap water reaches 15 ppm, certain remedial actions must be taken. At this concentration,
what mass of lead (μg) would be contained in a typical glass of water (300 mL)? Suppose this solution is diluted by a factor of
one hundred. Express the concentration of the diluted solution in ppm.

Using Concentration Units

A sample of air at atmospheric pressure and ambient temperature was found to contain 2.0 ppm SO2 . Under these conditions
the density of the air is 0.0012 g ⋅ mL−1 . What volume of this air (m3 ) will contain 1.0 g of the pollutant?

Gas Solubility

A closed bottle of soda-water has a headspace pressure of 5.0 atm at 25 °C. The Henry’s Law Constant is 3.1 × 10−2 mol ⋅ L−1 ⋅−1 .

(a) Determine the solubility of the gas (in mol ⋅ L−1 ) in the closed bottle.

(b) Determine the solubility of the gas (in mol ⋅ L−1 ) in the bottle after it has been standing open to the atmosphere for some
hours. The partial pressure of CO2 in air under these conditions is 4.05 × 10−4 bar.

Colligative Properties: Vapor Pressure Lowering

Glycerin (C3 H8 O3 ) is a non-volatile non-electrolyte with a density of 1.26 g ⋅ mL−1 at 25 °C. Determine the vapour pressure at
25 °C of solution made by adding 50.0 mL of glycerin to 500.0 mL of water . The vapour pressure of pure water at 25 °C is 23.8
torr, and it’s density is 1.00 g ⋅ mL−1 .

101 University of Pretoria | Department of Chemistry

13.7 Additional Practice Problems CMY 117 | General Chemistry

Colligative Properties: Vapor Pressure Lowering (Determining Molar Mass)

The vapor pressure of pure carbon tetrachloride (CCl4 ) at 50.0 ∘ C is 0.437 atm. When 7.42 g of a pure nonvolatile substance is
dissolved in 100.0 g of CCl4 , the vapor pressure of the solution is 0.411 atm. alculate the molar mass of the solute.

Colligative Properties: Boiling Point Increase and Freezing Point Depression

Calculate the freezing and boiling points of an aqueous solution of ethylene glycol (HOCH2 CH2 OH) containing 39.5 g of solute
−1 −1
dissolved in 750.0 mL of solvent. (𝐾bp = 0.52 °C⋅kg ⋅ mol and 𝐾fp = −1.86 °C⋅kg ⋅ mol )

Colligative Properties: Osmotic Pressure I

At 25.0 °C the osmotic pressure of blood is 7.70 atm. Determine the mass of glucose (C6 H12 O6 ) required to make 1.50 L of a
solution that is isotonic with blood.

Colligative Properties: Osmotic Pressure II

A solution is prepared by dissolving 0.0350 kg of hemoglobin in enough water to make up 1.00 L in volume. The osmotic
pressure of the solution is found to be 10.0 mm Hg at 25.0 °C. Calculate the molar mass of hemoglobin.

Colligative Properties: Osmotic Pressure III

A biochemical engineer isolates a bacterial gene fragment and dissolves a 17.6 mg sample of the material in enough water to
make 31.5 mL of solution. The osmotic pressure of the solution is 3.40 torr at 25.0 °C.

(a) What is the molar mass of the gene fragment?

(b) If the solution density is 0.997 g ⋅ mL−1 , how large is the freezing point depression for this solution?

Colligative Properties: Osmotic Pressure IV

The observed osmotic pressure for a 0.10 M solution of Fe(NH4 )2 (SO4 )2 at 25.0 °C is 10.8 atm. Compare the calculated and
expected experimental values of of 𝑖.

University of Pretoria | Department of Chemistry 102

 Theme
Chemical Kinetics
14 Click Here to access this Theme’s YouTube Playlist

14.1 Introduction

Chemical kinetics is the study of the rates of chemical reactions. On the macroscopic level, the field of chemical kinetics addresses
what reaction rate means, how to determine a reaction rate experimentally, and how factors such as temperature and reactant
concentrations influence rates. At the particulate level, the concern is with the reaction mechanism, the detailed pathway of
atoms and molecules as a reaction proceeds. The goal is to use data from the macroscopic world of chemistry to understand
how chemical reactions occur at the particulate level, and then to apply this information to control important reactions.

To explain the rates of reactions, we use a simple collision model, which basically states that for two species to react, their
molecules must collide with the correct orientation and with sufficient energy. From a macroscopic point of view, we control
reaction rates using concentration, temperature, and catalysts.

14.2 How Fast Does a Reaction Occur? – The Rates of Reactions

Learning Outcomes for This Section: How Fast Does a Reaction Occur? – Rates of Reactions

What are our aims for this section?

▷ Calculate the average rate of a reaction from concentration–time data.

▷ Relate the rates for the disappearance of reactants and formation of products for a chemical reaction.

