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 2026, I will be teaching Themes 7.4 - 12. For full notes on Themes 1 through 7.3, kindly refer to Prof. Nombona’s Lecture
notes for 2026.

My YouTube Channel
I have a YouTube Channel called The van der Poll Method. It contains old lecture material and examples, as well as the
solutions to additional problems. 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.

Preparing for Lectures

To get the most out of my lectures, you must ensure that you have prepared the sections outlined in the study calendar below.
Of special importance are those for the first lecture. Ensure that you read ahead and stay up to date. By you preparing, the idea
is to increase the time we have to discuss the nuance of the work rather than having to rush through all of the content.

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 CMY 117 | General Chemistry

Study Timetable

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 Table of Contents

Theme 7 Types of Chemical Reactions and 8.6 How do We Measure Changes in Enthalpy and
Reactions in Aqueous Solution 1 Internal Energy? . . . . . . . . . . . . 26

8.6.1 Measuring Enthalpy Change Using

7.4 Aqueous Reactions and Chemical Analysis . . . 1
Calorimetry . . . . . . . . . . . . . . . . . . . . . . 26

7.4.1 Quantitative Chemical Analysis (Gravimetric 8.6.2 Measuring Internal Energy Change Using
Analysis) . . . . . . . . . . . . . . . . . . . . . . . . 1 Calorimetry . . . . . . . . . . . . . . . . . . . . . . 27

7.4.2 The pH Scale — A Concentration Scale for 8.7 Enthalpy Calculations . . . . . . . . . . 28

Solutions of Acids and Bases . . . . . . . . . . . 3
8.7.1 Hess’s Law — Using Known Reaction
7.4.3 Stoichiometry of Reactions in Aqueous Enthalpies to Calculate Other Reaction
Solution . . . . . . . . . . . . . . . . . . . . . . . . . 4 Enthalpies . . . . . . . . . . . . . . . . . . . . . . . 28

7.5 Additional Practice Problems. . . . . . . . 12 8.7.2 Standard Enthalpies of Formation. . . . . . . . . 29

8.8 Additional Practice Problems. . . . . . . . 31

Theme 8 Energy and Chemical Reactions 16

8.1 Introduction . . . . . . . . . . . . . 16 Theme 9 Physical Properties of Gases 34

8.2 The Basic Definitions of Energy and Energy 9.1 Introduction . . . . . . . . . . . . . 34

Changes . . . . . . . . . . . . . . . 16
9.2 How Do We Model Gases and Gas Pressure? . . 34
8.2.1 The Universe Consists of a System and the
9.3 The Gas Laws . . . . . . . . . . . . . 35
Surroundings . . . . . . . . . . . . . . . . . . . . . 16
9.4 The Ideal Gas Law . . . . . . . . . . . 35
8.2.2 How do the System and the Surroundings
Interact?. . . . . . . . . . . . . . . . . . . . . . . . . 16 9.4.1 The Density of a Gas . . . . . . . . . . . . . . . . . 36

8.3 How Much Heat Can an Object Absorb? — 9.4.2 We can Calculate the Molar Mass of a Gas
Heat Capacity . . . . . . . . . . . . . 18 from P, V, and T Data . . . . . . . . . . . . . . . . 36

8.3.1 What Happens When Energy is Absorbed and 9.5 Gas Laws and Chemical Reactions . . . . . . 38
a Substance Changes State? . . . . . . . . . . . . . 20
9.6 What Happens When We Mix Ideal Gases? —
8.4 The First Law of Thermodynamics . . . . . . 22 Partial Pressures . . . . . . . . . . . . 40

8.4.1 What is Work? . . . . . . . . . . . . . . . . . . . . . 22

9.7 Additional Practice Problems. . . . . . . . 41

8.4.2 The Heat and Work Gives the Total Energy

(The Internal Energy) . . . . . . . . . . . . . . . . 22 Theme 10 Physical Properties of Liquids 43

8.5 The Enthalpy Change and Chemical Reactions . 24 10.1 Introduction . . . . . . . . . . . . . 43

8.5.1 What is Enthalpy Change? . . . . . . . . . . . . . 24 10.2 Intermolecular Forces . . . . . . . . . . 43

8.5.2 The Enthalpy Change in Chemical Reactions. . 24 10.3 Vapourisation and Condensation of Liquids . . 43

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Table of Contents CMY 117 | General Chemistry

10.4 Vapour Pressure . . . . . . . . . . . . 44 11.5.5 Colligative Properties of Electrolyte Solutions

— The van’t Hoff Factor for Ionic Solutions . . 58
10.4.1 The Clausius-Clapeyron Equation. . . . . . . . . 45
11.6 We Can Use Colligative Properties to do Further
10.5 Other Properties of Liquids . . . . . . . . 45
Calculations . . . . . . . . . . . . . 59
10.5.1 Boiling Point . . . . . . . . . . . . . . . . . . . . . . 45
11.7 Additional Practice Problems. . . . . . . . 61
10.5.2 Critical Temperature and Pressure . . . . . . . . 45

10.5.3 Surface Tension, Capillary Action, and

Viscosity . . . . . . . . . . . . . . . . . . . . . . . . 46
Theme 12 Chemical Kinetics 63

10.6 Additional Practice Problems. . . . . . . . 47 12.1 Introduction . . . . . . . . . . . . . 63

12.2 How Fast Does a Reaction Occur? — The Rates

of Reactions . . . . . . . . . . . . . 63
Theme 11 Physical Properties of Solutions 49
12.2.1 How do Chemical Reactions Take Place? . . . . 63
11.1 Introduction . . . . . . . . . . . . . 49
12.2.2 What Factors Influence the Number of
11.2 How Are Solutions Made? . . . . . . . . . 49
Collisions? . . . . . . . . . . . . . . . . . . . . . . . 63
11.2.1 Why do Solutes Dissolve in Solvents? . . . . . . . 49
12.2.3 How Do We Measure the Rate of a Reaction? . . 66
11.2.2 What are the Energy Consequences of Making
12.3 How Do Concentrations Affect The Reaction
a Solution? . . . . . . . . . . . . . . . . . . . . . . . 50
Rate? (Rate Equations) . . . . . . . . . . 67
11.3 Units of Concentration . . . . . . . . . . 50
12.3.1 What is a Rate Equation? . . . . . . . . . . . . . . 68
11.4 Pressure and Temperature Affect the Solubility
12.3.2 The Order of a Reaction — How the Rate
of Compounds . . . . . . . . . . . . . 52
Depends on the Concentration . . . . . . . . . . 68
11.4.1 Dissolving Gases in Liquids: Henry’s Law . . . . 52
12.3.3 How do We Determine a Rate Equation?. . . . . 69
11.4.2 Temperature Effects on Solubility — Le
Chatelier’s Principle . . . . . . . . . . . . . . . . . 53 12.4 Concentration–Time Relationships — Integrated
Rate Laws . . . . . . . . . . . . . . 72
11.5 Colligative Properties . . . . . . . . . . 54
12.4.1 Integrated Rate Laws . . . . . . . . . . . . . . . . . 72
11.5.1 Raoult’s Law is About Changes in Vapour
Pressure . . . . . . . . . . . . . . . . . . . . . . . . . 54 12.4.2 The Half-Life of a Reaction . . . . . . . . . . . . . 75

11.5.2 Boiling Points Increase When Solutes are 12.5 How Does Temperature Influence Reaction
Dissolved in Solvents . . . . . . . . . . . . . . . . . 55 Rates?. . . . . . . . . . . . . . . . 77
11.5.3 Freezing Points Decrease When Solutes are 12.5.1 The Graphical Use of the Arrhenius Equation . 77
Dissolved in Solvents . . . . . . . . . . . . . . . . . 56
12.5.2 The Arrhenius Equation with only Two Points . 77
11.5.4 Osmotic Pressure: How Solutions Equilibrate
Their Concentrations . . . . . . . . . . . . . . . . 56 12.6 Additional Practice Problems. . . . . . . . 80

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 Theme Types of Chemical
7 Reactions and Reactions
in Aqueous Solution
Click Here to access this Theme’s YouTube Playlist

7.4 Aqueous Reactions and Chemical Analysis

Aqueous reactions and chemical analysis focus on determining the amount or concentration of a substance in solution. We
will examine several methods and tools for conducting this analysis.

7.4.1 Quantitative Chemical Analysis (Gravimetric Analysis)

Gravimetric analysis is a quantitative analytical technique used to determine the amount of an analyte in a sample by
converting it into a pure, stable compound of known composition, typically via precipitation. For example, Figure 7.1 illustrates
the process where we determine the amount of Na2 SO4 in a sample as follows:

(a) A sample containing an unknown amount of the sulfate ion (here Na2 SO4 ) can be analysed by adding barium chloride.

(b) When BaCl2 is added to the solution containing the sulfate ion, insoluble BaSO4 is precipitated. Sufficient Ba2+ ions are
added to ensure complete precipitation.

(c) Solid BaSO4 is collected in a weighed filter paper. For an accurate analysis all of the solid must be carefully collected.

(d) After drying the BaSO4 in the filter paper, the paper and solid are weighed and the mass of BaSO4 determined.

Figure 7.1: The procedure for analyzing a solution for the sulfate ion content by precipitation. This procedure is an
example of a gravimetric analysis.

