Che Module 3a

MUKUBA UNIVERSITY
DISTANCE LEARNING
DEGREE PROGRAMME.
CHE110: INTRODUCTION TO CHEMISTRY

MODULE 3 (A)
Chemical equilibrium, acids and bases and thermochemistry
[base]
pH= pK+
a log
[acid]
Mukuba university
Kitwe-Zambia
Science Department
Copyright
© Copperbelt University College 2013.
No part of this module may be reproduced or transmitted in any form or by any

means, electronic or mechanical, including photocopying, recording or by any
information storage and retrieval system, without permission in writing from the
publisher.
Mukuba University
Science Department
P.0 Box, 20382
Kitwe – Zambia
Phone: +260212239003
E-mail: cosetco@ zamtel.zn
Acknowledgements
The Copperbelt University College, Science Department wishes to thank the following for
their contribution to this module:
EDITORS
Directorate of Distance Education (DODE)-

Lusaka
AUTHORS
Mweshi E : Lecturer CBUC
Muma E : Lecturer CBUC
Mukonde B: Lecturer CBUC
Changwe P: Lecturer CBUC

out Content
About Content iii
About this Module 1

How this module is structured .......................................................................................... 1
Welcome to the module on Introduction to Chemistry ..................................................... 1
Module outcomes .............................................................................................................. 3
Timeframe ......................................................................................................................... 3
Study skills ........................................................................................................................ 4
Need help? ........................................................................................................................ 5
Assignments ...................................................................................................................... 5
Assessments ...................................................................................................................... 6
Getting around this Module 7

Margin icons ..................................................................................................................... 7
Unit 1 9
Chemical equilibrium ....................................................................................................... 9
1.0 Introduction ....................................................................................................... 9
1.1 The Equilibrium Constant ............................................................................... 10
1.2 Calculation of the Equilibrium concentrations ................................................ 23
1.3 Le Chatelier’s Principle ................................................................................... 26
Unit summary ................................................................................................................. 35
Assessment...................................................................................................................... 36
Unit 2 37
Ionic Equilibria –Acids and Bases .................................................................................. 37
2.0 Introduction ..................................................................................................... 37
2.1 Three concepts of acids and bases ................................................................... 38
2.2 Equilibrium and Acidity-basicity .................................................................... 50
2.2.1 Relative strength of an acid .......................................................................... 50
2.3 The pH (potential of hydrogen) of solutions ................................................... 55
2.3 The pH, pOH, pKw, pKa and pkb ................................................................... 58
2.4 Calculations of the pH ..................................................................................... 62
2.5 Buffer solutions ............................................................................................... 72
2.6 Acid – Base Titrations .................................................................................... 78
Unit summary ................................................................................................................. 84

Assessment...................................................................................................................... 85
Unit 3 86
Thermochemistry ............................................................................................................ 86
3.0 Introduction ..................................................................................................... 86
3.1 Measuring of Heat ........................................................................................... 87
3.2 Hess’s Law ...................................................................................................... 98
3.3 Standards Heat of Formation......................................................................... 102
3.4 Bond Energy .................................................................................................. 107
Unit summary ............................................................................................................... 116
Assessment.................................................................................................................... 117
Answers to Activities .................................................................................................... 118
Activity 2.1 .......................................................................................................... 119
Answers to Assessments ............................................................................................... 121
Readings........................................................................................................................ 122
About this Module

This module is structured as outlined below.
How this module is structured
The module overview
Welcome to the module on

Introduction to Chemistry
This module is part of Introduction to Chemistry Courses in the

Bachelor of Education Science programme. The module introduces
you to chemical equilibrium, acids and base and thermolchemistry.
These concepts will help you to understand subsequent topics in
chemistry. In addition the module lays a very strong foundation in
chemistry as you pursue your studies.
To complete this module successfully, you will need to spend three
(3) hours per week studying the module, and make sure you work
out all the activities in each unit. Don’t move to another unit before
you understand the previous unit. In case you need help contact the
course tutors.
You are expected to do all the self marked activities and one tutor
marked assignment which will accompany this module. You are
required to summit the assignment to the nearest resource centre in
your district. This module has five units.
We strongly recommend that you read the overview carefully

before starting your study.
1
The module content

The module is broken down into units. Each unit comprises:
 An introduction to the unit content.
 Unit outcomes..
 Core content of the unit with a variety of learning activities.
 A unit summary.
 Assignments and/or assessments, as applicable.
Resources
For those interested in learning more on this subject, we provide
you with a list of additional resources at the end of this module;
these may be books, articles or web sites.
Your comments
After completing this module we would appreciate if you would
take a few moments to give us your feedback on any aspect of this
course. Your feedback might include comments on:
 Course content and structure.
 Course reading materials and resources.
 Course assignments.
 Course assessments.
 Course duration.
 Course support (assigned tutors, technical help, etc.)
Your constructive feedback will help us to improve and enhance

this course.
2
Module outcomes
Upon completion of this module you will be able to:
 Explain chemical equilibrium, and apply le chaterlier’s

principle to chemical systems.
 describe Arrhenius, Bronsted-Lowry and Lewis theories of
Outcomes
acids and bases
 Calculate the pH of weak and strong and weak acids and

bases
 Use the equilibrium constants ( K a & K b ) of weak acids and
bases to determine their pH
 Determine the Enthalpy change of a chemical change
Timeframe
This module is expected to be covered within a period of 100
hours. The 100 hours will include studying the actual module
including all the activities.
How long?
3
Study skills
As an Open and Distance Learner your approach to learning will be
different to that from your school days: you will choose what you
want to study, you will have professional and/or personal
motivation for doing so and you will most likely be fitting your
study activities around other professional or domestic
responsibilities.
Essentially you will be taking control of your learning

environment. As a consequence, you will need to consider
performance issues related to time management, goal setting, stress
management, etc. Perhaps you will also need to reacquaint yourself
in areas such as essay planning, coping with exams and using the
web as a learning resource.
Your most significant considerations will be time and space i.e. the
time you dedicate to your learning and the environment in which
you engage in that learning.
We recommend that you take time now—before starting your self-

study—to familiarize yourself with these issues.
4
Need help?
Should you require help in the course of your studies, do not
hesitate to contact the following course tutors
Help
Mr Mweshi E Cell: 0955-881340
E. Mail: emweshi@yahoo.com
Mr Muma E Cell: 0977-185244 / 0969735302
E. Mail: eliasmuma@ymail.com
Assignments
You will be expected to write at least two assignments in an
academic year. The first assignment is this module
The assignments should be handed in to course tutors during the

Assignments
residential sessions.
You will be required to submit the assignments in the order in

which they are given to you.
5
Assessments
You will be expected to write two tutor- marked test which will be
written during each residential session. You are also expected to
Assessments answer the self- marked assessments in each unit of this module.
6
Getting around this Module
Margin icons
While working through this module you will notice the frequent
use of margin icons. These icons serve to “signpost” a particular
piece of text, a new task or change in activity; they have been
included to help you to find your way around the module.
A complete icon set is shown below. We suggest that you

familiarize yourself with the icons and their meaning before
starting your study.
Activity Assessment Outcomes Note it!
Summary Help
7
Unit 1
Chemical equilibrium
1.0 Introduction
Welcome to unit 1. In this unit we are going to discuss chemical
equilibrium. The term equilibrium is used in our daily life which
may mean; the same, stability or equal. But in chemistry the term is
used to describe a chemical system in which the rate of forward
reaction is equal to the rate of backward (reverse) reaction.
During and upon completion of this unit you will be able to:
 Use the law of mass action to express the law of equilibrium.
 Calculate the equilibrium constant for an equilibrium mixture.
Outcomes  Calculate the equilibrium concentrations of reactants and

products in an equilibrium mixture
 Compare the value of the reaction quotient and the equilibrium

constant to determine the direction of a reaction
 Use the Le chatelier’s principle to determine the shift in the