All rates are an expression of change over time (e.g. kph). Similarly, the rate of a chemical reaction refers to the change in
concentration of a reactant or product per unit of time:

Change in Concentration
Rate of Reaction = (14.1)
Change in Time

14.2.1 How Do We Calculate the Rate of a Reaction?

If we think about rates, say in terms of the speed of a car, how would we determine the ”rate” (average speed) of the car?
We would say Δ(distance)/Δ(times). Hence we can do something similar for chemical reactions! To determine the rate of a
reaction we need to measure two things, the time and concentration. The methods to do so are not relevant for our course.

Consider the decomposition reaction

A −
→ B

What will happen if we have 1 M of A and let it decompose? What will we see if we plot the concentration A versus time on a
graph?

103
14.2 How Fast Does a Reaction Occur? – The Rates of Reactions CMY 117 | General Chemistry

The average rate of this reaction for any interval of time can be expressed as the negative of the change in A concentration
divided by the change in time:

Change in [A] Δ[A]

Rate of Decomposition of A = − =−
Change in Time Δ𝑡

The negative sign is required because N2 O5 is a reactant and its concentration decreases with time (that is, Δ[A] = Δ[A]final −
Δ[A]initial is negative), but rate is always expressed as a positive quantity.

You might also ask what the instantaneous rate is at a single point in time. In car, the instantaneous rate can be read from
the speedometer. For a chemical reaction, you can determine the instantaneous rate from the concentration-time graph by
drawing a line tangent to the concentration-time curve at a particular time and determining its slope.

Example 14.1
Rate of Reaction
Data collected on the concentration of a dye as a function of time are given in the following graph. Using these data,
estimate the value of (a) the average rate of change in the dye concentration over the first 2.0 minutes, and (b) the
average rate of change during the fifth minute (from 𝑡 = 4.0 min to 𝑡 = 5.0 min).

University of Pretoria | Department of Chemistry 104

CMY 117 | General Chemistry 14.2 How Fast Does a Reaction Occur? – The Rates of Reactions

Solution to be discussed during lecture period

14.2.2 Relative Rates and Stoichiometry

During a chemical reaction, amounts of reactants decrease with time, and amounts of products increase. Also, if we have
a reaction containing different stoichiometry, we will see that each reactant and product has a different rate associated with its
change over time.

For example, the reaction 2 A + B −

→ C + D. This reaction implies that A is consumed twice as fast as B (2:1 stoichiometry). In
a general sense it helps to use a reaction of the form

𝛼 A + 𝛽 B −−−→ 𝛾 C + 𝛿 d

we then define the reaction rate as:

1 Δ[A] 1 Δ[B] 1 Δ[C] 1 Δ[d]

Reaction Rate = − =− =+ =+
𝛼 Δ𝑡 𝛽 Δ𝑡 𝛾 Δ𝑡 𝛿 Δ𝑡

Note that the reaction rate is now on a per mole of reaction basis.

Example 14.2
Relative Rates and Stoichiometry
Relate the rates for the disappearance of reactants and formation of products for the following reaction:

4 PH3 (𝑔) −
→ P4 (𝑔) + 6 H2 (𝑔)

105 University of Pretoria | Department of Chemistry

14.3 How Does the Conditions of a Reaction Affect the Rate? CMY 117 | General Chemistry

Solution to be discussed during lecture period

New Page

14.3 How Does the Conditions of a Reaction Affect the Rate?

Learning Outcomes for This Section: How Does the Conditions of a Reaction Affect the Rate?

What is our aim for this section?

▷ Describe how reaction conditions (reactant concentrations, temperature, presence of a catalyst, and the state of
the reactants) affect reaction rate.

Several factors (reactant concentrations, temperature, and presence of catalysts) affect the rate of a reaction. If the reactant
is a solid, the surface area available for reaction is also a factor. To start, we know two aspects of reactions in general:

▷ If the concentration of a reactant is increased, the reaction rate also increases.

▷ Chemical reactions occur more rapidly at higher temperatures.

Another way we can change the rate of a reaction is by using a catalyst. Catalysts are substances that accelerate chemical
reactions but are not themselves consumed.

The surface area of a solid reactant can also affect the reaction rate. Only molecules at the surface of a solid can come in contact
with other reactants. The smaller the particles of a solid, the more molecules are found on the solid’s surface. With very small
particles, the effect of surface area on rate can be quite dramatic. Farmers know that fine dust particles (suspended in the air
of an enclosed space such as a silo or feed mill where grain is stored) represent a major explosion hazard.

University of Pretoria | Department of Chemistry 106

CMY 117 | General Chemistry 14.4 How Will Changing Concentrations Affect The Reaction Rate?

14.4 How Will Changing Concentrations Affect The Reaction Rate?

Learning Outcomes for This Section: How Will Changing Concentrations Affect The Reaction Rate?

What is our aim for this section?

▷ Derive a rate equation from experimental information using the method of initial rates.

One important goal in studying the kinetics of a reaction is to determine its mechanism, that is, how the reaction occurs at
the molecular level. The place to begin is to learn, by experiment, how reactant concentrations affect the reaction rate. The
resulting relationship between reactant concentrations and the reaction rate is expressed by an equation called a rate equation,
or rate law.