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7.4 Aqueous Reactions and Chemical Analysis CMY 117 | General Chemistry

Example 7.1
Analysis of a Mineral
Sodium sulfate, Na2 SO4 , occurs naturally as the mineral thenardite. To analyse 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 7.1).

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 to be discussed during lecture period

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CMY 117 | General Chemistry 7.4 Aqueous Reactions and Chemical Analysis

7.4.2 The pH Scale — A Concentration Scale for Solutions of Acids and Bases

We know that an acid is a proton donor and forms hydronium ions (H3 O+ ) when placed in water. We also know that a base is
−
a proton acceptor and dissociates to form hydroxide ions in water (OH ). Hence, we can use these concentrations to define a
scale of what is considered ”acidic” and ”basic”.

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 ] (7.1)

These pH values are more convenient numbers to use than the numbers in scientific notation often associated with the
concentration of hydronium. You can see that, for example, vinegar (an acid) 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 (7.2)

The pOH Scale

A pOH scale analogous to the pH scale can be defined using the negative base-10 logarithm of the hydroxide ion concentration
−
of a solution, [OH ] as follows
−
pOH = − log[OH ] (7.3)

Rearranging Equation (7.3) to solve for hydroxide ion concentration gives

−
[OH ] = 10−pOH (7.4)

A completely neutral solution (i.e. pure water) must have a pH of 7.00, and the words completely neutral imply that the
concentration of the hydronium ions must be equal to the hydroxide ion concentration, hence the pOH must also be 7.00.
If we sum these quantities, it totals 14.00, and hence the following relationship always holds

pH + pOH = 14.00 (7.5)

Therefore, any increase in the concentration of hydronium ions must be accompanied by a decrease in the concentration of
hydroxide ions, and vice versa. So as a result, if the pH increases, the pOH must decrease etc.

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7.4 Aqueous Reactions and Chemical Analysis CMY 117 | General Chemistry

Example 7.2
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 to be discussed during lecture period

7.4.3 Stoichiometry of Reactions in Aqueous 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 as shown in the following problem solving tip:

Problem Solving Tip 7.1: Stoichiometry Calculations Involving Solutions

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CMY 117 | General Chemistry 7.4 Aqueous Reactions and Chemical Analysis

Example 7.3
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

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7.4 Aqueous Reactions and Chemical Analysis CMY 117 | General Chemistry

Example 7.4
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 is done during a chemical analysis

▷ 150. mL of a 0.810 M HNO3 was accurately diluted to 500. mL by adding distilled water.

▷ 4.000 g of powdered Cu was added to the diluted 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

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CMY 117 | General Chemistry 7.4 Aqueous Reactions and Chemical Analysis

Acid-Base Titrations

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 process we call a titration. Figure 7.2 illustrates the procedure of a titration.

Figure 7.2: Titration of an acid in aqueous solution with a base.

The titration shown in Figure 7.2 follows the following steps:

1. A buret (a volumetric measuring device calibrated in divisions of 0.1 mL), is filled with an aqueous solution of a base of
known concentration.

2. In a flask, we add a specific volume (and so a fixed amount) of the acid and a few drops of a dye called an indicator.

3. The base is added slowly from the buret to the solution in the flask at the bottom.
−
4. When the amount of NaOH (i.e. the [OH ]) added from the buret equals the amount of H3 O+ supplied by the acid, we
reach a point called the equivalence point. At this point, the indicator changes colour, which is our indication that all
the acid at the bottom has reacted. (The indicator used here is phenolphthalein.)

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7.4 Aqueous Reactions and Chemical Analysis CMY 117 | General Chemistry

Example 7.5
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

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CMY 117 | General Chemistry 7.4 Aqueous Reactions and Chemical Analysis

Example 7.6
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

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7.4 Aqueous Reactions and Chemical Analysis CMY 117 | General Chemistry

We can also determine the Molar Mass of a substance 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 7.7
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

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CMY 117 | General Chemistry 7.4 Aqueous Reactions and Chemical Analysis

Oxidation-Reduction (Redox) Titrations

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 7.8
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

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7.5 Additional Practice Problems CMY 117 | General Chemistry

7.5 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
gases 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.

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CMY 117 | General Chemistry 7.5 Additional Practice Problems

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.

(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?

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7.5 Additional Practice Problems CMY 117 | General Chemistry

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 0.125 g sample of chalk. The student
placed the chalk sample in a 250 mL conical flask and added 50.00 mL 0.200 M HCl using a pipette. The excess HCl was then
titrated with 0.250 M NaOH. The average NaOH titre was 32.12 mL 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. 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.

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CMY 117 | General Chemistry 7.5 Additional Practice Problems

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.

15 University of Pretoria | Department of Chemistry

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

8.1 Introduction

Energy plays a central role in everyday life and in chemical processes, from heating homes and generating electricity to
powering transport and sustaining biological systems. Much of this energy arises from chemical reactions, particularly the
combustion of fossil fuels and the metabolic reactions that occur in living organisms.

Thermodynamics is the branch of science concerned with energy and its relationship to heat and work. In chemistry,
thermodynamics focuses on measuring and understanding the energy changes associated with chemical reactions, particularly
those involving heating and cooling, to better describe and predict chemical behaviour.

8.2 The Basic Definitions of Energy and Energy Changes

Energy is the capacity to perform work, categorised into kinetic energy related to motion and potential energy derived from
an object’s position or state, with thermal energy referring to molecular kinetic energy in chemistry. Though energy can be
converted from one type into another, the total amount of energy is always 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.

8.2.1 The Universe Consists of a System and the Surroundings

Because energy must be conserved, we must define how energy flows between objects in order to conserve the total energy. In
thermodynamics, the terms system and surroundings have precise and important meanings. The entire universe can be split
into two ideas as follows

▷ A system is defined as an object, or a collection of objects, that we are interested in studying.

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

Hence, we can 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.

8.2.2 How do the System and the Surroundings Interact?

In thermodynamics, the system and surroundings interact through the exchange of energy as heat (𝑞) and work (𝑤), and in
some cases through the transfer of matter. This leads to the classification of different types of systems as we will discuss now.

16
CMY 117 | General Chemistry 8.2 The Basic Definitions of Energy and Energy Changes

An Isolated System

Consider a system that cannot exchange matter or energy with the surroundings. This means only objects within the system
may exchange heat. So, let’s place two objects at different temperatures in contact with each other in this system and discuss
what happens:

1. We expect the spontaneous transfer of heat from the object at a higher temperature to the object at a lower temperature.
We say that the object whose temperature increases gains thermal energy, and the object whose temperature
decreases loses thermal energy.

2. This transfer of energy as heat will continue until both objects are at the same temperature. We call this point thermal
equilibrium.

Hence, if we completely isolate the system from the surroundings, the only process that can happen is that objects in the system
can exchange their own heats. This defines the idea of an isolated system.

A Closed System

Now let’s allow the system to exchange energy with the surroundings, but still not matter. When only energy can be
transferred as heat between a system and its surroundings (see Figure 8.1), we define this as a closed system. How the energy
flows, specifically how the energy flows in terms of heat, is described as either exothermic or endothermic, meaning the
following:

▷ In an exothermic process, energy is transferred as heat from the 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).

▷ In an endothermic 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.

Figure 8.1: Exothermic and endothermic processes. The symbol q represents the energy transferred as heat, and the subscript
sys refers to the system.

An Open System

In our final type of system, we will allow the system to exchange both matter and energy. In such a case, we call it an open
system. The system is completely open to interact with the surroundings. We rarely study this type of system in thermodynamics.

17 University of Pretoria | Department of Chemistry

8.3 How Much Heat Can an Object Absorb? — Heat Capacity CMY 117 | General Chemistry

8.3 How Much Heat Can an Object Absorb? — Heat Capacity

When an object is heated or cooled without a change in its physical state, its temperature change is proportional to the quantity
of thermal energy gained or lost by the object, i.e. 𝑞 ∝ 𝑇. Hence, a proportionality constant exists so that the energy gained or
lost as heat (𝑞, in joules) is described by Equation (8.1)

𝑞 = 𝐶Δ𝑇 (8.1)

The constant, 𝐶, is called the heat capacity. This constant is usually reported in units of J⋅K−1 and 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 .

However, it is often more useful to know how the amount of substance (i.e. its mass) influences the amount of heat absorbed.
For this, the specific heat capacity (𝑐s ) 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 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 (8.2)
𝑞 = 𝑐s 𝑚Δ𝑇 (8.2)

In a similar fashion, the 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, 𝑐m .

Interestingly, specific heat capacity strongly influences energy transfer in everyday systems. Water’s high specific heat capacity
(4.184 J ⋅ g−1 ⋅ K−1 ) allows large bodies of water to moderate the area’s climate by warming and cooling slowly. In contrast,
aluminium foil has a low specific heat capacity (0.897 J ⋅ g−1 ⋅ K−1 ), so even when heated in an oven, it transfers relatively little
energy to your fingers if you take it out.

Example 8.1
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

University of Pretoria | Department of Chemistry 18

CMY 117 | General Chemistry 8.3 How Much Heat Can an Object Absorb? — Heat Capacity

Example 8.2
Using Specific Heat Capacity
Consider an 88.5 g piece of iron at 78.8 °C (352.0 K) placed in a beaker containing 244 g of water at 18.8 °C (292.0 K),
forming an isolated system. When thermal equilibrium is reached, what is the final temperature?