equilibrium.
9
1.1 The Equilibrium Constant

Most chemical reactions do go to completion, but in some reactions
once the products are formed the reverse reaction can take place to
form reactants. If two reactants A and B react together to form
products C and D in a closed container, then it is possible for C and
D to react together to form A and B. This is called a reversible
reaction. A reversible reaction is a reaction that may proceed in
either direction depending on the applied condition.
When the rates of the two opposing processes are equal. (Forward
and backward reaction), the system is in equilibrium. In an
equilibrium system the products of the forward reaction A + B → C
+ D are being formed at the same rate as they being decomposed to
form the reactants. A + B  C + D. such a system is said to be in a
state of dynamic equilibrium. Both forward and reverse reactions
take place simultaneously and continuously. A chemical
equilibrium may be homogeneous or heterogeneous. A
homogeneous equilibrium is established if the mixture is in one
phase while a heterogeneous equilibrium is composed substances
two more phases.
Reversible reactions are shown by double arrows between reactants

and products in the equation.
A+B  C+D
At equilibrium the speed of the forward reaction is equal to the
speed of backward reaction. It means that at equilibrium there is no
observable change with time. There is a relationship between the
rates of reactions, forward and reverse, and the rate at which the
reactants and products are formed. This is expressed by the law of
mass action which states that the rate of a chemical reaction is
proportional to the product of the actions mass of the reacting
substances raised to the power of stiochiometric coefficients.
10
Action mass is the molar concentrations of the reacting substances,

molarity (mol/dm3).
Let as consider this law using a general form of a balanced

chemical equation below.
aA + bB  cC + d D
a, b, c, d, are stoichiometric coefficient for a balanced chemical
equation.
Concentrations of A, B, C, and D are written as follows [A], [B],
[C] and [D] respectively
According to the law of mass action:
The rate at which substances react (A and B) is proportional to
product of the actions masses.
Rate of combination of A and B product of the action

masses.
Forward reaction
Rateforward [Concentration A ]a x [Concentration B]b
Ratef [A]a [B]b
Rateforward = Kf [A]a [B]b _ _ _ (1)
forward velocity constant

Reverse reaction
The rate of combination of C and D to form the reactants A and B
is proportional to the product of [C]c [D]d.
Ratereverse [C]c [D]d
Ratereverse = Kr [C]c [D]d _ _ _ _ (2)
Reverse velocity constant
11
At equilibrium, the two rates are equal
Rateforward = Ratereverse
Kfoward [A]a [B]b = Kreverse [C]c[D]d -------------- (3)
To find the equilibrium constant we make we divide both sides by

Kreverse and make Kfoward / Kreverse the subject of the formula by
dividing both sides by [A]a [B]b and the equation becomes;
K forward [C]c [D]d

=
K reverse [A]a [B]b
K forward
= K equilibrium constant (K c or K eq )
K reverse
Thus the equilibrium constant expression is
[C]c [D]d
Kc = ..................................... (4)
[A]a [B]b
This expression is also called the law of equilibrium which states
that; the product of the concentration in mol dm -3 of the products
raised to their stiochiometric coefficients divided by the product of
the concentration in mol dm-3 of the reactants raised to their
stiochiometric coefficients is constant for a given equilibrium
system
If the system is NOT at equilibrium, the ratio is different from the

equilibrium constant. In such cases, the ratio is called a reaction
quotient which is designated as Q.
[C]c [D]d
Q=
[A]a [B]b
A system which is not at equilibrium tend to become equilibrium,
by causing the value of Q to approach Kc
Q  Kc.
12
For gases equilibria, the equilibration constant can be expressed in

terms of partial pressures of the gases in the equilibrium mixture.
(PC )c ( PD ) d
Kp =
( PA ) a ( PB )b
The partial pressure of a gas in a gaseous mixture is the pressure
which that gas would have if it occupied the same volume of space.
For ideal gases, KC and KP conversions are done by applying the

following relationship.
KP = KC (RT)∆n
Where ∆n is the number of moles of product – number of moles of
reactants in the balanced equation. R is gas constant
( 8.206×10-2 l.atm/mol.K ) and T is absolute temperature (Kelvin
scale). Let us now look the rules governing the writing of the
equilibrium expression.
1.1.1 Rules for writing the equilibrium expression

 An equilibrium constant expression can only be written for
a balanced chemical equation.
 The equilibrium expression contains the concentration

terms for gases and substances in solution only.
 The concentration term [solid] or [liquid] for pure solid or

liquid does not appear in the normal equilibrium expression
because they are constant.
At a particular temperature each reaction has a unique equilibrium

constant value. The value of the equilibrium constant changes with
the temperature.
13
Now let use these rules to write the equilibrium constant expression
for the equilibrium mixture in the following example.
Example 1.1
Write the equilibrium expression for the following equilibrium

mixtures; (a) A mixture of H 2 gas, I 2 gas and HI gas at 679K
(b) Silver chloride solution at 250C
(a) The equilibrium constant expression for a equilibrium mixture

of
H 2 Gas, I 2 gas and HI gas at 679K
We need first to write a balanced reversible reaction
H 2 (g) + I2 (g)  2HI(g)
Since all the components are the gaseous state they are going to be
included in the expression
[HI]2
Kc =
[H 2 ][I 2 ]
(b) The equilibrium expression for silver chloride solution.

Dissociation equation of AgCl
AgCl(s)  Ag + (aq) + Cl- (aq)
AgCl(s) is a solid and is left out from the expression
K c = [Ag + ][ Cl- ]
Now do the following activity on your own.
14
Activity 1.1
Write the equilibrium constant expression of the following

reactions
(a) CaCO 3( s )  CaO (s ) + CO 2( g )
………………………………………………………………….
…………………………………………………………………..
…………………………………………………………………..
(b) CH 2Cl ( g ) + 3Cl 2 ( g )  CCl 4 ( l ) + 3HCl ( g )
……………………………………………………………………
……………………………………………………………………..
…………………………………………………………………….
(c) 4 NH 3( s ) + 5O 2 ( g )  4 NO ( g ) + 6 H 2O ( g )
……………………………………………………………………..
…………………………………………………………………….
…………………………………………………………………….
15
1.1.2 Calculating the equilibrium constant (Kc and Kp)
When you know the concentration or partial pressure of all

substances at equilibrium, it is easy to calculate Kc and Kp. We just
substitute the numbers into the reaction quotient. Let us work
through the following example together.
Example 1.2
A mixture of SO2 , O 2 and SO3 is allowed to reach equilibrium at

852K. The equilibrium concentrations are;
[O 2 ] = 6.11 x 10-4 mol/dm 3 , [ SO2 ] = 3.61 x 10-3 mol/dm 3 ,
and [SO3 ] = 1.01 x 10-2 mol/dm 3 . Calculate the Kc and Kp for this
reaction.
The reaction for the equilibrium system

2SO 2 (g) + O 2 (g)  2SO 3 (g)
The equilibrium expression for the reaction
[SO3 ]2
Kc =
[SO 2 ]2 [O2 ]
We substitute in the concentrations
[1.01 x 10-2 ]2
Kc = = 1.28 x 104
[3.61 x 10-3 ]2 x 6.11 x 10-4
We know that:
KP = KC (RT)∆n
∆n is the change in the number of moles and from the equation:
2SO 2 (g) + O 2 (g)  2SO3 (g)
There are 3moles of gases ( 2 mol SO2 + 1mol O2) in the reactant
and 2 moles of gase (2 mol SO3) in the product
16
Thus; ∆n = 2mol product - 3mol reactant = -1mol
R = 0.08206
T = 852K
Kc = 1.28 x 10 4
KP = KC (RT)∆n = 1.28 x 10 4 (0.08206  852)-1

= 1.83  102
Let us discuss the meaning of the value of Kc. What does it tell us
about the reaction and the composition of the equilibrium mixture?
This question will be answered in the next sub section
1.1.3 Interpreting the value of kc