14.4.1 What is a Rate Equation?

The effect of concentration can be determined by evaluating how the rate is affected when the concentrations of the reactants
are varied (with the temperature held constant).

When the concentration of species in the reaction is varied, we get to a point where we notice that the rate of reaction is
proportional to the concentration. So for example, on the reaction A −
→ B + C, if we look at the rate of the reaction for [A] =
1.0 M and [A] = 2.0 M, we will see the rate increase with the same ”factor”. Mathematically we can write this as

Rate of Reaction ∝ [A]

From this we can then relate

Δ[A]
Rate of Reaction = − = 𝑘[A]
Δ𝑡
where the proportionality constant, 𝑘, is called the rate constant. This rate equation tells you that this reaction rate is proportional
to the concentration of the reactant. Figure 14.1 illustrates this effect for the decomposition of N2 O5 .

So generally, for a reaction such as

𝛼A + 𝛽B −
→ 𝜒Χ

the rate equation has the form

Rate of reaction = 𝑘[A]𝑚 [B]𝑛

The rate equation expresses the fact that the

rate of reaction is proportional to the reactant
concentrations, each concentration being raised
to some power. The exponents (𝑚 and 𝑛)
in the rate equation must be determined by
experiment; they are not necessarily the
stoichiometric coefficients (𝛼 and 𝛽) for the
Figure 14.1: Reactant concentration versus time data for the gas-phase
balanced chemical equation. The exponents in
decomposition of N2 O5 , beginning with two different concentrations of
this equation are often positive whole numbers,
N2 O5 .
but they can also be negative numbers, fractions, or zero.

One interesting fact, is that because catalysts are not written as reactants, they are not included in the rate equations. However,

107 University of Pretoria | Department of Chemistry

14.4 How Will Changing Concentrations Affect The Reaction Rate? CMY 117 | General Chemistry

if you have a homogenous catalyst (a catalyst in the same phase as the reactants), then they can appear in the rate equation.

14.4.2 The Idea of The Order of a Reaction

The order of a reaction with respect to a particular reactant is the exponent of its concentration term in the rate law expression,
and the overall reaction order is the sum of the exponents on all concentration terms.

For example, consider the reaction A + B −

→ C, and say you have an expression

Rate of Reaction = 𝑘[A]2 [B]

Then the reaction is 2nd order in terms of A and 1st order in terms of B, and 3rd order overall.

14.4.3 More on This Rate Constant, k

The rate constant, 𝑘, is a proportionality constant that relates rate and concentration at a given temperature. It is an
important quantity because it lets you find the reaction rate for a new set of concentrations.

The rate constant also has units. These differ according to the overall order of a reaction:

▷ First-order reactions: The units of 𝑘 are time−1 .

▷ Second-order reactions: The units of 𝑘 are L⋅mol−1 ⋅time−1 .

▷ Zero-order reaction: The units of k are mol⋅L−1 ⋅time−1 .

14.4.4 How do We Determine a Rate Equation?

One way to determine a rate equation is by using the method of initial rates. The initial rate is the instantaneous reaction
rate at the start of the reaction (the rate at 𝑡 = 0). An approximate value of the initial rate can be obtained by mixing the
reactants and determining the reaction rate after 1% to 2% of the limiting reactant has been consumed. Measuring the rate
during the initial stage of a reaction is convenient because initial concentrations are known. This is best illustrated by the use
of an example.

Example 14.3
Determining a Rate Equation
The rate of the reaction between CO and NO2 at 540 K

CO(𝑔) + NO2 (𝑔) −

→ CO2 (𝑔) + NO(𝑔)

was measured starting with various concentrations of CO and NO2 . Determine the rate equation and the value of the
rate constant.

Experiment Initial Concentrations (mol⋅L−1 ) Initial Rate (mol⋅L−1 ⋅h−1 )

[CO] [NO2 ]
1 5.10 × 10 −4
0.350 × 10−4 3.4 × 10−8
2 5.10 × 10 −4
0.700 × 10 −4
6.8 × 10−8
3 5.10 × 10−4 0.175 × 10−4 1.7 × 10−8
4 1.02 × 10−3 0.350 × 10−4 6.8 × 10−8
5 1.53 × 10−3 0.350 × 10−4 10.2 × 10−8

University of Pretoria | Department of Chemistry 108

CMY 117 | General Chemistry 14.4 How Will Changing Concentrations Affect The Reaction Rate?