Solution to be discussed during lecture period

19 University of Pretoria | Department of Chemistry

8.3 How Much Heat Can an Object Absorb? — Heat Capacity CMY 117 | General Chemistry

8.3.1 What Happens When Energy is Absorbed and a Substance Changes 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 (Δ𝐻fus ).

▷ The energy transferred as heat to convert a liquid to a vapour is called the heat of vaporization (Δ𝐻vap ).

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 (the intermolecular forces), and hence there is no
energy left to increase the temperature. This can be shown graphically as follows:

Example 8.3
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 . You will also need the following
values:

𝑐s, ice = 2.06 J ⋅ g−1 ⋅ K−1 𝑐s, liquid water = 4.184 J ⋅ g−1 ⋅ K−1 𝑐s, water vapour = 1.86 J ⋅ g−1 ⋅ K−1

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 20

CMY 117 | General Chemistry 8.3 How Much Heat Can an Object Absorb? — Heat Capacity

Extra Space

21 University of Pretoria | Department of Chemistry

8.4 The First Law of Thermodynamics CMY 117 | General Chemistry

8.4 The First Law of Thermodynamics

Thermodynamics is the science of how energy is transferred as heat and work. Up to this point in the theme, we have only
spoken of heat. The work (𝑤) done by a system or on a system also affects the energy in the system.

8.4.1 What is Work?

We will specifically consider 𝑝–𝑉 work (pressure-volume work). This means we look at the work of systems in terms of their
pressure and volume. For example, if a gas expands against a constant external pressure, the gas molecules do work (use some
of their energy) to push against the external pressure and expand their container volume. We can calculate the work they do
as follows:
𝑤 = −𝑝Δ𝑉 (8.3)

A Closer Look 8.1: 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.

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; and the work is positive, 𝑤 > 0.

8.4.2 The Heat and Work Gives the Total Energy (The Internal Energy)

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 (8.4),

Δ𝑈 = 𝑤 + 𝑞 (8.4)

University of Pretoria | Department of Chemistry 22

CMY 117 | General Chemistry 8.4 The First Law of Thermodynamics

Equation (8.4) is the mathematical statement of the First Law of Thermodynamics. In words, the first law states that:

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 (8.4) provides a means for determining Δ𝑈, simply measure the energy transferred as heat and work to or from
the system. Because the work and heat may be positive or negative quantities, they will have different impacts on the internal
energy change 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

Lastly, Equation (8.4) implies that in a constant-volume process, where Δ𝑉 = 0, the energy transferred as work must be zero:
𝑤 = −𝑝Δ𝑉 = 0. Thus, the change in internal energy of the system under constant-volume conditions is equal only to the
energy transferred as heat (Δ𝑈 = 𝑞𝑉 ), where the subscript 𝑉 indicates conditions of constant volume.

Example 8.4
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

23 University of Pretoria | Department of Chemistry

8.5 The Enthalpy Change and Chemical Reactions CMY 117 | General Chemistry

8.5 The Enthalpy Change and Chemical Reactions

8.5.1 What is Enthalpy Change?

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, the internal energy is

Δ𝑈 = 𝑞𝑝 + 𝑤𝑝

where the subscript 𝑝 indicates conditions of constant pressure. If the only type of work that occurs is 𝑝–𝑉 work. So,

Δ𝑈 = 𝑞𝑝 − 𝑝Δ𝑉 ⟹ 𝑞𝑝 = Δ𝑈 + 𝑝Δ𝑉

This means that the heat at constant pressure is a defined quantity that describes a reaction under constant pressure conditions.
This is of such importance, we introduce a new thermodynamic quantity called The Enthalpy, symbol 𝐻, and its change, the
change in enthalpy, can be calculated as follows

Δ𝐻 = 𝑞𝑝 = Δ𝑈 + 𝑝Δ𝑉 (8.5)

Hence, for a system at constant pressure, the heat transferred is the enthalpy change. 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:

▷ If 𝑞𝑝 < 0 then Δ𝐻 < 0, and so energy is transferred as heat from the system to the surroundings (exothermic process).

▷ If 𝑞𝑝 > 0 then Δ𝐻 > 0, and so energy is transferred as heat from the surroundings to the system (endothermic process).

The Enthalpy and Internal Energy are Called State Functions

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 for a given reaction. A quantity that has
this property is called a state function.

On the other hand, work and heat are quantities whose value depends on the path taken. 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.

8.5.2 The Enthalpy Change in Chemical Reactions

A chemical reaction leads to a change in enthalpy, because heat is either lost or absorbed at constant pressure during the
reaction. We call this change in enthalpy the standard reaction enthalpy, Δr 𝐻 −∘ . There are two important things to know
about Δr 𝐻 −∘ :

1. The standard reaction 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.
−1
2. It has units of kJ ⋅ mol , where the ”per mol” means that this is the enthalpy change for one mole of 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.

University of Pretoria | Department of Chemistry 24

CMY 117 | General Chemistry 8.5 The Enthalpy Change and Chemical Reactions

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, so the number of times the reaction as written is
carried out.

▷ Δr 𝐻 −∘ has a negative value for an exothermic reaction and 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.

Example 8.5
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 −∘ = −5645 kJ ⋅ mol

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

25 University of Pretoria | Department of Chemistry

8.6 How do We Measure Changes in Enthalpy and Internal Energy? CMY 117 | General Chemistry

8.6 How do We Measure Changes in Enthalpy and Internal Energy?

The energy evolved or absorbed as heat in a chemical or physical process can be measured by a technique called calorimetry.
The apparatus used in this kind of experiment is a calorimeter.

8.6.1 Measuring Enthalpy Change Using Calorimetry

A constant-pressure calorimeter (called a coffee-cup calorimeter) can be used to

measure the quantity of energy transferred as heat under constant-pressure conditions.
Because the heat under constant pressure is equal to the change in enthalpy, this
technique allows us to measure the change in enthalpy for a given reaction.

In this situation, we define the reacting chemicals and the solution as the system. The
cup provides an isolated system, and so we assume there is no energy transfer to the
surroundings (the cup and beyond).

This means that two energy changes occur within the system. One is the energy
released or gained as heat by the chemical reaction (𝑞r ) itself and The other energy Figure 8.2: Coffee-cup calorimeter
change is the corresponding energy gained or lost as heat by the solution. Hence, by the law of conservation of energy

𝑞r + 𝑞solution = 0 ⟹ 𝑞r = Δr 𝐻 = −𝑞solution

Where the value of 𝑞solution can be calculated from the specific heat capacity, mass, and change in temperature of the solution.

Example 8.6
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

University of Pretoria | Department of Chemistry 26

CMY 117 | General Chemistry 8.6 How do We Measure Changes in Enthalpy and Internal Energy?

8.6.2 Measuring Internal Energy Change 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, which is then submerged in water. Therefore,
we can call the bomb and the water in which it is submerged an isolated system. This
means that our system consists of a reaction, a bomb, and water.

The combustion reaction generates heat (𝑞r ) which is absorbed by the bomb and the
water, to reach thermal equilibrium once more. Then by the conservation of energy

𝑞r + 𝑞bomb + 𝑞water = 0 ⟹ 𝑞r = Δr 𝑈 = −𝑞bomb − 𝑞water

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
Figure 8.3: Bomb caliometer
the calorimeter.

Because the volume does not change in a constant-volume calorimeter, no energy is transferred as work. Therefore, the energy
transferred as heat at constant volume (𝑞𝑉 ) is equal to the change in internal energy of the reaction, Δr 𝑈, often called the heat
of combustion.

Example 8.7
Constant-Volume Calorimetry
Octane, C8 H18 , a primary constituent of gasoline, burns in air

C8 H18 (ℓ) + 25/2 O2 (g) −−−→ 8 CO2 (g) + 9 H2 O (ℓ)

A 1.15 g sample of octane is burned in a constant-volume calorimeter submerged in 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 capacity was previously
determined to be, 𝐶bomb = 837 J ⋅ K−1 . What is the heat of combustion per gram and per mole of octane?

Solution to be discussed during lecture period

27 University of Pretoria | Department of Chemistry

8.7 Enthalpy Calculations CMY 117 | General Chemistry

8.7 Enthalpy Calculations

Chemists often want to know if an unstudied reaction is expected to be exothermic or endothermic and to what extent. We can
determine this using enthalpy data from other reactions and performing specific calculations, which we will discuss in this
section.

8.7.1 Hess’s Law — Using Known Reaction Enthalpies to Calculate Other Reaction Enthalpies

The calculations in this section are 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 8.8
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
−1
Equation 2: H2 (g) + 1/2 O2 (g) −−−→ H2 O (ℓ) Δr 𝐻2−∘ = −285.8 kJ ⋅ mol
−1
Equation 3: CH4 (g) + 2 O2 (g) −−−→ CO2 (g) + 2 H2 O (ℓ) Δr 𝐻3−∘ = −890.3 kJ ⋅ mol

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 28

CMY 117 | General Chemistry 8.7 Enthalpy Calculations

8.7.2 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. 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 in the Appendices, 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 compounds 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 be used to compare the stabilities of related compounds.