The degree to which the reactants are converted to products before
chemical equilibrium is reached is related to the magnitude of Kc.
The equilibrium constant gives a measure of the concentration of
products [C] [D] compared with reactant [A] [B] concentration at
equilibrium.
[C]c [D]d
Kc =
[A]a [B]b
If the equilibrium constant is large > 1 x 102 , then the equilibrium
system will be made up mostly of products. It means that the
reaction has proceeded to the right. From the expression;
[C]c [D]d
Kc = > 1 x 102
[A] [B]
a b
It clearly shows that the concentrations of the product [C] [D], the
numerator, are much greater than the denominator, the
concentrations of the reactants [A] [B]: the forward reaction will go
to completion. We say that the equilibrium favours the products
17
If Kc < 1 x 10-2 then the equilibrium condition will consist mainly

of reactants. The equilibrium is said to be to the left: more
reactants are present than products at equilibrium. If Kc < 1 x 10-2
then it is clear from the equilibrium expression that the
denominator, [A] [B], the concentrations of the reactants is more
than the numerator [C] [D] the concentrations of the products. This
reaction will not go to completion because the equilibrium favours
the reactants.
For the reactants whose Kc is between 1 x 10-2 and 1 x 102 , the

equilibrium state will be a mixture containing significant
quantities of products and reactants.
The equilibrium state refers only to the rates of the two reaction,
forward and backward (reverse) reactions not to the
concentrations of the reactants and the products. Equilibrium does
NOT mean the state at which amount products formed are equal
the reactants BUT the state at which each there is no noticeable
change at rate at which reactants and products are formed.
18
Activity 1.2
An equilibrium mixture at 1500K contains N 2 O 4 ( g ) and
NO 2 ( g ) at the following concentrations: [N 2 O 4 ]  3.2  1010 mol/l ,
and [NO 2 ] = 5.0×10-3 mol/l . Calculate K for the
reaction N 2 O 4 (g)  2NO 2 (g) and describe quantitatively the

equilibrium composition for this reaction:
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
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We discussed ealier that before the reaction reaches the equilibrium

state, the reaction quotient Q is not equal to equilibrium constant
Kc. Thus the value of Q can be used to predict the direction of a
reaction before and after reaching the equilibrium.
19
1.1.4 Predicting the direction of a reaction

Let us consider the reaction. 2 SO 2 (g) + O2 (g)  2SO3 (g)
At equilibrium the reaction quotient Q is equal to the equilibrium
constant K c
[SO3 ]2
Q= = Kc
[SO 2 ]2 [O 2 ]
Before and after the equilibrium is reached the reaction quotient Q
is not equal to the equilibrium constant K c
[SO3 ]2
Q=  Kc
[SO 2 ]2 [O2 ]
[SO3 ]2
Thus Q=
[SO 2 ]2 [O2 ]
When the concentration of the product [ SO 3] is smaller than it

could be at equilibrium and the concentrations of the
reactants [SO 2 ] and [ O 2] are larger, then Q is less than K c (Q <
K c ). The net reaction (if any) must then be in the forward
direction, 2SO 2 (g) + O 2 (g)  2SO3 (g) to produce more [ SO 3] so

that Q gets closer to K.
When the [ SO 3] is greater than it could be at equilibrium, and the

of [SO2 ] and [ O2 ] are smaller then Q is greater than K c (Q > K c )
The net reaction must then be in the reverse direction
2SO 2 (g) + O 2 (g)  2SO 3 (g) to produce more [SO2 ] and [ O2 ] so
that Q gets closer to K
The table below summarises the above discussion
20
Table 1.1 Relationship between Q and Kc and the direction of a

reaction
When Q < K When Q > K
Numerator (Product Numerator (Product

concentrations) is too small OR concentration) is too large OR
Denominator (reactant Denominator (reaction
concentrations) too large concentrations) is too small
Q is too small Q is too large.
Reactions can only proceed  Reaction can proceed only 
(reactants to products). (products to reactants)
The reaction can only proceed in the direction that makes Q more
nearly equal to Kc.
Example 4.3
A mixture of SO2 , O2 and SO3 at 1000 K contains the gases at the

following concentrations [SO2] = 5.0 x 10-3 mol/dm3, [SO3] =
6.9 x 10-3 mol/dm3, [O2] = 1.9 x 10-3
Which way will the reaction go to reach equilibrium? K = 279.
SO 2 (g) + O 2 (g)  2SO 3 (g)
[SO 3 ]2
Q=
[SO 2 ]2 [O 2 ]
(6.9  10-3 ) 2
Q=  1.0 103
(5.0  103 ) 2 1.9 103
Since Q is greater than K (103 > 239) the concentration of the
product SO3 Is too large relative to the concentrations of the
reactants SO2 and O2 . To reach equilibrium the reaction must go
from right to left. SO 2 (g) + O 2 (g)  2SO 3 (g) to make Q
equal to K
21
Activity 1.3
The equilibrium constant for the reaction

2NOCl(g)  2NO(g) + Cl 2 (g)
is 3.9 10 3 at 3000 C . A mixture contains the gases at the following
concentrations [NOCl] = 5.0  103 mol/L, [NO]= 2.5  10 3 mol/L
and [ Cl 2 ] = 2.0 10 3 mol/L. (a) Calculate the reaction quotient Q.
(b) Which way can the reaction go?

…………………………………………………………………
…………………………………………………………………
…………………………………………………………………
…………………………………………………………………
…………………………………………………………………
…………………………………………………………………
………………………………………………………………….
22
1.2 Calculation of the Equilibrium concentrations

When Kc and the actual concentrations of the reactants are known
before equilibriumm we follow the following steps to find the
equilibrium concentration of reactants and products.
1. Write or rewrite the balanced chemical equation leaving

plenty of space between formulas.
2. Express the initial concentration of the specimens
present
3. Assume the change in concentration ( let say -x on
reactants and +x on products taking into consideration
the coefficients in the equation) before equilibrium is
reached.
4. Express the concentration at equilibrium in terms of x
5. Write the equilibrium constant expression in terms of

equilibrium concentrations.
6. Knowing the value of the equilibrium constant. Solve

the equation for x
7. Having solved for x calculate the equilibrium

concentrations of the specimens
Example 1.4
A mixture of 0.500mol H2 and 0.500 mol I2 was present in 1litre
flask at 4300C Calculate the concentrations of H 2, I 2 and HI at
equilibrium. The equilibrium constant for the reaction at this
temperature is 54.3
H 2 (g) + I 2 (g)  2HI(g)
23
Solutions.
H 2 (g) + I 2 (g)  2HI(g)
Initial concentrations 0.500mol/dm3 0.500mol/dm3
0
Change in concentrations - x -x
+2x
Equilibrium concentrations (0.500 – x) (0.500- x)
2x
Kc = 54.3
[HI]2 (2x) 2
Kc = = = 54.3
[H 2 ] [I 2 ] (0.5 - x) (0.5 - x)
4x 2
54.3 =
0.25 - 0.5x - 0.5x + x 2
We solve for x using a quadratic expression
54.3 (0.25 - x + x 2 ) = 4x 2
13.575 - 54.3x + 54.3x 2 = 4x 2

13.575 - 54.3x = -50.3x 2
50.3x 2 - 54.3x + 13.575 = 0
-b± b 2 -4ac
Using the formula; x =
2a
The values for x are ; x = 0.688 or x = 0.393
X can not be equal to 0.688 because the value is more than the
initial concentrations. Thus x= 0.393.
The equilibrium concentrations of H 2, I 2 and HI are;
[ H 2, ] = 0.500 – 0.393 = 0.107mol/dm 3
[ I 2 ] = 0.500 – 0.393 = 0.107mol/dm3
[ HI ] = 2  0.393 = 0.786mol/dm3
24
Now try to find the find the equilibrium concentration of the

components of an equilibrium system using the above illustrated
steps.
If the value of K is very much smaller 1.0 10-2 then the change (-x) in
the reactant is negligible, ignore the change in the numerator and use the
initial concentrations of the reactants and solve for x in the numerator.
Then use the value of x to find the concentrations for each species in the
mixture
Activity 1.4
The reaction N 2 (g)+O 2 (g)  2NO(g) contributes to air

pollution whenever fuel is burned in air at high temperature, as
in gasoline engine. At 1500K, K c = 1.0×10-5 . A sample of air
is compressed and heated to 500K. Before any reaction occurs,
[ O 2 ]=0.20mol/L and [ N 2 ]= 0.80 mol/L. Calculate the
concentration N 2 , O 2 and NO at equilibrium.
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25
We have discussed the equilibrium constant; how it is calculated

and used in the calculation of the equilibrium concentration of
the components of an equilibrium mixture. We have also
looked at how the constant is used to predict the direction of a
net reaction when compared to the reaction quotient. Its now
time to look at what happens when the equilibrium system is
disturbed by discussing the Le Chetalier’s principle in the next
section
1.3 Le Chatelier’s Principle