Solution to be discussed during lecture period

New Page

109 University of Pretoria | Department of Chemistry

14.4 How Will Changing Concentrations Affect The Reaction Rate? CMY 117 | General Chemistry

Problem Solving Tip 14.1: Determining a Rate Equation (A Logarithmic Approach)

In Example 14.3, the ratio of the rate equations simplified to 2 = 2𝑛 , allowing for the determination of the exponent
(𝑛 = 1) by inspection. What do you do when the ratio of the reactant concentrations or the exponents are not integers?
The answer is we use logarithms! Say for example, if we got that

2.25 = (1.50)𝑛 ⟹ log(2.25) = log(1.50)𝑛 ⟹ log(2.25) = 𝑛 log(1.50)

We can then solve for 𝑛, which we see gives us the order of this reaction in terms of some reactant as second order

log(2.25)
𝑛= = 2.000
log(1.50)

Example 14.4
Using a Rate Equation to Determine Rates
Using the rate equation and rate constant determined for the reaction of CO and NO2 at 540 K in the previous example,
determine the initial rate of the reaction when [CO] = 3.8 × 10−4 mol⋅L−1 and [NO2 ] = 0.650 × 10−4 mol⋅L−1 .

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 110

CMY 117 | General Chemistry 14.5 Concentration–Time Relationships: Integrated Rate Laws

14.5 Concentration–Time Relationships: Integrated Rate Laws

Learning Outcomes for This Section: Concentration–Time Relationships – Integrated Rate Laws

What are our aims for this section?

▷ Use the relationships between reactant concentration and time for zero-order, first-order, and second-order
reactions.

▷ Apply graphical methods for determining reaction order and the rate constant from experimental data.

▷ Use the concept of half-life (𝑡1/2 ), especially for first-order reactions.

A chemist often needs to know how long a reaction must proceed to reach a particular concentration of some reactant or
product, or what the reactant and product concentrations will be after some time has elapsed. For this reason, it would be
useful to have a mathematical equation that relates time and concentration.

Hence, an equation that can plot the concentration-time graphs of earlier. With such an equation, you could calculate the
concentration at any given time or the length of time needed for a given amount of reactant to react. This would prove to be
immensely helpful.

14.5.1 The Integrated Rate Law for First-Order Reactions

Suppose the reaction R −

→ P is first-order. This means the reaction rate is directly proportional to the concentration of R raised
to the first power, or, mathematically
Δ[R]
− = 𝑘[R]
Δ𝑡
The relationship can be transformed into a very useful equation called an integrated rate equation (because integral calculus
is used in its derivation). By separating the variables and integrating we obtain:

[R]𝑡
ln ( ) = −𝑘𝑡 (14.2)
[R]0

Here, [R]0 and [R]𝑡 are concentrations of the reactant at time 𝑡 = 0 and at a later time, 𝑡, respectively. The ratio of concentrations,
[R]𝑡 /[R]0 , is the fraction of reactant that remains after a given time has elapsed.

Finally, notice that 𝑘 for a first-order reaction is independent of concentration; 𝑘 has units of time−1 (s−1 , for example). This
means you can choose any convenient unit for [R]𝑡 and [R]0 : moles per liter, moles, grams, number of atoms, number of
molecules, or gas pressure.

Example 14.5
The First-Order Integrated Rate Law
In the past, cyclopropane, C3 H6 , was used in a mixture with oxygen as an anesthetic. (This practice has almost ceased
today because the compound is flammable.) When heated, cyclopropane rearranges to propene in a first-order process.

111 University of Pretoria | Department of Chemistry

14.5 Concentration–Time Relationships: Integrated Rate Laws CMY 117 | General Chemistry

If the initial concentration of cyclopropane is 0.050 mol⋅L−1 , how much time (in hours) must elapse for its concentration
to drop to 0.010 mol⋅L−1 ?

Solution to be discussed during lecture period

Example 14.6
Using the First-Order Rate Equation
Hydrogen peroxide decomposes in a dilute sodium hydroxide solution at 20 °C in a first-order reaction:

1
H2 O2 (𝑎𝑞) −
→ H2 O(𝑙) + O
2 2 (𝑔)
−1
Rate = 𝑘[H2 O2 ] with 𝑘 = 1.06 × 10−3 min

What is the fraction of H2 O2 remaining after 100. minutes? If the initial concentration of H2 O2 is 0.020 mol⋅L−1 , what
is the concentration of H2 O2 at this time?

University of Pretoria | Department of Chemistry 112

CMY 117 | General Chemistry 14.5 Concentration–Time Relationships: Integrated Rate Laws

Solution to be discussed during lecture period

14.5.2 The Integrated Rate Law for Second-Order Reactions

Suppose the reaction R −

→ P is second-order. The rate equation is

Δ[R]
− = 𝑘[R]2
Δ𝑡

Using calculus, this relationship can be transformed into the following equation that relates reactant concentration and time:

1 1
− = 𝑘𝑡 (14.3)
[R]𝑡 [R]0

Just as for the integrated first-order rate equation, [R]0 is the concentration of the reactant at time 𝑡 = 0, and [R]𝑡 is the
concentration at a later time, but now 𝑘 is the second-order rate constant, which has the units of L⋅mol−1 ⋅time−1 .