Using Enthalpies of Formation to Calculate Reaction Enthalpies

Using standard molar enthalpies of formation and Equation (8.6), it is possible to calculate the enthalpy change for a reaction
under standard conditions.
Δr 𝐻 −∘ = ∑ 𝑛𝑖 Δf 𝐻 −∘ (products) − ∑ 𝑛𝑖 Δf 𝐻 −∘ (reactants) (8.6)
𝑖 𝑖

Example 8.9
Using Enthalpies of Formation
Nitroglycerin, C3 H5 (NO3 )3 , is a powerful explosive that forms four different gases when detonated:

2 C3 H5 (NO3 )3 (ℓ) −−−→ 3 N2 (g) + 1/2 O2 (g) + 6 CO2 (g) + 5 H2 O (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 your textbook to find other Δf 𝐻 −∘ values that are needed.

Solution to be discussed during lecture period

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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 m 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 m 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

29 University of Pretoria | Department of Chemistry

8.7 Enthalpy Calculations CMY 117 | General Chemistry

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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 30

CMY 117 | General Chemistry 8.8 Additional Practice Problems

8.8 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.

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.

31 University of Pretoria | Department of Chemistry

8.8 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

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 , 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 , (ℳC6 H12 O6 = 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
−1
850. g of water and the bomb had a heat capacity of 874 J ⋅ °C , 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

−1
C3 H8 (g) + 5 O2 (g) −−−→ 3 CO2 (g) + 4 H2 O (ℓ) Δr 𝐻 −∘ = −2220 kJ ⋅ mol
−1
C (s) + O2 (g) −−−→ CO2 (g) Δr 𝐻 −∘ = −393.5 kJ ⋅ mol
−1
H2 (g) + 1/2 O2 (g) −−−→ H2 O (ℓ) Δr 𝐻 −∘ = −285.5 kJ ⋅ mol

University of Pretoria | Department of Chemistry 32

CMY 117 | General Chemistry 8.8 Additional Practice Problems

Enthalpy Change of Reaction

−1
Determine the enthalpy change that occurs when 65.14 g of ethylene (ℳC2 H2 = 26.04 g ⋅ mol ) 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 O2
−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

33 University of Pretoria | Department of Chemistry

 Theme Physical Properties
9 of Gases
Click Here to access this Theme’s YouTube Playlist

9.1 Introduction

Gas behaviour is the easiest state of matter to understand at the molecular level, allowing its properties to be described both
qualitatively through molecular motion and quantitatively using simple mathematical models. Studying gases introduces the
use of scientific models to explain and predict natural phenomena.

9.2 How Do We Model Gases and Gas Pressure?

A gas can be accurately described using four variables: pressure (𝑝), volume (𝑉), temperature (𝑇, in kelvins), and amount
(𝑛). Pressure is defined as the force exerted per unit area and is commonly expressed in several units, including millimetres
of mercury (mmHg), atmospheres (atm), pascals (Pa), kilopascals (kPa), and bar. At sea level, standard atmospheric pressure
is defined as
1 atm = 760 mmHg = 101.325 kPa = 1.01325 bar

We can also equate the units to bar as follows

1 bar = 1 × 105 Pa = 1 × 102 kPa = 0.98692 atm

A Closer Look 9.1: 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.

34
CMY 117 | General Chemistry 9.3 The Gas Laws

Example 9.1
Pressure Unit Conversions
Convert a pressure of 635 mmHg into its corresponding value in units of atmospheres (atm), bars, and kilopascals (kPa).

Solution discussed in Video Lecture

9.3 The Gas Laws

This section is self-study since it formed part of the Grade 12 curriculum. See your textbook and the Additional Study Material and
ensure that you understand the basis of the gas laws (Boyle’s law, Charles’s law, Avogadro’s hypothesis).

9.4 The Ideal Gas Law

From the gas laws, four quantities can be used to describe a gas: pressure, volume, temperature, and amount (moles). We can
summarise the relations below:

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, when quantities are proportional to each other, we can equate them if we introduce some proportionality constant.
In this case, let us denote the constant by 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 (9.1)
𝑝
The equation 𝑃𝑉 = 𝑛𝑅𝑇 is called the Ideal Gas Equation. It describes the behaviour of a so-called ideal gas. There are no
ideal gases, but the law holds under certain conditions for most gases. The value of 𝑅 is determined experimentally and can be
confirmed by doing a calculation at STP (standard temperature and pressure).

35 University of Pretoria | Department of Chemistry

9.4 The Ideal Gas Law CMY 117 | General Chemistry

Example 9.2
Ideal Gas Law
The nitrogen gas in a car 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

9.4.1 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
ℳ
we use this for 𝑛 in Equation (9.1), we can write

𝑚 𝑚 𝑝ℳ
𝑝𝑉 = ( ) 𝑅𝑇 ⟹ =
ℳ 𝑉 𝑅𝑇

Notice that 𝑚/𝑉 is the density of the gas, so 𝑚/𝑉 = 𝑑, and hence

𝑝ℳ
𝑑= (9.2)
𝑅𝑇

Example 9.3
Density and Molar Mass
Calculate the density (in units of g⋅L−1 ) of CO2 at STP.

Solution discussed in Video Lecture

9.4.2 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.

University of Pretoria | Department of Chemistry 36

CMY 117 | General Chemistry 9.4 The Ideal Gas Law

Example 9.4
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

37 University of Pretoria | Department of Chemistry

9.5 Gas Laws and Chemical Reactions CMY 117 | General Chemistry

9.5 Gas Laws and Chemical 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 9.1 connects these calculations for gas reactions with the stoichiometry calculations. The amount of A
(in moles) can be determined from its mass, from the concentration and volume of a solution, or from pressure, volume, and
temperature using the ideal gas law. Using the mole ratio from the balanced equation, the amount of B is then calculated and
converted to the required quantity, such as mass, solution concentration, solution volume, or gas properties.

Figure 9.1: A general scheme for stoichiometric calculations relates substances A and B, which may be reactants or products.

Example 9.5
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

University of Pretoria | Department of Chemistry 38

CMY 117 | General Chemistry 9.5 Gas Laws and Chemical Reactions

Example 9.6
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

39 University of Pretoria | Department of Chemistry

9.6 What Happens When We Mix Ideal Gases? — Partial Pressures CMY 117 | General Chemistry

9.6 What Happens When We Mix Ideal Gases? — Partial Pressures

The air we all breathe is a mixture of nitrogen, oxygen, argon, carbon dioxide, water vapour, 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, this law states that

𝑝total = 𝑝A + 𝑝B + 𝑝C + … (9.3)

where 𝑝A , 𝑝B , and 𝑝C are the pressures of the different gases A, B, and C 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:

𝑅𝑇 𝑅𝑇 𝑅𝑇
𝑝total = 𝑝A + 𝑝B + 𝑝C = 𝑛A ( ) + 𝑛B ( ) + 𝑛C ( )
𝑉 𝑉 𝑉

𝑅𝑇
= (𝑛A + 𝑛B + 𝑛C ) ( )
𝑉

𝑅𝑇
= 𝑛total ( )
𝑉

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 + 𝑛B + 𝑛C 𝑛total 𝑋A

And so, combining our results, we find:

𝑛A 𝑅𝑇 𝑛A 𝑅𝑇
𝑝total = ( )( ) ⟹ 𝑋A 𝑝total = = 𝑝A
𝑋A 𝑉 𝑉

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.

Example 9.7
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 mmHg. What
is the partial pressure of each gas?

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 40

CMY 117 | General Chemistry 9.7 Additional Practice Problems

9.7 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 ⋅ atm ⋅ 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 vapour:

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

41 University of Pretoria | Department of Chemistry

9.7 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 42

 Theme Physical Properties
10 of Liquids
Click Here to access this Theme’s YouTube Playlist

10.1 Introduction

This theme develops an understanding of liquids at the molecular level. Liquids consist of closely packed particles that interact
strongly but lack the long-range order of solids, making them more complex than gases or solids. Here, we will use these
molecular interactions to explain the physical properties of liquids.

10.2 Intermolecular Forces

This section is left as Self-Study, which means you need to refer to the Additional Study Material Document made available
to you. In the YouTube Playlist, I added old videos for the theme.

10.3 Vapourisation and Condensation of Liquids

Vapourisation, or evaporation, 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.

Therefore, we can deduce that vaporisation 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 vaporise 1 mole of a liquid is the
−
∘
standard molar enthalpy of vaporisation, Δ𝐻vap :

Vapourisation
−
∘
Liquid −−−−−−−−−−−−−−−−→ Vapour Δ𝐻vap = molar enthalpy of vapourisation
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 − Δ𝐻vap = molar enthalpy of condensation
Energy Released By Vapour

Condensation is the reverse of vaporisation 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 vapourisation.

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

43
10.4 Vapour Pressure CMY 117 | General Chemistry

10.4 Vapour Pressure

Water completely evaporates (due to diffusion) in an open beaker, but not in a sealed one. What happens in the sealed case? In
Figure 10.1, this process is illustrated. A volatile liquid is placed in an evacuated flask. At the beginning, no molecules of the
liquid are in the vapour phase. After a short time, some liquid evaporates, and the molecules now in the vapour phase exert
a pressure. The pressure of the vapour measured when the liquid and the vapour are in equilibrium is called the equilibrium
vapour pressure.

Figure 10.1: An illustration of how vapour pressure is measured.