The Le Chatelliers principle states that when a system in
equilibrium is disturbed, the equilibrium shifts in the direction that
decreases the effect of the disturbance. That is the net reaction
proceeds in the direction that off sets the effect of a disturbance. In
this section we will specifically discuss the disturbances in terms
of; the quantities of the components of an equilibrium mixture
when temperature and pressure are constant, the change in
temperature of the equilibrium mixture when quantities and
pressure is constant, and the change in the pressure or volume of
the container when the quantities and the temperature of the system
is constant
When we consider change in quantities, pressure and temperature,

using Le Chatelier’s principles we can that:
 When you add a reactant or product to a chemical system in

equilibrium it responds by using up what is added.
 When you squeeze it so as to increase the pressure it reacts
in a way that tends to decrease the pressure
 When you try to raise its temperature and it will react in a
way that tends to keep it cool.
26
Let us discuss in details detail the effects of each of the above

mentioned disturbances on the equilibrium system
1.3.1 Change in Quantity

Assume that we have 1.00 litre of an equilibrium mixture of
SO 3, SO2 and O 2 at 1000 K with [ SO3 ] = 0.00412 mol/L, [ SO2 ] =
0.00377 mol/L and [O2 ] = 0. 00430 mol/L. Then for the reaction
SO 2 (g) + O 2 (g)  2SO3 (g)

at equilibrium the reaction quotient Q is;
[SO 3 ]2 (0.00412) 2
Q=   278  K c
[ SO2 ][O2 ] (0.00377) 2 (0.00430)
Since the mixture is at equilibrium the rate of the forward reaction

(2 SO2 + O 2  2SO 3 ) is the same as the rate of the reverse
reaction (2 SO2 + O 2  2SO 3 ) . If we disturb the mixture by
pumping an additional 0.00500 mole of O2 in to the 1.00L
container making the new concentration.
[O 2 ] = 0.00430 mol/dm 3 + 0.00500mol = 0.00930mol/dm3
The increase in [O 2 ] increases the number of collisions between
O 2 and SO 2 molecular therefore the forward reaction
2SO 2 + O 2  2SO3 becomes faster than the reverse
reaction 2SO3  2SO 2 + O 2 . To restore equilibrium, the net
process, 2SO 2 + O 2  2SO3 must occur it means the equilibrium

shifts to the right. The mixture is no longer at equilibrium. This can
be seen by the calculation of Q immediately after the O 2 is
introduced.
[SO3 ]2 (0.00412) 2
Q=   128  K c
[ SO2 ][O2 ] (0.00377) 2 (0.00930)
The reaction quotient (Q) is now not equal to the equilibrium

constant (Kc) because the system is no longer at equilibrium.
27
Since Q  Kc (128  278) the added [O 2 ] (the disturbance) must
be consumed in order for Q to be equal to K c again.
Similarly, adding SO 2 causes a shift to the right, while adding SO3
causes a shift to the left, (formation of more SO 2 and O 2 ). The

general rule is that:
 Increasing the concentration (or partial pressure) of one

substance in an equilibrium mixture displaces the
equilibrium in the direction that consumes the added
substance.
 Decreasing the concentration of a substance causes the

production of more of that substance.
1.3.2 change in volume or total pressure

If the volume of the container is changed, the pressure or
concentrations of gases are changed and equilibrium mixture is
disturbed.
When the volume is changed and the number of moles is not, the
concentrations must change and so must partial pressure.
nRT
(P  )
v
Let us consider 1 litre of the same mixture we just discussed.
Suppose we suddenly double the volume of the container to
2.00litres at constant temperature. Each concentration is hereby
divided by 2.
28
Table 1.2 Effect of changing the volume on concentrations
Old Concentration New Concentration
0.00412 mol 0.00412

[ SO3 = = 0.00412mol/L = 0.00206 mol/L
1L 2L
0.00377 mol / L
0.00377 mol = 0.00189mol
[ SO2 ] = = 0.00377 mol/L 2L
1L
0.00430mol / L
0.00430 mol = 0.00215mol
[O2 ] = = 0.00430 mol/L 2L
1L
The new reaction Quotient is;
(0.00206) 2
Q = 553
(0.00189) 2 x 0.00215
Since Q > K (553 > 278), the mixture is no longer in equilibrium.

To restore equilibrium, Q must become smaller. To make Q smaller
more SO 2 and O2 must form at the expense of SO3 . The rule is
that increasing the volume of the container shifts the equilibrium in
the direction that produces more moles of gas.
Since 2 SO2 + O 2 is 3 moles of gas and 2SO3 is 2 moles of gas, the
equilibrium 2SO 2 + O 2  2SO 3 shifts to the left when the

volume increases. Decreasing the volume favours that side of the
equation showing fewer moles of gas; the right in this case.
Here are some examples of the effect in equilibrium of a change in

volume.
29
Table 1.3 Effect of the change in volume on the equilibrium
Equilibrium mixture Increasing Decreasing

Volume Volume
CO( g ) + Cl 2 (g)  COCl 2 ( g )  Shifts Shifts 

2 moles 1 mole
N 2 (g)+O 2 (g)  2NO(g) No effect No effect
2 moles 2 moles
1
H 2S(g)  H 2 (g) + SO (g)
2 2 Shifts   Shifts
1
1mole 1 moles
2
That when there is no change in the number of moles of gas a

volume change does not shift the equation.
A change in volume causes a change in the total pressure of the gas

mixture.
 When the volume is decreased the total pressure is

increased. Increasing the total pressure shifts to equilibrium
towards fewer moles of gas
 When the volume is increased the total pressure is

decreased. Decreasing the total pressure shifts the
equilibrium towards more moles of gas
30
Introducing in a gas that is not taking part in a chemical reaction

does not affect the equilibrium of the system. The gas will increase
the total pressure but has no effect on the partial pressure of the
reacting gases. The partial pressure of the individual gases
determines the equilibrium of the mixture .
1.3.3 Change in temperature

From the Le Chatelier’s principle it is clear that:
 Increasing the temperature causes a reaction in the direction
that result in absorption of heat.
 Decreasing the temperature causes a reaction in the

direction that results in emission of heat
From the above interpretation of the principles we can say that

raising the temperature favours the endothermic process while
lowering the temperature favours the exothermic process.
In the formation of SO 3 heat is given off

2 SO2 + O 2  2SO3 H = - 197 kJ
Thus raising the temperature shifts the equilibrium to the left, and
lowering the temperature shifts the equilibrium to the right. To
understand this it is to imagine that heat is a product.
2SO 2 + O 2  2SO 3 + 197kJ of heat given out.

Raising the temperature, means you are adding heat, this shifts the
equilibrium to the left because you are adding the product.
To lower the temperature, you remove heat, which shifts the

equilibrium right, its like you are removing the product. On the
other hand, in an endothermic reaction heat considered as a
reactant.
31
N 2 ( g )  O2 ( g )  2 NO ( g ) H  179 KJ
N 2 ( g )  O2 ( g )  179 KJ  2 NO( g ) Heat as reactant

This time raising the temperature will shift the equilibrium to the
right (it is like you are adding heat, the reactant). Reducing the
temperature (remove heat, the reactant) shifts the equilibrium the
left.
That the change in temperature affects Kc, it changes the value of

the equilibrium constant. Kc remains constant as long as the
temperature is kept constant.
The presence of a catalyst affects both rates of the forward and

reverse reaction in the same way. Therefore it changes the
approach to the equilibrium. But the composition of the equilibrium
mixture is unchanged.
32
Activity 1.5
For the reaction, PCl3 (g)+Cl2 (g)  PCl5 (g) H  93KJ . An
equilibrium mixture of PCl3 , Cl 2 and PCl5 is in a container.
(a) Cl2 is added to the container. What is the effect on the quantity
of
PCl3 in the container? What is the effect on the quantity of
Cl2 ?
What is the effect on K p ?
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
…………………………………………
(b) The volume of the container is decreased. What is the effect on
the quantity of PCl3 and PCl5 ?
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
……………………………………………………………………..
33
(c) The temperature is increased. What is the effect on the quantity

of Cl2 , PCl3 and PCl5 ? What is the effect on the equilibrium
constant?
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
………………………………………………………………………
……………………………………
If you have successfully completed the above activity let us sum up
what we have discussed in this unit.
34
Unit summary
Reactions can reach equilibrium when the reactants and products are kept
in a closed container at constant temperature. The reaction is said to reach
the equilibrium state when the rate of a forward reaction is equal the rate
Summary
of the reverse reaction. At equilibrium the reaction quotient Q is equals
the equilibrium constant Kc. The reaction quotient is a function of the
concentrations of reactants and products. The value of the equilibrium
constant is used to describe quantively the composition of the equilibrium
mixture and the calculation of the equilibrium concatrations of reactants
and products. Before the equilibrium is reached the value of Q compared
with Kc can help us to determine the direction of net reaction in order the
system to reach the equilibrium state. Le Chateliers principle says that
when a system in equilibrium is disturbed, the equilibrium shifts the
direction that decreases the effect of the disturbance.
35
Assessment
Answer the following questions in the spaces provided
Assessment
1.1.00 moles of SO2 1.00 moles of O2 are confined at 1000K in a
1.00litre container. At equilibrium 0.925 mol of SO3 has been
formed. Calculate Kc for the reaction.