113 University of Pretoria | Department of Chemistry

14.5 Concentration–Time Relationships: Integrated Rate Laws CMY 117 | General Chemistry

Example 14.7
Using the Second-Order Integrated Rate Equation
The gas-phase decomposition of HI
1 1
HI(𝑔) −
→ H2 (𝑔) + I2 (𝑔)
2 2
has the rate equation
Δ[HI]
− = 𝑘[HI]2
Δ𝑡
−1 −1
where 𝑘 = 30. L ⋅ mol ⋅ min at 443 °C. How much time does it take for the concentration of HI to drop from 0.010
−1 −1
mol⋅L to 0.0050 mol⋅L at 443 °C?

Solution to be discussed during lecture period

14.5.3 The Integrated Rate Law for Zeroth-Order Reactions

If a reaction (R −
→ P) is zero-order, the rate equation is

Δ[R]
− =𝑘
Δ𝑡

This equation leads to the integrated rate equation where the units of 𝑘 are mol⋅L−1 ⋅time−1 , and is

[R]𝑡 − [R]0 = −𝑘𝑡 (14.4)

Zero-order kinetics are observed, for example, with gas-phase reactions that occur on metal surfaces. Here, the rate of the
reaction, such as the decomposition of ammonia on platinum, is independent of reactant concentrations so long as the number
of gas-phase reactant molecules is much greater than the number of binding sites on the metal surface. Note, however, that
as the reaction proceeds and the number of reactant molecules decreases, the reaction order, and thus the rate law, is likely to
change.

University of Pretoria | Department of Chemistry 114

CMY 117 | General Chemistry 14.5 Concentration–Time Relationships: Integrated Rate Laws

14.5.4 Graphical Methods for Determining Reaction Order and the Rate Constant

Chemists often determine the order of a reaction and its rate constant using graphical methods. If rearranged slightly, Equations
(14.2), (14.3), and (14.4) have the form 𝑦 = 𝑚𝑥 + 𝑏. They look as follows:

Hence, the idea is to plot these versions of the equations and see which straight line fits the data the best and then we deduce
the order of that reaction. We can summarise this as follows:

Characteristic Properties of Reactions of the Type R ⟶ Products

Order Rate Equation Integrated Rate Equation Straight-Line Plot Slope 𝑘 Units
0 −Δ[R]/Δ𝑡 = 𝑘[R]0 [R]𝑡 − [R]0 = −𝑘𝑡 [R]𝑡 vs. 𝑡 −𝑘 mol⋅L−1 ⋅time−1
1 −Δ[R]/Δ𝑡 = 𝑘[R]1 ln ⒧[R]𝑡 /[R]0 ⒭ = −𝑘𝑡 ln[R]𝑡 vs. 𝑡 −𝑘 time−1
2 −Δ[R]/Δ𝑡 = 𝑘[R]2 ⒧1/[R]𝑡 ⒭ − ⒧1/[R]0 ⒭ = 𝑘𝑡 1/[R]𝑡 vs. 𝑡 𝑘 L⋅mol−1 ⋅time−1

14.5.5 Half-Life and First-Order Reactions

The half-life, t1/2 , of a reaction is the time required for the concentration of a reactant ([R]𝑡 ) to decrease to one-half its initial
value ([R]0 ). It is a convenient way to describe the rate at which a reactant is consumed in a chemical reaction: The longer
the half-life, the slower the reaction.

We determine the half-life of a first-order reaction when the following equations are satisfied:

1 [R]𝑡 1
[R]𝑡 = [R] or =
2 0 [R]0 2

Half-life is used primarily when dealing with first-order processes. To evaluate t1/ 2 for a first-order reaction, substitute
1
[R]𝑡 /[R]0 = and 𝑡 = 𝑡1/2 into the integrated first-order rate equation (Equation (14.2)),
2

Rearranging this equation (and substituting ln 2 = 0.693) provides a useful equation that relates half-life and the first-order
rate constant:
0.693
𝑡1/2 = (14.5)
𝑘
This equation identifies an important feature of first-order reactions: 𝑡1/2 is independent of concentration. The half-life of a
reaction makes it easier to see if a reaction is fast or slow, rather than using the rate constants.

115 University of Pretoria | Department of Chemistry

14.5 Concentration–Time Relationships: Integrated Rate Laws CMY 117 | General Chemistry

Example 14.8
Half-Life and a First-Order Process
Sucrose, C12 H22 O11 , decomposes to fructose and glucose in acid solution with the rate law

−1
Rate = 𝑘[C12 H22 O11 ] 𝑘 = 0.216 h at 25 ∘ C

(a) What is the half-life of sucrose at this temperature?

(b) What amount of time is required for 87.5% of the initial concentration of sucrose to decompose?

Solution to be discussed during lecture period

Example 14.9
Half-Life and Radioactive Decay
Radioactive decay is a first-order process. Radioactive radon-222 gas (222 Rn) occurs naturally as a product of the
uranium decay series. The half-life of 222 Rn is 3.8 days. Suppose a flask originally contained 4.0 × 1013 atoms of 222 Rn.
How many atoms of 222 Rn will remain after one month (30. d)?