We can plot the 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 of vapour pressure curves are shown in Figure 10.2. We can use these curves to deduce
the relative strength of intermolecular forces in different substances.

Figure 10.2: vapour pressure curves for diethyl ether [(C2 H5 )2 O], 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.

University of Pretoria | Department of Chemistry 44

CMY 117 | General Chemistry 10.5 Other Properties of Liquids

10.4.1 The Clausius-Clapeyron Equation

We saw in Figure 10.2 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
−∘
Δ𝐻vap
ln(𝑝) = − ( ) + Constant (10.1)
𝑅𝑇

Equation (10.1) is called the Clausius-Clapeyron Equation.

−
∘
An alternative equation allows you to estimate Δ𝐻vap if you
know the vapour pressure of a liquid at two temperatures
−
∘
𝑝2 Δ𝐻vap 1 1
ln ( )=− ( − ) (10.2)
𝑝1 𝑅 𝑇2 𝑇1

−
∘
We can then solve this equation for Δ𝐻vap to estimate its
value. We start the rearrangement as follows

𝑝2 −
∘ 1 1
−𝑅 ln ( ) = Δ𝐻vap ( − ) Figure 10.3: 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 ( −
∘
) = Δ𝐻vap ( 1 )
𝑝1 𝑇2 𝑇1
and so
𝑝2 𝑇𝑇
−
∘
∴Δ𝐻vap = −𝑅 ln ( )[ 2 1 ]
𝑝1 𝑇1 − 𝑇2

10.5 Other Properties of Liquids

10.5.1 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.

10.5.2 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 . The 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 10.4.

45 University of Pretoria | Department of Chemistry

10.5 Other Properties of Liquids CMY 117 | General Chemistry

Figure 10.4: 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.

Figure 10.4 first shows the separate phases of CO2 through a window in a high-pressure vessel. As the sample warms and the
pressure increases, the meniscus becomes less distinct. Once the critical 𝑇 and 𝑝 are reached, distinct liquid and vapour phases
are no longer in evidence. This homogeneous phase is called supercritical CO2 .

10.5.3 Surface Tension, Capillary Action, and Viscosity

Molecules in a liquid have no net force acting on them. However, molecules at the surface of a liquid experience 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 is the movement of a liquid up a thin tube and the observation of a curved meniscus when liquids are in
various containers. These are the consequences of intermolecular forces.

Another important property of liquids that intermolecular forces play a role in is viscosity. Viscosity is 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 46

CMY 117 | General Chemistry 10.6 Additional Practice Problems

10.6 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 10.2 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 10.2 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?

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10.6 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 48

 Theme Physical Properties
11 of Solutions
Click Here to access this Theme’s YouTube Playlist

11.1 Introduction

Building on the properties of liquids, this Theme introduces solutions and the key factors that govern solubility in liquid
solvents, explaining why some substances dissolve readily while others form separate phases, and why the solubility of
gases in liquids depends on temperature. The addition of a solute alters the physical properties of a liquid, an effect central
to many practical applications such as antifreeze and intravenous fluids; these changes, including shifts in freezing point,
boiling point, vapour pressure, and osmotic pressure, are known as colligative properties and depend on the number of
dissolved particles rather than their chemical identity.

11.2 How Are Solutions Made?

Let’s consider making a solution of copper(II) chloride (the solute) in water (the solvent). A solution is saturated once the
solute has reached its maximum concentration in the solution. Hence, the liquid will no longer dissolve the solute even if you
add more of it. 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. We can visualise this process as
follows

11.2.1 Why do Solutes Dissolve in Solvents?

The ability of a solute to dissolve in a solvent depends on the intermolecular interactions between their particles. In general,
polar solids dissolve in polar solvents, while non-polar solids dissolve in non-polar solvents. This observation is summarised
by the like-dissolves-like principle, which states that substances of similar polarity are more likely to form stable solutions.

Liquids may also dissolve in other liquids, still following the like-dissolves-like guideline. If two liquids mix in all proportions
to form a single homogeneous phase, they are said to be miscible (e.g. ethanol and water). In contrast, immiscible liquids do
not mix completely and instead form separate layers, as in the case of oil and water.

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11.3 Units of Concentration CMY 117 | General Chemistry

11.2.2 What are the Energy Consequences of Making a Solution?

The like-dissolves-like guideline is based on changes in enthalpy and entropy (more of this in CMY 127) during dissolution.
Solvation is energetically favourable when the intermolecular forces between solute and solvent are similar, resulting in only
a small energy change upon mixing.

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

1. NaCl (s) ⟶ Na+ (s) + Cl− (s), where the energy required to do this is −Δ𝐻lattice .

2. Na+ (s) + Cl− (s) ⟶ Na+ (aq) + Cl− (aq), where the energy here is called Δ𝐻hydration .

So, the enthalpy of the overall reaction, called the enthalpy of solution (Δ𝐻soln ), is the sum of the two enthalpy changes:

Δ𝐻soln = −Δ𝐻lattice + Δ𝐻hydration

As a general rule, an ionic compound is water-soluble if its enthalpy of solution is exothermic or only slightly endothermic.
In the endothermic case, the positive enthalpy is negated by a favourable entropy of solution. If the enthalpy of solution is
strongly endothermic, the compound is unlikely to dissolve. This is why dissolving ionic compounds in non-polar solvents is
energetically unfavourable, because the solvent cannot stabilise the ions effectively.

11.3 Units of Concentration

By dissolving a solute in a solvent, we need to know how much solute and solvent are present. Quantitatively, we define this
as the concentration of a solute. Thus far, the only concentration unit we have looked at was molarity (M or mol ⋅ L−1 ), which
was the amount of solute (mol) per litre of solution. However, we can define several other concentration units.
−1
The first of which is the molality (𝑚 or mol ⋅ kg ), of a solution, which is defined as the amount of solute (mol) per kilogram
of solvent
amount of solute (mol) −1
𝑐 = molality of solute = = mol ⋅ kg = 𝑚 (11.1)
mass of solvent (kg)
We have also looked at the mole fraction, 𝑋, of a solution component, which 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 = and 𝑋A + 𝑋 B + 𝑋 C + … = 1 (11.2)
𝑛A + 𝑛 B + 𝑛 C + …

Another concentration unit is Percent by Mass, which is the mass of one component divided by the total mass of the mixture,
multiplied by 100%:
Mass of A
Mass Percent A = × 100% (11.3)
Mass of A + Mass of B + Mass of C + …

The term percent literally means “parts per hundred”. If we were to use Equation (11.3) but multiply by 1000 instead of 100,
we would get “parts per thousand” and multiplying by 106 would give “parts per million” or ppm as follows

Mass of A
ppm of A = × 106 (11.4)
Mass of A + Mass of B + Mass of C + …

The units parts per million (ppm), parts per billion (ppb), and parts per trillion (ppt) are usually used to express very low
concentrations, such as those of some pollutants in the atmosphere or a body of water. In a physical sense, 1.0 ppm represents
a solution containing 1.0 gram of a substance in a sample with a total mass of 1.0 million gram (equivalent to 1 mg in 1000 g).

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CMY 117 | General Chemistry 11.3 Units of Concentration

Example 11.1
Calculating Mole Fraction, Molality, Molarity, Mass Percent and ppm
−1
Suppose you add 1.2 kg of ethylene glycol, HOCH2 CH2 OH (ℳ = 62.07 g ⋅ mol ), as an antifreeze to 4.0 kg of water
−1
(ℳ = 18.015 g ⋅ mol ) in your car. What are the mole fraction, molality, mass percent and ppm of the ethylene glycol
in the solution? The density of water is 1.00 L⋅kg−1 .

Solution to be discussed during lecture period

51 University of Pretoria | Department of Chemistry

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

11.4 Pressure and Temperature Affect the Solubility of Compounds

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.

11.4.1 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 𝑆g ∝ 𝑝g . Hence, by introducing a proportionality constant this can be
Gases in Water (25 °C)
represented as
Gas k H (mol⋅kg ⋅bar )
−1 −1 𝑆g = 𝑘H 𝑝g (11.5)

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 to the left), a constant characteristic of
H2 7.8 × 10−4 the solute and solvent. A good example of Henry’s law in action is that of carbonated
N2 6.0 × 10 −4 soft drinks.

O2 1.3 × 10−3 The effect of pressure on gas solubility can be understood at the particulate level.
Gas solubility is the concentration of a gas dissolved in a liquid when equilibrium
CO2 0.034 exists between the dissolved and gaseous states. Increasing pressure causes more gas
CH4 1.4 × 10−3 molecules to enter the solution, raising the dissolved gas concentration until a new
equilibrium is established where the rates of gas molecules entering and leaving the
C2 H6 1.9 × 10−3 solution are equal.

Example 11.2
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, given that the mole fraction of O2 in air is 0.21 and its Henry’s Law
−1 −1
Constant in water is 𝐾H, O2 = 1.3 × 10−3 mol ⋅ kg ⋅ bar .