2SO 2 (g) + O 2 (g)  2SO3 (g) at 100k and the equilibrium
concentrations
2. A mixture of the three gases NOCl, NO, and Cl2 is in equilibrium:

2NOCl(g)  2NO(g) + Cl 2 (g) H  35 KJ . What will be the mass
of NO affected by each of the following disturbances? (a) Cl 2 is
added. (b) NO is added. (c ) The volume of the container is increased

(d) Argon is added. (e) The temperature is decreased.
Note that the answers to the above exercise are given at the end of the
module. However, you are encouraged to work through first before
referring to the answers.
36
Unit 2
Ionic Equilibria –Acids and Bases

2.0 Introduction
For thousands of years people have known that vinegar, lemon
juice and many other foods taste sour. However, it was not until a
few hundred years ago that it was discovered why these things taste
sour - because they are all acids. The term acid, in fact, comes from
the Latin term acere, which means "sour". While there are many
slightly different definitions of acids and bases, in this unit we will
introduce the fundamentals of acid/base chemistry.
 Describe Arrhenius, Bronsted-Lowry and Lewis theories

of acids and bases
Outcomes
 Explain the concept of acid-base conjugate pairs
 Calculate pH of strong acids and bases,
 Apply the equilibrium constants of weak acids and bases

( K a & K b ) to determine their pH.
 Describe the buffer action of buffer solutions
 Calculate the pH of a buffer solution.
 Determine the indicator suitable for a given acid-base

titration
37
2.1 Three concepts of acids and bases

Before we define what an acid is and what a base is, can you make
a list of what you consider to be the properties of an acid and that
of a base. Check through your list. Your list could have captured
the following points:
Properties of acids:
1. They have a sour taste, for example, vinegar, citric acids.

2. They react with bases to form salts and water
(neutralisation)
3. They react with carbohydrates and hydrogen carbonates to
form carbon dioxide.
4. They cause colour change in plant dyes. They change litmus
from blue to red/pink
5. when in aqueous state, they conduct electricity
6. They react with metals above hydrogen in the
electrochemical series to produce hydrogen gas.
Properties of bases:
1. They have a bitter taste

2. They feel slippery
3. They cause colour change in plant dyes, for example, they
change litmus from red to blue
4. They react with acids to form salts and water
5. They conduct electricity when in aqueous solution
38
Having looked at the characteristics of acids and bases, we shall

now discuss the following three concepts of acids and bases.
1. Arrhenius concept
2. Bronsted-Lowry concept
3. Lewis concept
These concepts will help us to gain a better understanding of acids

and bases.
2.1.1 Arrhenius Theory

According to Arrhenius theory an acid is a substance that yields
H + ion. (H 3O + ) in an aqueous solution; and a base is a substance
that yields OH - in an aqueous solution, for example, HCl is an

Arrhenius acid and NaOH is an Arrhenius base.
HCl(aq)  H+(aq) +Cl- (aq)
NaOH(aq)  OH-(aq) +Na+ (aq)
According to Arrhenius, in water, HCl and NH3 exist as ionic

solutions of hydrochloric acid and ammonium hydroxide. The
products of their reaction are salt and water.
H +
+ Cl
 +
-
NH +4 + OH -  H 2 O + NH + + Cl-
   (l ) 4
Hydrocloric acid Ammonium Hydroxide Ammonium Chrolide
Arrhenius concept of acids and bases proved to be very useful in

the study of chemical reactions; however, it has the following
limitation. The Arrhenius theory is limited to water only. Let us use
HCl and NH 3 to serve as examples. Dry gases, HCl and NH 3 react
in the absence of water (H + and OH - ) ion to form ammonium

chloride, NH 4 Cl(l)
39
HCl(g) + NH 3 (g)  NH 4Cl(l)
It means that the reaction occurs without the dissociation of the

acid into H + and OH - ions. Further more, HCl and NH 3 may
dissolve in non polar solvent such as benzene, they will still react
without the dissociation process to give NH 4Cl . The formation of
NH 4Cl in this reaction cannot be interpreted by the Arrhenius
concept. NH 3 gas cannot furnish OH - , and HCl gas does not
dissociate into H + and Cl- .
This limitation of the Arrhenius acid-bases concept was resolved

with a more general theory of acids and bases, the Bronsted-
Lowry theory, that explains both the aqueous and gaseous
reactions of NH3 and HCl. Let us now discuss this theory.
2.1.2 Bronsted – Lowry theory

The Bronsted – Lowry theory states that and acid – base reaction
involves a proton transfer. An acid is defined as a proton donor and
the base as the proton acceptor. In other words, an acid is any
molecule or ion that donates a proton (H+) and a base is any
molecule or ion that can accept a proton. An acid qualifying
Bronsted-Lowry concept is termed a Bronsted-Lowry acid or
simply Bronsted acid. A base qualifying Bronsted-Lowry concept
is termed a Bronsted-Lowry base or simply Bronsted base.
The theory implies that there is interdependence of an acid and a

base; one is defined in terms of the other.
We can now see how the Bronsted-Lowry theory extended the

Arrhenius theory. HCl does not simply form H+ in water:
HCl(aq)  H+(aq) +Cl- (aq) (Arrhenius’s theory)
40
Instead, it gives up the proton to water, the base, to form H 3O+ , the
hydronium ion and Cl-
Since HCl gives up the proton to water to form the hydronium

(H 3O + ) ion and Cl- ion, hydrogen chloride is a Bronsted acid and
water that accepts a proton is a Bronsted base.
Arrhenius was correct when he said that all substances that furnish
OH - are bases. The hydroxide ion is indeed is a base:
But according to Bronsted–Lowly OH - is not the only base known.

Another example, is a reaction between HCl gas with ammonia
( NH 3 ) to form solids NH 4Cl . In this reaction, HCl is a proton
donor and hence a Bronsted acid, while NH 3 is a proton acceptor

and a Bronsted base.
The ammonium chloride appears as a white cloud consisting of

small crystals. This reaction is one of the many that show that the
Bronsted – Lowry concept is much broader than Arrihenius
concept. It is not limited to water solution, nor is it restricted to
OH- ion as the only base.
41
Since NH 3 is a base, we can now see how ammonium hydroxide is
formed when NH 3 is added to water. In this case water acts as an

acid
Molecules of NH 4OH do not exist in this reaction. For this, reason

water solution of NH 3 should be called “aqueous ammonia” and
not ammonium hydroxide.
Activity 2.1
Now give the products in the following acid-base reactions,
indicate the acid and the base.
(a) HNO3 + H 2O
............................................................................................................
............................................................................................................
............................................................................................................
(b) H 3O + + F-
............................................................................................................
............................................................................................................
............................................................................................................
42
Conjugate acid – base pairs