Solution to be discussed during lecture period potato

University of Pretoria | Department of Chemistry 116

CMY 117 | General Chemistry 14.6 A Microscopic View of Reaction Rates

Potato

14.6 A Microscopic View of Reaction Rates

Learning Outcomes for This Section: A Microscopic View of Reaction Rates

What are our aims for this section?

▷ Describe the collision theory of reaction rates and use collision theory to describe the effects of reactant
concentration, molecular orientation, and temperature on reaction rate.

▷ Relate activation energy (𝐸𝑎 ) to the rate of a reaction.

▷ Understand reaction coordinate diagrams.

▷ Use the Arrhenius equation, or one of its modified forms, to calculate the activation energy from rate constants
at different temperatures.

Chemists often turn to the particulate level of chemistry to explain chemical phenomena. Looking at the way reactions occur
at the atomic and molecular levels can give some insight into the various influences on rates of reactions.

For a specific reaction, factors that influence reaction rate include the concentrations of the reactants, the temperature of the
reaction system, and the presence of catalysts. Each of these influences can be explained using the collision theory of reaction
rates, which states that three conditions must be met for a reaction to occur:

1. The reacting molecules must collide with one another.

2. The reacting molecules must collide with sufficient energy to initiate the process of breaking and forming bonds.

3. The molecules must collide in an orientation that can lead to the rearrangement of the atoms and the formation of
products.

14.6.1 Collision Theory: Concentration and Reaction Rate

It is reasonable to propose that the rate of reaction should be related to the number of collisions, which is in turn related to the
species concentrations. If you have more molecules (higher concentration) then more collisions will result.

Thus, the dependence of reaction rate on concentration can be explained: The number of collisions between the two reactant
molecules is directly proportional to the concentration of each reactant, and the rate of the reaction shows a first-order
dependence on each reactant.

117 University of Pretoria | Department of Chemistry

14.6 A Microscopic View of Reaction Rates CMY 117 | General Chemistry

14.6.2 Collision Theory: Activation Energy

Molecules require some minimum energy to react. Chemists visualize this as an energy barrier that the reactants must
surmount for a reaction to occur (Figure 14.2). The energy required to cross the barrier is called the activation energy, 𝐸a .
If the activation energy is low, a high proportion of the molecules in a sample may have sufficient energy to react. The reaction
will be fast. If the activation energy is high, only a few reactant molecules in a sample may have enough energy. The reaction
will be slow.

Figure 14.2: Activation energy for the reaction of NO2 and CO to give NO and CO2 .

The process can be described with an energy diagram called a reaction coordinate diagram (Figure 14.2). The horizontal
axis describes the reaction progress as the reaction proceeds, and the vertical axis represents the potential energy of the system
during the reaction.

When the energy of the system reaches a maximum we obtain the transition state of the reaction. At the transition state,
sufficient energy has been concentrated in the appropriate bonds; bonds in the reactants can now break, and new bonds can
form to give products. The system is poised to go on to products, but it could also return to the reactants. Because the transition
state is at a maximum in potential energy, a molecular species with this structure cannot be isolated.

14.6.3 Collision Theory: Activation Energy and Temperature

How does temperature affect the rate of a reaction? The molecules in a

sample have a wide range of energies, described earlier as a Boltzmann
distribution of energies. In any sample of a gas or liquid, some molecules
have very low energies, others have very high energies, but most have
some intermediate energy. As the temperature increases, the average
energy of the molecules in the sample increases, as does the fraction
having higher energies.

Raising the temperature increases the reaction rate by increasing the

fraction of molecules with enough energy to surmount the activation
Figure 14.3: Energy distribution curve.
energy barrier (Figure 14.3).

University of Pretoria | Department of Chemistry 118

CMY 117 | General Chemistry 14.6 A Microscopic View of Reaction Rates

14.6.4 Collision Theory: Effect of Molecular Orientation on Reaction Rate

Not only must reacting molecules have sufficient energy to react, but the reactant molecules must also come together in the
correct orientation. The lower the probability of achieving the proper alignment, the smaller the value of 𝑘, and the slower
the reaction.

Imagine what happens when two or more complicated molecules collide. In only a small fraction of the collisions will the
molecules come together in exactly the right orientation. Thus, only a tiny fraction of the collisions can be effective. No
wonder some reactions are slow. Conversely, it is amazing that so many are fast!

14.6.5 The Arrhenius Equation

The observation that reaction rates depend on the energy and frequency of collisions between reacting molecules, on the
temperature, and on whether the collisions have the correct geometry is summarized by the Arrhenius equation:
𝐸a
−
𝑘 = 𝐴𝑒 𝑅𝑇 (14.6)

−1
In this equation, 𝑘 is the rate constant, 𝑅 is the gas constant with a value of 8.31446 × 10−3 kJ ⋅ K−1 ⋅ mol , and 𝑇 is the
kelvin temperature. The parameter A is called the frequency factor. It is related to the number of collisions and to the fraction
of collisions that have the correct geometry; 𝐴 is specific to each reaction and is temperature-dependent. The factor 𝑒−𝐸a /𝑅𝑇
represents the fraction of molecules having the minimum energy for reaction; it always has a value less than 1.