Solution to be discussed during lecture period

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CMY 117 | General Chemistry 11.4 Pressure and Temperature Affect the Solubility of Compounds

11.4.2 Temperature Effects on Solubility — Le Chatelier’s Principle

The Solubility of All Gases in Water Decreases with Increasing Temperature

You may realise this from everyday observations, such as the appearance of air bubbles as water is heated below the boiling
point, that the solubility of all gases in water decreases with increasing temperature. It is possible to predict the effect of
temperature 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
Δ𝐻soln is negative

Exothermic Process
Gas + liquid solvent −
↽−−−−−−−−−−−−−−−−−−−−−−
⇀− saturated solution + energy Δ𝐻soln < 0
Endothermic Process

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. For example, the addition of energy will cause the system
to shift towards the left, and vice versa.

The Solubility of Solids in Water is also Affected by Temperature

Unlike the situation involving solutions of gases, no general pattern of behaviour is observed for how the solubility of solids in
water varies with temperature. In Figure 11.1, 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 exploit the temperature dependence of solid solubility 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 reduce solubility
(see the photos in Figure 11.1). When the limit of solubility is reached at the lower temperature, crystals of the pure compound
form.

Figure 11.1: 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.

53 University of Pretoria | Department of Chemistry

11.5 Colligative Properties CMY 117 | General Chemistry

11.5 Colligative Properties

Colligative properties are the physical changes that result from adding solute to a solvent. Colligative Properties depend on
how many solute particles are present as well as the solvent amount, but they do not depend on the type of solute particles,
although they do depend on the type of solvent. They are solution characteristics, like freezing point, boiling point, vapour
pressure, and osmotic pressure.

11.5.1 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, 𝑝solvent , is proportional to the mole fraction (𝑋) of the solvent. Raoult’s law
expresses this relationship:
𝑝solvent = 𝑋solvent 𝑝−
∘
solvent (11.6)

We can also calculate the change in vapour pressure of the solvent over the solution as follows

Δ𝑝solvent = −𝑋solute 𝑝−
∘
solvent (11.7)

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 ) and 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.

Example 11.3
Using Raoult’s Law
You dissolve 651 g of ethylene glycol, HOCH2 CH2 OH, in 1.50 kg of water. What is the vapour pressure of the water
over the solution at 90 °C? Assume ideal behaviour for the solution. At 90 °C, 𝑝−
∘
water = 525.8 mmHg.

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 54

CMY 117 | General Chemistry 11.5 Colligative Properties

11.5.2 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 (11.8)

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 11.4
Boiling Point Elevation
−1
Eugenol, a compound found in nutmeg and cloves, has the formula C10 H12 O2 (ℳeugenol = 164.20 g ⋅ mol ).
What is the boiling point of a solution containing 0.144 g of this compound dissolved in 10.0 g of benzene
−1
(𝐾bp, benzene = 2.53 °C ⋅ m−1 , ℳbenzene = 78.11 g ⋅ mol ), if the normal boiling point of benzene is 80.10 °C?

Solution to be discussed during lecture period

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11.5 Colligative Properties CMY 117 | General Chemistry

11.5.3 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 (11.9)

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 11.5
Freezing Point Depression
−1
What mass of ethylene glycol, HOCH2 CH2 OH (ℳethylene glycol = 62.07 g ⋅ mol ), must be added to 5.50 kg of water
−1
(𝐾fp, water = −1.86 °C ⋅ m−1 , ℳwater = 18.015 g ⋅ mol ) to lower the freezing point of the water from 0.0 °C to −10.0 °C?

Solution to be discussed during lecture period

11.5.4 Osmotic Pressure: How Solutions 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 equilibrium is reached, and the concentration on both
sides of the membrane remains constant. Figure 11.2 illustrates the process of osmosis.

In order for the particles to move across the membrane, we can think of the driving force like 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, this is called
Osmotic Pressure (Π), because it quantifies the pressure exerted on the molecules to reach equilibrium.

University of Pretoria | Department of Chemistry 56

CMY 117 | General Chemistry 11.5 Colligative Properties

Figure 11.2: 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
an equation similar to the ideal gas equation:
Π = 𝑐𝑅𝑇 (11.10)

Where 𝑐 is the molar concentration (in moles per litre), 𝑅 is the gas constant, and 𝑇 is the absolute temperature (in Kelvins).

Example 11.6
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

57 University of Pretoria | Department of Chemistry

11.5 Colligative Properties CMY 117 | General Chemistry

11.5.5 Colligative Properties of Electrolyte Solutions — The van’t Hoff Factor for Ionic Solutions

Salt (NaCl) is often added to snow or ice on roads to lower the melting temperature of the ice or snow and thereby facilitate its
removal from the road. Now recall, for example, that when NaCl dissolves in water, it dissociates into Na+ (aq) and Cl− (aq). So,
for every mole of NaCl dissolved, we get two moles of ions in solution. Similarly, when a formula unit of CaCl2 dissolves, we
get three ions: one Ca2+ ion and two Cl− ions. Thus, for every mole of CaCl2 dissolved, we get three moles of ions in solution.

Colligative properties depend only on the number of dissolved particles and not on the type of particles. This means that a 0.1
𝑚 solution of NaCl will exhibit a freezing-point depression twice that of a 0.1 𝑚 solution of a nonelectrolyte, such as sucrose.
Similarly, we expect a 0.1 𝑚 solution of CaCl2 to depress the freezing point of water three times as much as a 0.1 𝑚 sucrose
solution.

To account for this effect, we introduce and define a quantity called the van’t Hoff factor (𝑖), which is given by:

actual number of particles in solution after dissociation

𝑖= (11.11)
number of formula units initially dissolved in solution

Thus, 𝑖 = 1 for all non-electrolytes. For strong electrolytes such as NaCl and KNO3 , 𝑖 = 2, and for strong electrolytes such as
Na2 SO4 and CaCl2 , 𝑖 = 3. Consequently, the equations for colligative properties must be modified as follows

Δ𝑝solvent = −𝑖𝑋solute 𝑝−
∘
solvent Δ𝑇bp = 𝑖𝐾bp 𝑚solute Δ𝑇fp = 𝑖𝐾bp 𝑚solute Π = 𝑖𝑐𝑅𝑇 (11.12)

In reality, the colligative properties of electrolyte solutions are usually smaller than predicted by the equations, especially at
higher concentrations, because of the formation of ion pairs or ion clusters. An ion pair is made up of one or more cations
and one or more anions held together by electrostatic forces. The presence of an ion pair reduces the number of particles in
solution, thus reducing the observed colligative properties and hence the van’t Hoff factors.

Example 11.7
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
−1
(ℳwater = 18.015 g ⋅ mol and 𝐾fp, water = −1.86 °C ⋅ 𝑚−1 )?

Solution to be discussed during lecture period

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CMY 117 | General Chemistry 11.6 We Can Use Colligative Properties to do Further Calculations

11.6 We Can Use Colligative Properties to do Further Calculations

The colligative properties of non-electrolyte solutions provide a means of determining the molar mass of a solute. Although any
of the four colligative properties can be used in theory for this purpose, only freezing-point depression and osmotic pressure
are used in practice because they show the most pronounced, and therefore the most easily measured, changes. From the
experimentally determined freezing-point depression or osmotic pressure, we can calculate the solution’s molality or molarity,
respectively. Knowing the mass of dissolved solute, we can readily determine its molar mass.

Example 11.8
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
−1
(𝐾bp, benzene = 2.53 °C ⋅ m−1 , ℳbenzene = 78.11 g ⋅ mol ), which has a boiling point of 80.31 °C. Determine the
molar mass of methyl salicylate if the normal boiling point of benzene is 80.10 °C.

Solution to be discussed during lecture period

59 University of Pretoria | Department of Chemistry

11.6 We Can Use Colligative Properties to do Further Calculations CMY 117 | General Chemistry

Example 11.9
Osmotic Pressure and Molar Mass
Beta-carotene is the most important of the A vitamins. If 7.68 mg of 𝛽-carotene is dissolved in chloroform
−1
(ℳchloroform = 119.378 g ⋅ mol ), to form a 10.0 mL solution, which has an osmotic pressure of 26.57 mmHg at 25.0°C.
What is the molar mass of 𝛽-carotene?

Solution to be discussed during lecture period

University of Pretoria | Department of Chemistry 60

CMY 117 | General Chemistry 11.7 Additional Practice Problems

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.

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 ⋅
atm−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 .

61 University of Pretoria | Department of Chemistry

11.7 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 62

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

12.1 Introduction

Chemical kinetics is the study of chemical reaction rates, focusing on how rates are measured, what factors influence them,
and how macroscopic data are used to understand and control reactions at the particulate level.

12.2 How Fast Does a Reaction Occur? — The Rates of Reactions

The rate at which, or how fast, a chemical reaction occurs depends on how frequently and how effectively reacting particles
collide. To explain the rates of reactions, we use the Collision Theory of Reaction Rates.

12.2.1 How do Chemical Reactions Take Place?

A microscopic view of reactions will indicate to us that reactions take place via collisions between molecules. These collisions
have a couple of requirements according to the collision theory, as follows

1. Reacting molecules must collide with one another and do so with sufficient energy to initiate the process of breaking
and forming bonds.

2. Molecules must collide with an orientation that leads to the rearrangement of the atoms and the formation of products.

12.2.2 What Factors Influence the Number of Collisions?

So, the rate of reactions depends on the number of collisions that take place in a reaction vessel. But, what factors can we alter
on a macroscopic level to vary reaction rate? In principle, there are four factors which influence the reaction rate, these are

1. The Concentration of a Reactant. By increasing the reactant concentrations the reaction rate also increases. This is
because if you have more molecules (higher concentration), then more collisions will result.