In an acid-base reaction the acid (HA) gives up its (H+) and
produces a new base (A-). The new base that is formed is related to
the original acid and is called a conjugate (meaning related) base.
Similarly the original base (B) after accepting a proton (H+) gives a
new acid (HB) which is called a conjugate acid. A hypothetical
reaction between the acid HA and the base B will illustrate the
above definitions.
HA + B-  HB + A-
Acid base conjugate acid conjugate base
According to Bronsted–Lowry theory, in an aqueous solution, an

acid (HA) transfers its proton to the base (H 2O) , forming
H 3O + and leaving A -
Once H 3O+ is formed it can act as an acid by transferring a proton
back to A - which acts as a base, this acid-base reaction is

reversible and equilibrium is quickly established. In general, the
reaction of an acid and a base always leads to the formation of a
new acid and a new base. From the above example the product acid
(H 3O + ) arises when a reactant base (H 2O) accepts a proton. This
(H 3O + ) and (H 2O) are known as a conjugate acid – base pair.
Similarly, the product base (A - ) results when the reactant acid
43
(HA) loses a proton. HA and A - also make up a conjugate acid –

base pair.
We can summarise this conjugate acid- base relationship with the

help of some typical examples:
Notice that when an acid losses a proton, H+, its conjugate base
formed has one less H and one less positive charge (or one more
negative charge) than the acid. From these examples you can see
that acids can be molecules (HBr), positive ions (H 3O + ) , or
negative ions ( HCO3- ).
When a base gains a proton, H + , it’s conjugate acid has one more
H than the base (or one less negative charge). It can be seen that
bases can also be molecules (H 2O), negative ions (F - SO 42- ), or
positive ions (H 3 NNH +2 )
One conjugate acid – base pair in the reaction is designated by the

subscript 1 and the other pair by subscript 2.
44
In this reaction NH 3 is the base and H 2 O is the acid. The

ammonium ion, NH +4 , is the conjugate acid of NH 3 and OH - is
the conjugate base of. H 2 O .
When gaseous NH 3 and HCl react, HCl (acid) donates a proton

to NH3 (base). The products are Cl-, the conjugate base of HCl, and
NH +4 the conjugate acid of NH 3 , which form a salt ( NH 4 Cl )
Structural formulae have been used in the preceeing equations to

reveal an important structural feature of all bases: all bases have a
pair of unshared electrons that can form a covalent bond with the
transferred proton. . The unshared pair of electrons acts as the
basic site for accepting the H + .
Now let us consider the reaction between ethanoic acid and water
to form the conjugate base CH 3COO - and the conjugate acid
H 3O + .
CH 3COOH(l) + H 2 O(l)  H 3O + ( aq)  CH 3COO - ( aq)

Weak acid weak base strong acid strong base
45
A weak acid ( CH 3COOH ) produces a strong conjugate base
( CH 3COO - ), and a weaker base ( H 2O ) gives a strong conjugate
acid ( H 3O + ). From this example we can conclude that, a weak
base has a strong conjugate acid and a weak acid has a strong
conjugate base
Since CH 3COO - is a stronger base than H 2 O , and the H 3O + is a
stronger acid than CH 3COOH the reverse reaction will be highly

favoured. It means that the equilibrium is very much displaced
towards the left. This explains why ethanoic acid ionization in
water is less than 1%.
Since an acid is a proton donor it means that a strong acids ( H 3O + )

will have a greater tendency to donate the proton: while weaker
acids ( CH 3COOH for instance) have a tendency to hold on to the
proton. Like wise the greater the tendency for a base
( CH 3COO - for example) to accept a proton the stronger the base is,
while a weak base ( H 2 O ) has little tendency to accept the proton.

Once a strong base captures a proton, it tends to hold on to it: this
result’s in a weak conjugate acid. Once a strong acid readily
donates a proton, its conjugate base does not readily hold on to the
proton, this results in a weak conjugate base. This behaviour leads
to the generalization that: the stronger an acid, the weaker is its
conjugate base: the stronger the base the weaker it its conjugate
acid and vise versa.
Now do the following activity to see if you have understood the

concept of conjugate acid- base pairs.
46
Activity 2.2
(a) Give the conjugate acid of each of theses bases: NH 3 , OH - , O 2-
and H -
……………………………………………………………………………
……………………………………………………………………………
……………………………………………………………………………
……………………………………………………………………………
(b) Give the conjugate base of each of these acids: NH +4 , HNO3 , HSO -4
and H 2 PO -4
…………………………………………………..........................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
2.1.3 Lewis concept of acids and base

In the early 1930s G.N. Lewis proposed even a more general model
of acids and bases. According to Lewis an acid is an electron-pair
acceptor and a base is an electron donor. Lewis pictured an acid
and a base as sharing the electron pair provided by the base. This
creates a covalent bond (or coordinate bond) between the Lewis
acid and the Lewis base. If the Lewis acid be denoted by A and the
Lewis base by B, then the fundamental equation of the Lewis
theory can be written as:
A + :B  A–B
Lewis acid Lewis base complex
47
It may be noted that:
(i) All cations or molecules short of an electron-pair act as Lews

acids.
(ii) All anions or molecules having a lone electron-pair act as Lews
bases.
Now let us now study very carefully the following examples of

Lewis reactions:
(i) Reaction between H + and OH - . A proton ( H + ) is an electron

pair
acceptor and therefore, a Lewis acid. Thus Lewis reaction
between
H  and OH - .can be written as follows:
(ii) Reaction between BF3 and NH 3 . BF3 has six valence electrons
with B atom which can accept an electro-pair and is thus, a Lewis
acid. The N atom of NH 3 has a lone electron-pair and is Lewis
base. Lewis reaction between BF3 and NH 3 may be written as:
The useful but limited model of Arrhenius was replaced by a more

general model of Bronsted and Lowry . Even a more general
model was proposed by Lewis. However, the Bronsted-Lowry
model is now used in common practice. Below is a table which
attempts to compare the three models against one another.
48
Table 2.1: three models for acids and bases
Model Definition of acid Definition of base
Arrhenius (1884) H  producer OH  producer
Bronsted-Lowry H  donor H  acceptor

(1923)
Lewis (1939) electron-pair Electron-pair donor

acceptor
It is now time for you to put into practice what you have learnt
from the above section
Activity 2.3
Describe the reaction between ammonium molecules and
hydrogen ions in terms of Lewis acids and bases.
NH3 (aq) + H+ (aq)  NH4+ (aq)
………………………………………………………………
………………………………………………………………
………………………………………………………………
………………………………………………………………
………………………………………………………………
………………………………………………………………
………………………………………………………………
………………………………………………………………
49
2.2 Equilibrium and Acidity-basicity
2.2.1 Relative strength of an acid
The strength of an acid depends on its ability to transfer its proton

( H + ) to a base to form its conjugate base. When a monoprotic acid
(HA) dissolves in water, it transfers its proton to water (a Bronsted
–Lowry base) to form hydronium ion ( H 3O + ) and a conjugate base.
(When an acid HA is in water, it dissociates as follows)
HA + H 2 O  H 3O + + A -
This equation represents the dissociation of the acid HA into A -

ion. The equilibrium expression for the dissociation of water is
[H3O + ] [A - ]
Ka =
[HA]
Where K a is called acid dissociation constant. Therefore the value
of K a for a particular acid is a measure of its strength or its

acidity. The strength of an acid is defined as the concentration of
H+ ions in its aqueous solution at a given temperature. In other
words, acid strength is a measure of acidity or strength in water ;
the larger the value of K a , the stronger the acid. The units of K a
are mole/L but are customarily omitted.
Let us consider the dissociation of hydrochloric acid in water
HCl + H 2O  H 3O + + Cl- K a = 107
Acid1 Base2 Acid2 Base1
 Stronger acid than   Stronger base than   weaker acid than   Weaker base than 
       H O 
 H3O+   Cl-   HCl   2 
 
50
For a strong acids like HCl the equilibrium lie almost entirely to the
right (Very large Ka). The dissociation is 100% such that the
species present in the solution are H 3O + and Cl- . This is because
HCl will very easily release the H+ than the H 3O+ which a weaker
acid as a result the hydronium ion will hold to the proton and the
Cl- ion is a weaker base than H 2 O will not easily accept a proton.
This prevents a reverse reaction and the HCl a strong acid
dissociates completely.
In general a strong acid HA dissociates completely in water to yield