The Arrhenius equation is significant because

▷ it can be used to calculate 𝐸a from the temperature dependence of the rate constant, and

▷ it can be used to calculate the rate constant, if 𝐸a , 𝑇, and 𝐴 are known.

If rate constants for a given reaction are measured at several temperatures then you can use graphical techniques to determine
the activation energy of a reaction. Taking the natural logarithm of each side of Equation (14.6) gives

Rearranging this expression slightly shows that ln(𝑘) and 1/𝑇 are related linearly:

𝐸a 1
ln(𝑘) = − ( ) + ln(𝐴) The Arrhenius Equation
𝑅 𝑇

𝑦 = 𝑚𝑥 + 𝑏 The Equation for a Straight Line

This means that, if the natural logarithm of 𝑘 (ln(𝑘)) is plotted versus 1/𝑇, the result is a downward-sloping straight line with
a slope of (−𝐸a /𝑅). The activation energy, 𝐸a , can be obtained from the slope of this line (𝐸a = −𝑅 × slope).

119 University of Pretoria | Department of Chemistry

14.6 A Microscopic View of Reaction Rates CMY 117 | General Chemistry

Example 14.10
Determination of E a Using the Arrhenius Equation
Using the experimental data shown in the table, calculate the activation energy 𝐸a for the reaction

2 N2 O(𝑔) −
→ 2 N2 (𝑔) + O2 (𝑔)

Experiment Temperature (K) k (L⋅mol−1 ⋅s−1 )

1 1125 11.59

2 1053 1.67

3 1001 0.380

4 838 0.0011

Solution to be discussed during lecture period

The activation energy, 𝐸a , for a reaction can be obtained algebraically if 𝑘 is known at two different temperatures. You can
write an equation for each set of these conditions:

Subtracting these two equations leads to

𝑘2 𝐸 1 1
ln(𝑘2 ) − ln(𝑘1 ) = ln ( )=− a[ − ]
𝑘1 𝑅 𝑇2 𝑇1

University of Pretoria | Department of Chemistry 120

CMY 117 | General Chemistry 14.6 A Microscopic View of Reaction Rates

Example 14.11
Calculating E a Numerically
Use values of 𝑘 determined at two different temperatures to calculate the value of 𝐸a for the decomposition of HI:

2 HI(𝑔) −
→ H2 (𝑔) + I2 (𝑔)

−1
𝑘1 = 2.15 × 10−8 L ⋅ mol ⋅ s−1 at 6.50 × 102 K (𝑇1 )

−1
𝑘2 = 2.39 × 10−7 L ⋅ mol ⋅ s−1 at 7.00 × 102 K (𝑇2 )

Solution to be discussed during lecture period

121 University of Pretoria | Department of Chemistry

14.7 What are Catalysts? CMY 117 | General Chemistry

14.7 What are Catalysts?

Learning Outcomes for This Section: What are Catalysts?

What are our aims for this section?

▷ Describe the functioning of a catalyst and its effect on the activation energy of a reaction.

▷ Understand the lock-and-key and induced-fit models for substrate binding to enzymes.

▷ Understand the basics of the Michaelis-Menten model of enzyme kinetics.

A catalyst is a substance that speeds up the rate of a chemical reaction. Catalysts are not consumed in a chemical reaction.
They are, however, intimately involved in the details of the reaction at the particulate level. A catalyst’s function is to provide
a different pathway with a lower activation energy for the reaction.

14.7.1 What Effect does Catalysts Have on Reaction Rates?

An energy profile for a catalyzed reaction (Figure 14.4) shows that the overall energy barrier is much lower than for the
uncatalyzed reaction. Five separate steps are identified for the mechanism in the energy profile. This proposed mechanism
also includes a series of reaction intermediates, species formed in one step of the reaction and consumed in a later step.

Figure 14.4: Energy profile for the iodine-catalyzed reaction of cis-2-butene to form trans-2-butene. A catalyst accelerates a
reaction by altering the mechanism so that the activation energy is lowered. With a smaller barrier to overcome, more reacting
molecules have sufficient energy to surmount the barrier, and the reaction occurs more rapidly.

Acids and bases catalyze many reactions. Acid catalysts are often used in the synthesis of organic molecules, and an example
is an esterification reaction.

It is important to know that although a catalyst increases the rate of a chemical reaction, it does not influence whether a
reaction is product-favored or reactant-favored at equilibrium. A catalyst simply enables a reaction to reach equilibrium
more quickly.

University of Pretoria | Department of Chemistry 122

CMY 117 | General Chemistry 14.7 What are Catalysts?

14.7.2 Enzymes

The biological catalysts in our bodies are called, enzymes, which are typically large proteins. For an enzyme to catalyze a
reaction, several key steps must occur:

1. The reactant (often called the substrate) must bind to the enzyme.

2. The chemical reaction must take place.

3. The products(s) of the reaction must leave the enzyme so that more substrate can bind and the process can be repeated.