2. The Temperature. Chemical reactions occur more rapidly at higher temperatures, because the average kinetic energy
of the reactants is higher, leading to more collisions and overall, more successful collisions.

3. The Physical State of Reagents. Heterogeneous reactions occur at the surface of a solid, so the reaction rate depends
on surface area, with larger surface areas leading to more collisions. Homogeneous reactions generally occur faster.

4. Catalysts. These are substances that accelerate chemical reactions but are not themselves consumed. They do so by
providing an alternative pathway for the reaction, one with lower activation energy.

In the sections to follow we discuss each of these factors in light of the collision theory model. Hence, with a focus on their
microscopic origins.

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

The Molecules Require Sufficient Energy — The Activation Energy

In terms of the sufficient energy requirement, the colliding molecules need some minimum energy to overcome an energy
barrier 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 and the reaction will be fast. If the activation energy is high, only a few reactant molecules in a
sample may have enough energy and the reaction will be slow.

Chemists visualise this energy barrier that the reactants must surmount for a reaction to occur in a reaction coordinate
diagram (Figure 12.1). The horizontal axis shows the reaction progress, and the vertical axis the system’s potential energy.
When the energy of the system reaches a maximum, we obtain the transition state of the reaction. At the transition state,
sufficient energy is concentrated in the appropriate bonds, the reactant bonds can now break, and new bonds can form to give
the products. The system is ready to proceed to products, but it could also revert to reactants. Because the transition state is at
a maximum in potential energy, a molecular species with this structure cannot be isolated.

Figure 12.1: Activation energy for the reaction of NO2 and CO to give NO and CO2 .

If the molecules have insufficient energy, it leads to an elastic collision where the molecules simply ”bounce back” after collision,
as shown in Figure 12.2 (a). If the collision has sufficient energy to overcome this activation energy barrier, bonds can break,
and others can form as shown in Figure 12.2 (b).

Figure 12.2: Molecular collisions require sufficient energy to lead to reaction.

Molecules Require the Correct Orientation to React

Not only must reacting molecules have sufficient energy to react, but the reactant molecules must also come together in the
correct orientation to form and break bonds. The lower the probability of achieving the proper alignment, the slower the
reaction. In Figure 12.3 (a), the incorrect orientation does not lead to bond formation, whereas in Figure 12.3 (b), the correct
collision orientation leads to the products being formed.

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CMY 117 | General Chemistry 12.2 How Fast Does a Reaction Occur? — The Rates of Reactions

Figure 12.3: Molecular collisions require sufficient energy to lead to reaction.

Imagine what happens when two or more complicated molecules collide. In only a small fraction of the collisions will the
molecules have exactly the right orientation. Thus, only a small fraction of collisions are effective. No wonder some reactions
are slow, but conversely, it is amazing that so many are fast!

Increasing Temperature Increases the Reaction Rate

The molecules in a sample have a wide range of energies, described by the

Boltzmann distribution of energies. Essentially what this means is that 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, and so
does the fraction of molecules with higher energies.

Hence, by raising the temperature the reaction rate increases, because we

are increasing the fraction of molecules with enough energy to surmount the
Figure 12.4: Energy distribution curve.
activation energy barrier (Figure 12.4).

How do Catalysts Increase the Rate of Reaction?

A catalyst is a substance that increases the rate of a chemical reaction without being consumed itself. It provides an alternative
reaction pathway (known as a mechanism) with a lower activation energy, allowing more particles to react in a given time
(Figure 12.5). Catalysts speed up reactions and enable systems to reach equilibrium more quickly, but they do not affect the
position of equilibrium. Common examples of catalysts include acids and bases, such as those used in esterification reactions.

Figure 12.5: Energy profile for the iodine-catalysed reaction of cis-2-butene to form trans-2-butene.

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

12.2.3 How Do We Measure the Rate of a Reaction?

Any type of rate is 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 Δ[ ] mol ⋅ L−1

Rate of Reaction = = = (12.1)
Change in Time Δ𝑡 s, min, hour etc.

A reaction rate must be a positive quantity, because a reaction is always proceeding at that rate. However, in a reaction,
reactants are consumed, and products are produced. Hence, we need to account for this difference in some manner. For
example, consider the decomposition reaction
A ⟶ B

Let’s plot how the concentrations of A and B change over time during the reaction

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, or the positive of the change in B concentration divided by the change in time:

Change in [A] Δ[A] Change in [B] Δ[B]

Rate of Decomposition of A = − =− Rate of Formation of B = =+
Change in Time Δ𝑡 Change in Time Δ𝑡

The negative sign is required because A is a reactant and its concentration decreases with time (that is, Δ[A] = Δ[A]final −
Δ[A]initial < 0), but rate is always expressed as a positive quantity.

Does Stoichiometry Influence the Rate?

Consider the reaction 2 A + B ⟶ 3 C + D. This reaction implies that A is consumed twice as fast as B (2:1 stoichiometry). In
a similar way, we expect C to form three times as fast as D. So, how can we calculate the overall reaction rate from the rates of
consumption and formation? Intuitively, we have to scale the rates of formation and consumption as follows

1 Δ[A] 1 Δ[B] 1 Δ[C] 1 Δ[d]

Reaction Rate = × (− ) = × (− ) = × (+ ) = + × (+ )
2 Δ𝑡 1 Δ𝑡 3 Δ𝑡 1 Δ𝑡

Note that the reaction rate is now on a per mole of reaction basis. We can generalise this result by looking at a general reaction

𝛼 A + 𝛽 B −−−→ 𝛾 C + 𝛿 d

and then we 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

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CMY 117 | General Chemistry 12.3 How Do Concentrations Affect The Reaction Rate? (Rate Equations)

Instantaneous Rates

In experiments, only average reaction rates can be measured directly, Δ[ ]/Δ𝑡. However, the instantaneous rate of a
chemical reaction can be obtained from a concentration-time graph by drawing a tangent to the curve at a specific time. The
instantaneous rate is defined as the limit of the average rate as the time interval becomes infinitesimally small, that is, as a
differential
d[concentration]
Instantaneous Rate = (12.2)
d𝑡
This corresponds to the slope of the tangent line to the concentration-time curve at a particular point and requires calculus for
its formal definition.

Example 12.1
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)

Solution to be discussed during lecture period

12.3 How Do Concentrations Affect The Reaction Rate? (Rate Equations)

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.

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12.3 How Do Concentrations Affect The Reaction Rate? (Rate Equations) CMY 117 | General Chemistry

12.3.1 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). We know from the collision theory that the rate of a reaction is proportional
on the concentration of the reacting species. Figure 12.6 illustrates this effect for the decomposition of N2 O5 . By doubling the
initial concentration, the average rate also doubles.

Because of this proportionality, we can mathematically

represent it as

Δ[Reactant]
Rate of Reaction = − ∝ [Reactant]
Δ𝑡

So, we can then relate the rate and concentration

using a proportionality constant 𝑘

Δ[Reactant]
Rate of Reaction = − = 𝑘[Reactant]
Δ𝑡

We call an equation of this form a Rate

Equation, where 𝑘 is called The Rate Constant.
The rate constant depends on temperature,
which is the reason we kept the temperature Figure 12.6: Reactant concentration versus time data for the decomposition
constant in this experiment. of N2 O5 , beginning with two different concentrations of N2 O5 .

Now, what if the reaction rate does not double if the concentration is doubled? This means that we need to consider that the
relationship between the rate and the concentration, may not be linear. So, let’s consider a general reaction of the form

𝛼A + 𝛽B ⟶ 𝛾C

The rate equation for this reaction needs to accommodate if the rate and concentration are not linearly dependent. We do this
by defining the relationship in a general sense as follows

Reaction Rate = 𝑘[A]𝑚 [B]𝑛

This rate equation shows that the rate of reaction is proportional to the reactant concentrations, but with each concentration
being raised to some power. This allows for different orders of dependence. The exponents (𝑚 and 𝑛) in the rate equation
must be determined by experiment and they are not necessarily the stoichiometric coefficients (𝛼 and 𝛽) for the balanced
chemical equation. The exponents are often positive whole numbers, but they can also be negative, fractions, or zero.

One interesting fact is that because catalysts are not written as reactants, they are not included in the rate equations. However,
if you have a homogenous catalyst (a catalyst in the same phase as the reactants), then they can appear in the rate equation.

12.3.2 The Order of a Reaction — How the Rate Depends on the Concentration

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 rate equation of

Reaction Rate = 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.

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CMY 117 | General Chemistry 12.3 How Do Concentrations Affect The Reaction Rate? (Rate Equations)

Does the Rate Constant Have Units?

The rate constant, 𝑘, is a proportionality constant that relates rate and concentration at a given temperature. Because the
−1
rate must always have the units of mol⋅L−1 ⋅time , the rate constant has different units depending on the order of the reaction,
as follows

▷ For Zeroth-Order Reactions, the units of 𝑘 are mol⋅L−1 ⋅time−1 .

▷ For First-Order Reactions, the units of 𝑘 are time−1 .

▷ For Second-Order Reactions, the units of 𝑘 are L⋅mol−1 ⋅time−1 .

12.3.3 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 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
measuring the reaction rate after 1% – 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 an example.