H+ and A-
HA + H 2 O  H 3O + + A -
The dissociation constant expression
[H3O + ] [A - ]
Ka =
[HA]
[HA] does not exist because it dissociates completely. Thus the

expression becomes
K a = [H 3O + ][A - ] or K a = [H + ][A - ]
For strong acids the acid dissociation constant is more than 102
( K a > 102 )
Having looked at dissociation constant of a strong acid, let us now

consider acid dissociation constant for a weak acid. What is a weak
acid? Well, a weak acid is one which does not ionize to a very large
extent in solution. Typical weak acids include most organic acids
and some inorganic ones like hydrofluoric acid, HF. One of the
commonest weak acids is ethanoic acid ( CH 3COOH ). Depending
on its concentration, about 1% of the ethanoic acid molecules are
ionized in solution. This means that the dissociation is very little
51
such that the solution is mainly composed of

CH 3COOH and H 2O .
CH 3COOH + H 2O  H 3O + + CH 3COO- Ka = 1.8 x 10-5
Acid1 Base2 Acid2 Base2
 weaker acid than   weaker base than   stronger acid than   stronger base than 
     CH COOH   H O 
 H3O+   CH COO-    
   3  3 2 
This is because the H 3O + ion is a stronger acid than CH 3COOH
and it will easily donate a proton to CH 3COO - ion which is a
stronger base than than H 2 O to form CH3COOH and H 2 O again

forcing a backward reaction than forward reaction. Thus at the
equilibrium of this system there is far much more concentrations of
reactants than products. The acid dissociation constant ( K a ) for
this weak acid, CH 3COOH , is very small and is given by;
[CH 3COO - ][H 3O + ]

Ka =
CH 3COOH
In genera a weak acid HA partially dissociates in water to yield
very small amounts of H+ and A-
HA + H 2 O  H 3O + + A -
The dissociation constant expression
[H3O + ] [A - ] [H + ] [A - ]
Ka = or K a =
[HA] [HA]
The equilibrium of this reaction is mainly to the left in that the Ka

is very small.
The difference in the behaviour of aqueous solution of strong and

weak acids is summarised as follows.
52
Strong acids
HA strong acid + H 2Ostrong base  H 3O weak acid + A - weak base

 
no molecule remain only species present
(100% dissociation)
Weak acids
HA weak acid + H 2 O weak base  H 3Ostrong acid + A -strong base

 
molecule remain in solution very small ions present in the solution
In general, Bronsted – Lowry acid – base equilibrium favours the

side with the weaker acid and weaker base. Thus the difference in
acid strength can be explained in terms of the position of these
equilibria for the dissociation of acids in water.
2.2.2 Relative strength of bases
Now that we have some understanding of acid dissociation

constant, let us look at the relative strength of bases. According to
the Arrhenius concept, a base is a substance which produces OH-
ions in aqueous solution. The basic properties of such a substance
are due to the presence of the hydroxyl ions. Let us consider a base
B whose dissociation can be represented as
B + H 2 O  BH + + OH -
The base dissociation constant K b expression for this base

expression is,
[BH + ] [ OH - ]
Kb =
[B]
53
K b is called the base dissociation constant or ionization constant.

The strength of a base is defined as the concentration of OH- in its
aqueous solution at a given temperature.
The value of K b for a certain base is a measure of its base strength.
Strong bases dissociate completely in aqueous solution, and they have a

high K b value while weak bases they partially dissociates in aqueous
solution, and they a small K b value.
Let as now express the dissociation constant of ammonia , NH3 , a weak
base.
NH 3 + H 2O  NH 4 + + OH - Kb = 1.77  10-5
NH 3 weak base + H 2 O weak acid  NH 4+strong acid + OH - strong base

   
large amounts of these molecule remain only very small amounts present
The K b for ammonia is very small this is because at equilibrium
very small amounts of [NH 4 + ] and [OH - ] ion are present.
For a very strong base like ammonium hydroxide (NaOH ), it will

dissociates completely in water.
NaOH  Na + + OH -
What exist in the solution are the Na+ ion and the OH- ion. Sodium
hydroxide solution will have more amounts of the concentration of
OH- ions than aqueous ammonium solution. Thus in the case of
bases the concentration of OH - ions determines the strength of a
Bronsted base
54
2.3 The pH (potential of hydrogen) of solutions

The pH stand for potential of hydrogen or hydrogen potential and it
is determined by the negative log of the concentration of hydrogen
ions in a solution. Mathematically, it can be expressed as
1
pH = - log[ H + ] or pH = log or [H + ] = 10-pH
[H + ]
Where [ H + ] is the concentration of hydrogen ions in moles per

litre.
The pH scale ranges from 1 to 14, and 7 is the mind point of the
scale. If the pH of the solution is less than 7 then it is acidic while
above 7 the solution is said to be basic. Since 7 is the mind point of
the pH scale, it means that if the pH of a solution is 7 then the
solution is neither basic or acidic, it is neutral. Pure water is a
neutral substance and its pH at 250C is 7, it means that the
conconcetrations of H+ and OH- ions in water are equal. Let us
verify this by looking at self - ionization of water at 250C.
2H 2 O  H 3O + + OH - (1)
The hydronium ion, H 3O+ , is the hydrogen ion and equation (1) is
simply written as;
H 2O  H + + OH - (2)
We can then write the dissociate constant of the self ionization of

water as follows
[H + ][OH - ]
Kw = (3)
[ H 2 O]
55
Where K W is called water dissociation constant or the water

ionization constant.
The water molecules, [H 2O] , in expression (3) is presumed to be
constant. Therefore, [H 2O] drops out from the equation so that the
water dissociation constant or the water ionization constant reduces
to:
K W = [H + ] [OH - ] (4)
This expression is also known as ion product of water and it is

represented by Kw.
We know that the pH of pure water is 7 that is
pH = - log[ H + ] = 7
7 = - log[ H + ]
Thus the concentration of H+ ions in pure water at 250C is given by
[H + ] = 10-pH
= 10-7
When the concentration of H  and OH  ions in water are

expressed in mole per litre, the value of K W found experimentally
is 1.0  1014 at 250C. The value of Kw. however, increases with

temperature. For instance, at 50 C Kw. = 5.35 x 10 14 .The ion
product of water ( K w ) increases with the increasing temperature.
0o C  1.14 x 10 -15
250 C  1.00 x 10-14 (mol 2 dm -6 )
350 C  2.06 x 10-14
50o C  5.35 x 10-14.
56
Let us now look at the relative concentration of H + and OH -
ions in pure water. The equilibrium concentration of H + and OH 

in pure water at 25 c are both equal, [ [H + ] = [OH - ] .
H 2 O  H + + OH -
This is because the dissociation of water shows that for a molecule

of water that undergoes ionization; one H + ion is formed for every
OH - ion that is formed. Additionally, if you look at the equilibrium
constant, you will easily notice that the total positive charge,
H + ions is equal to the total negative charge, OH - ions. This entails
that the [ H + ] = [OH  ].
Let x = [ H + ] = [OH  ].
K w  [H + ] [OH - ]
K w  x  x  x2
x 2  1.00  1014
x  1.00  1014  1.00  107
[H + ]  [OH - ]  1.00  107 mol dm3
Following this discussion we can say that, in a given solution, if

the:
[H + ] = [OH - ] then its pH = 7 and the solution is neutral
[H + ] > [OH - ], then its pH < 7 and the solution is said to be acidic
[H + ] < [OH - ], then its pH > 7 and the esolution is said to be basic or alkalin
57
2.3 The pH, pOH, pKw, pKa and pkb

The notation “p” has been extended to other concentration. It
means talking the – Log of the given concentrations / equilibrium
constant.
Thus;
pH = -log[H - ] pOH = -log[OH - ] pK w = -logK w
pK a = -logK a pK b = -logK b
2.3.1The Relationship among pH pOH & pKw.