The location in the enzyme where the substrate binds and the reaction occurs is called the active site. The active site often
consists of a cavity or cleft in the structure of the enzyme into which the substrate or part of the substrate can fit in just the
right orientation so that specific bonds can be broken and/or made.

How do enzymes bring about such fast and specific chemical reactions? An early model of enzyme binding is the lock-and-key
model (Figure 14.5 (a)). The shape of the substrate is pictured as fitting into the enzyme’s active site precisely, much like a
key (the substrate) fits a lock (the enzyme). The induced-fit model has supplanted this model (Figure 14.5 (b)) in which the
enzyme is not viewed as a rigid structure like a lock, but instead as a very large molecule that has some three-dimensional
flexibility. The enzyme begins with a structure that does not match the shape of the substrate exactly. Instead, binding of the
substrate causes the structure of the enzyme to change so that it fits the substrate.

Figure 14.5: Models of substrate binding.

This model can also incorporate another feature of enzyme action. A catalyst functions by providing a pathway for reaction that
has a lower activation energy for the reaction. An enzyme’s active site, therefore, should optimally bind to and thus stabilize the
transition state for the reaction, as opposed to the substrate. When a substrate binds, it undergoes changes in its shape, referred
to as conformational changes, that push it in the direction that leads to the formation of the transition state of the reaction. In
the induced-fit model, therefore, both the enzyme and the substrate undergo conformational changes upon binding that lower
the activation energy for the reaction, leading to a faster reaction.

123 University of Pretoria | Department of Chemistry

14.8 Additional Practice Problems CMY 117 | General Chemistry

14.8 Additional Practice Problems

Here I list some additional practice problems for you to do at home. The solutions to these problems are provided in the video
content on YouTube.

Determining the Rate Law of a Reaction using Initial Rates

Consider the reaction

2 NO(𝑔) + 2 H2 (𝑔) −−−→ N2 (𝑔) + 2 H2 O(𝑔)

(a) Using the following data, determine the overall reaction order and the value of the rate constant 𝑘

Experiment [NO] (mol⋅L–1 ) [H2 ] (mol⋅L–1 ) Initial Rate (M⋅s–1 )

1 5.00 × 10–3 2.00 × 10–3 1.3 × 10–5

2 1.00 × 10–2 2.00 × 10–3 5.2 × 10–5

3 1.00 × 10–2 4.00 × 10–3 1.04 × 10–4

(b) Determine the rate of the reaction when [NO] = 4.73 × 10−1 M and [H2 ] = 1.84 × 10−3 M.

Using Rate Laws

The following reaction has the rate law Rate = 𝑘[N2 O5 ] with 𝑘 = 6.93 × 10−3 s−1 .

2 N2 O5 (𝑔) −−−→ 4 NO2 (𝑔) + O2 (𝑔)

How long does it take for 87.5% of the original amount of N2 O5 to decompose?

More Uses of Rate Laws

Consider the reaction

2 C2 F4 (𝑔) −−−→ C4 F8 (𝑔)

This reaction has a rate constant of 0.0442 M−1 ⋅ s−1 . Answer the following questions:

(a) Starting with 0.135 mol C2 F4 in a 2.00 L container and no C4 F8 , what will be the concentration of C2 F4 after 1.00 hour?

(b) What percentage of the original amount of C2 F4 will be left after 1.00 hour?

(c) What percentage of the original amount of C2 F4 has been consumed after 1.00 hour?

(d) What will be the concentration of C4 F8 after one hour?

(e) Determine the half-life of this reaction, based on the original amount of C2 F4 present.

(f) Without doing any calculations, determine how long it will take, for half the C2 F4 present after one hour, to disappear?

University of Pretoria | Department of Chemistry 124

CMY 117 | General Chemistry 14.8 Additional Practice Problems

The Arrhenius Equation

Consider the reaction

2 N2 O5 (𝑔) −−−→ 4 NO2 (𝑔) + O2 (𝑔)

This reaction has the rate law of the form “Rate = 𝑘[N2 O5 ]” with 𝑡1/2 = 100 s at 25 °C. Answer the following questions:

(a) Determine the activation energy, given that 𝑘 has the value of 1.69 × 10−1 s−1 at 55 °C.

(b) Determine the value of the pre-exponential factor 𝐴.

Reaction Rate

Consider the reaction

2N2 O5 (𝑔) −−−→ 4NO2 (𝑔) + O2 (𝑔)

For this reaction

(a) Write the rate expression in terms of the consumption of N2 O5 and the formation of NO2 and O2 .

(b) If oxygen is being produced at a rate of 0.015 M⋅s−1 at a given time, calculate the rate of consumption of N2 O5 and the
rate of formation of NO2 at that same time instant.

125 University of Pretoria | Department of Chemistry

 What comes next?
We hope to welcome you to CMY 127 next
c
semester!