Example 12.2
Determining a Rate Equation
The rate of the reaction between CO and NO2 at 540 K as measured starting with various concentrations of CO and
NO2 . The reaction equation is as follows

CO (g) + NO2 (g) ⟶ CO2 (g) + NO (g)

For this reaction, answer the following questions

(a) Determine the rate equation and the value of the rate constant.

(b) 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 .

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

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12.3 How Do Concentrations Affect The Reaction Rate? (Rate Equations) CMY 117 | General Chemistry

Solution to be discussed during lecture period

Hello

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CMY 117 | General Chemistry 12.3 How Do Concentrations Affect The Reaction Rate? (Rate Equations)

Hello

Problem Solving Tip 12.1: Determining a Rate Equation (A Logarithmic Approach)

In Example 12.2, 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)

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12.4 Concentration–Time Relationships — Integrated Rate Laws CMY 117 | General Chemistry

12.4 Concentration–Time Relationships — Integrated Rate Laws

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.

12.4.1 Integrated Rate Laws

This mathematical equation relating time and concentration can be used to plot the concentration-time graphs previously
discussed. We call such an equation an Integrated Rate Law, and with it, you could calculate the concentration at any given
time, or the length of time needed for a given amount of reactant to react.

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]
Reaction Rate = − = 𝑘[R]
Δ𝑡
The relationship can be transformed into a very useful equation called an integrated rate law (because integral calculus is
used in its derivation). By separating the variables and integrating, we obtain

[R]𝑡
ln ( ) = −𝑘𝑡 (12.3)
[R]o

Here, [R]o 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]o , is the fraction of reactant that remains after a given time 𝑡 has elapsed. Notice that 𝑘 for a first-order reaction is
independent of concentration since it has units of time−1 . This means you can choose any convenient unit for [R]𝑡 and [R]o :
moles per litre, moles, grams, number of atoms, number of molecules, or gas pressure.

Example 12.3
The First-Order Integrated Rate Law
In the past, cyclopropane, C3 H6 , was used in a mixture with oxygen as an anaesthetic. (This practice has almost ceased
today because the compound is flammable.) When heated, cyclopropane rearranges to propene in a first-order process.

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

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CMY 117 | General Chemistry 12.4 Concentration–Time Relationships — Integrated Rate Laws

Example 12.4
Using the First-Order Rate Equation
Hydrogen peroxide decomposes in a dilute sodium hydroxide solution at 20 °C in a first-order reaction:

H2 O2 (aq) ⟶ H2 O (ℓ) + 1/2 O2 (g)

−1
Reaction 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?

Solution to be discussed during lecture period

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12.4 Concentration–Time Relationships — Integrated Rate Laws CMY 117 | General Chemistry

The Integrated Rate Law for Second-Order Reactions

Suppose the reaction R ⟶ P is second-order. The rate equation is then

Δ[R]
Reaction Rate = − = 𝑘[R]2
Δ𝑡

Using calculus, this relationship can be transformed into the following equation that relates reactant concentration and time

1 1
− = 𝑘𝑡 (12.4)
[R]𝑡 [R]o

Just as for the integrated first-order rate equation, [R]o 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 .

Example 12.5
Using the Second-Order Integrated Rate Equation
The gas-phase decomposition of HI
HI (g) ⟶ 1/2 H2 (g) + 1/2 I2 (g)

has the rate equation

Δ[HI]
Reaction Rate = − = 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

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CMY 117 | General Chemistry 12.4 Concentration–Time Relationships — Integrated Rate Laws

The Integrated Rate Law for Zeroth-Order Reactions

If a reaction (R ⟶ P) is zeroth-order, the rate equation is

Δ[R]
Reaction Rate = − =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]o = −𝑘𝑡 (12.5)

Zero-order kinetics is observed, for example, in gas-phase reactions occurring on metal surfaces. 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. However, as the reaction proceeds
and the number of reactant molecules decreases, the reaction order, and thus the rate law, is likely to change.

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
(12.3), (12.4), and (12.5) have the form 𝑦 = 𝑚𝑥+𝑏. Hence, the idea is to plot these versions of the equations, identify the straight
line that best fits the data, and then deduce the reaction order. 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]o = −𝑘𝑡 [R]𝑡 vs. 𝑡 −𝑘 mol⋅L−1 ⋅time−1
1 −Δ[R]/Δ𝑡 = 𝑘[R]1 ln ⒧[R]𝑡 /[R]o ⒭ = −𝑘𝑡 ln[R]𝑡 vs. 𝑡 −𝑘 time−1
2 −Δ[R]/Δ𝑡 = 𝑘[R]2 ⒧1/[R]𝑡 ⒭ − ⒧1/[R]o ⒭ = 𝑘𝑡 1/[R]𝑡 vs. 𝑡 𝑘 L⋅mol−1 ⋅time−1

We can plot each of these graphs as shown in Figure 12.7

Figure 12.7: Plots of integrated rate laws for zeroth, first and second order reactions.

12.4.2 The Half-Life of a Reaction

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]o ). 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.

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12.4 Concentration–Time Relationships — Integrated Rate Laws CMY 117 | General Chemistry

The Half-Life of First-Order Reactions

The half-life of a first-order reaction occurs when the following equations are satisfied:

1 [R]𝑡 1
[R]𝑡 = [R] or =
2 o [R]o 2

Half-life is used primarily when dealing with first-order processes. To evaluate t1/2 for a first-order reaction, substitute
either of the above equations and 𝑡 = 𝑡1/2 into the integrated first-order rate equation (Equation (12.3)), and you should find

1
ln ( [R]o ) = −𝑘𝑡1/2 + ln[R]o
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 = (12.6)
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.

The Half-Life of Zeroth and Second Order Reactions

In a similar fashion to how we determined the half-life expression for a first-order reaction, we can determine it for the zeroth-
and second-order reactions. You will find the following

[R]o 1
Zeroth-Order: 𝑡1/2 = Second-Order: 𝑡1/2 = (12.7)
2𝑘 𝑘[R]o

Example 12.6
Half-Life and a First-Order Process
Sucrose, C12 H22 O11 , decomposes to fructose and glucose in acid solution with the rate law

−1
Reaction 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

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CMY 117 | General Chemistry 12.5 How Does Temperature Influence Reaction Rates?

12.5 How Does Temperature Influence Reaction Rates?

Recall 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. These dependencies can be summarised by one equation. We call
this equation The Arrhenius Equation and it is shown in Equation (12.8)

−
𝐸a
𝐸a
𝑘 = 𝐴𝑒 𝑅𝑇 = 𝐴 exp (− ) (12.8)
𝑅𝑇
−1
In this equation, 𝑘 is the rate constant, 𝑅 = 8.31446 × 10−3 kJ ⋅ K−1 ⋅ mol is the gas constant, 𝑇 is the Kelvin temperature,
and the parameter 𝐴 is called the frequency factor. 𝐴 is related to the number of collisions and to the fraction of collisions
that have the correct geometry. It 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, and it always has a value less than 1.

The Arrhenius Equation is significant because it can be used to calculate the activation energy, 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.

12.5.1 The Graphical Use of the Arrhenius Equation

If the 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 (12.8) gives

−
𝐸a
−
𝐸a
𝐸a 1
ln(𝑘) = ln (𝐴𝑒 𝑅𝑇 ) = ln(𝐴) + ln (𝑒 𝑅𝑇 )=− × + ln(𝐴)
𝑅 𝑇

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).

12.5.2 The Arrhenius Equation with only Two Points

In principle, the activation energy, 𝐸a , for a reaction can be obtained algebraically if 𝑘 is known at least two different temperatures
(𝑘1 and 𝑘2 ), and if the activation energy remains constant over the temperature range 𝑇1 to 𝑇2 . You can write an equation for
each set of these conditions:

𝐸a 1 𝐸a 1
ln(𝑘1 ) = − ( ) + ln(𝐴) ln(𝑘2 ) = − ( ) + ln(𝐴)
𝑅 𝑇1 𝑅 𝑇2

And by subtracting these two equations, we obtain an algebraic relationship as follows

𝑘2 𝐸 1 1
ln(𝑘2 ) − ln(𝑘1 ) = ln ( )=− a[ − ] (12.9)
𝑘1 𝑅 𝑇2 𝑇1

Equation (12.9) allows us to calculate the activation energy from only two data points, without the need to measure and plot
additional data.

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12.5 How Does Temperature Influence Reaction Rates? CMY 117 | General Chemistry

Example 12.7
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

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CMY 117 | General Chemistry 12.5 How Does Temperature Influence Reaction Rates?

Example 12.8
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

79 University of Pretoria | Department of Chemistry

12.6 Additional Practice Problems CMY 117 | General Chemistry

12.6 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 Equation: Reaction 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 80

CMY 117 | General Chemistry 12.6 Additional Practice Problems

The Arrhenius Equation

Consider the reaction

2 N2 O5 (g) −−−→ 4 NO2 (g) + O2 (g)

This reaction has the Rate Equation of the form Reaction 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 frequency factor 𝐴.

Reaction Rate

Consider the reaction

2N2 O5 (g) −−−→ 4NO2 (g) + O2 (g)

For this reaction

(a) Write the Rate Equation 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.

81 University of Pretoria | Department of Chemistry

 What comes next?
We hope to welcome you to CMY 127 next
c
semester!