We already know that at 250C
Kw = [OH - ] [H + ] = 1.0 x 10-14
And that the [H + ] = [OH - ] = 1.0 x 10-7
Let us now take the negative log of K w , [H + ] and [OH - ]
pK w = - Log K w
= - Log 1.0 x 10-14
= 14
pH = -log [H + ] pOH = -log [OH - ]
= -log 1.0 x 10-7 = -log 1.0 x 10-7
= 7 = 7
From the above values of pKw, pH and pOH we can say that at
250 C the sum of pH and pOH of any aqueous solutions must be
pK w = 14
pH + pOH = 14
58
2.3.2 The relationship between pK a and pK b
We now know what pKa and pkb are, Let us now make an attempt
to find out whether or not the relationship exists between the two
concepts
We start by considering the following ‘reaction’ of an acid in

water.
HA + H 2O  H 3O + + A-
acid base
Now the simplified form of the equation:
HA  H+ + A-
acid base
There is a simple relationship between the conjugate constant K a

of the acid HA pair and K b of its conjugate base A -
The two equilibrium conditions for the ionisation constant for HA

and A  are
HA  H+ + A- A - + H 2O  HA + OH -
[H + ] [A - ] [HA] [OH]
Ka = Kb =
[HA] [A - ]
Now we multiply the two constant K a x Kb
59
[H + ] [A - ] [HA] [OH - ]
Ka x Kb = X = [H + ] [OH - ] = K w
[HA] A
Thus
K a × K b = K w = 1.0 x 10-14
Kw Kw
Ka  & Kb 
Kb Ka
Example 2.1
Find K b and pK b for the formate ion CHOO  ionization

constant for formate acid CHOOH is
K a  1.76 x 10 -4 at 25 o C
Kw
Kb 
Ka
1..00 x 10-14
Kb   5.68 x 10 -11
1.76 x 10-4
pK b  - log K b
= 10.6
Consider the following solution of ammonia in water.
NH 3 (aq) + H 2O(l) NH +4 (aq) + OH - (aq)

base acid
The equilibrium constant at 25 O C for this reaction is
K b  1.8 x 10-5 and pK a  4.8
60
The K a for NH 4 acting as an acid
NH +4 (aq)  H + (aq) + NH 3 (aq)
K w 1.00 x 10 -14
Ka    5.6 x 10 -10
Kb 1.8 x 10 - 5
pKa = - log K a
 - log 5.6 x 10- 10
= 9.25
Ka x Kb  5.6 x 10-10 x 1.8 x 10 -5
 1.00 x 10 - 14  K w
Let us now add the values of the pK a of the acid and pK b of its
conjugate base
pK a  pK b  ?
9.25  4.8  14
Thus pK a  pK b  14
For any pair of weak acid/conjugate base or weak base/ conjugate

acid in aqueous solution.
K a x K b  1.0 x 10 -14 at 25oC and pK a  pK b  14
Let us now use the above relationships to calculate the pH of strong

acids and bases, and weak acids and bases in the next subsection
61
2.4 Calculations of the pH

In this section will discuss the calculation so the pH in strong acids
and bases, and weak acids and basses.
2.4. 1 The pH of a Strong acids and bases

It is very easy to calculate the pH of a strong acids and bases at
250C by taking the following steps;
 For the acid calculate the concentration of hydrogen and

then take the negative log of [ H + ]
 For the base calculate the concentration of the hydroxide

ions [OH  ] present in the base, find the [ H + ] by using the
relation K w  [H + ] [OH - ] , then find the pH by taking the
negative log of the concentration of hydrogen ions. Or find
the pOH, taking the negative log of [OH  ] and then use the
relationship pOH + pH = 14
Example 2. 2
Calculate the pH of 0. 015mol dm-3 nitric acid, assuming that the

acid is completely dissociated.
solution
HNO3  H + + NO3-
Complete dissociation means that 1 mol of HNO3 yields 1 mol
H + and 1 mol NO3- . Thus 0.015mol dm-3 HNO3 yields
0.015mol dm-3 H + and 0.015mol dm-3 NO3-
[ H + ] = [NO 3- ] = 0.015 mol dm-3
62
pH = -log [H + ] = -log (0.015)
pH = 1.8
Example 2.3
Calculate the pH of 0.0250 mol dm-3 potassium hydroxide
solution, assuring that the alkali is completely ionized.
KOH  K + + OH -
Completely dissociation of 1 mol KOH into 1 mol K + and 1 mol

OH -
[K + ] = [OH - ] = 0.0250 mol dm -3
Kw = [H + ] [OH - ] = 1.0 x 10-14 mol 2 dm -6
Kw 1.0×10-14 mol2 dm -6
[H + ] = =
[OH - ] 0.025mol dm -3
[H + ] = 4.0×10-13 mol dm -3
pH = -log [H + ] = -log ( 4.0×10-13 mol dm -3 )
pH = 12.4
for strong bases and acids, [H + ] and [OH - ] is equal to the

concentration of the acid and base multiplied by the number of
moles of H + and, OH - ions produced by dissolving 1 mole of the
acid or base..
63
Activity 2.4
Calculate the pH of the following solutions
(a) 0.01M barium hydroxide
(b) 0.02 M sulphuric acid
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2.4.2 Calculations of the pH of weak acids
When an acid or base is weak it produces a concentration of

H + or OH - ions less than its concentration.
To find the concentration of H + or OH - of weak acids and bases,

its necessary to calculate the equilibrium constants K a or K b .
As a reminder, K a is known as acid ionisation constant and K b

is known as bases ionisation constant (These are constants; they
have been already determined). See appendix A
Let us work through the example below
64
Example 2.4
Find the pH of 0.20M solution of formic acid.
Solution:
We first write the dissociation equation of CHOOH with its K a
HCOOH(l)  H + (aq) + HCOO - ( aq) K a = 1.76 x 10-4
Then under each species in the equation we indicate the initial,

change and the equilibrium concentrations
HCOOH(l)  H + (aq) + HCOO - ( aq)
Initial 0.20 0 0
Change -x +x +x
At equilibrium (0.20-x) x x
X represents the number of moles of acid per litre that ionized
The K a expression for CHOOH is
[H + ][CHOO- ]
Ka = = 1.76 x 10-4
[CHOOH]
Replacing by equilibrium concentrations in (1) we get
(x)(x)
Ka = = 1.76 x 10-4
(0.2-x)
x2
= 1.76 x 10-4
(0.2-x)
65
This quadratic equation can be calculated without much problems.

However, this is a weak acid and we assume that the numbers of
moles is that ionized is far much less that the initial concentration
of the acid
0.2 M, then the amount of the acid that ionized is negligible
If x  0.20 then 0.20 -x  0.20
If this approximate is valid then 0.20  x is replaced by 0.20.
x2
= 1.76 x 10-4
0.20
x 2  [H + ]=[CHOO- ] the equilibrium concentrations
Solving for x
x2 = 1.76 x 10 -4  0.20
x 1.76 10-4  0.20
= 5.9×10-3 mol dm -3
In general
 0.20 is the concentration of a weak acid [HA]
 x is the concentration H + ions in a weak acid, [H + ] .
 1.76 x 10-4 is the dissociation constants of a weak acid

Ka
Thus the above calculations can be summarised in the following

general equations of finding the pH of a weak acid.
[H + ]= k a x  HA  (1)
That is the [H+] of a weak acid is equal the square root of the
product of k a value for the acid and the concentration of the acid.
66
Let us now find the pH of the weak acid by taking the negative log
of the value of x which is the [H + ]
pH = - log [H + ]
= -log ( 5.9×10-3mol dm -3 )
= 2.24
The [H + ] of a weak acid is equal to k a x  HA 
Thus all what we have just done in calculation the calculation of

the pH of a weak acid is summarised in the formula below
pH = -log k a x  HA  (2)
The pH of a solution of a weak acid is equal to ve logarithm of
the square root of the product of the k a value and the concentration
of the acid.
pH=-log k a x  concentration of the acids 
Using equation (2) the pH of formic acid is
pH = -log k a x  HA 
=-log 1.76 10-4  0.20
= 2.24
Let us see if our ealier assumption still holds some water by using
the value of x by finding the actual equilibrium concentration of
[CHOOH] and find the ionization percentage
67
We assumed that x  0.20 then 0.20 -x  0.20
X = 5.9×10-3 mol dm -3
0.20 mol dm -3 - 5.9×10-3mol dm -3 = 0.194 mol dm -3
0.194 mol dm -3 is almost 0.20 mol dm -3 our assumption was

correct
In terms of the ionisation percentage (%)
[H + ]
Ionization % = 100
[CHOOH]
5.9×10-3 mol dm -3
= 100  3%
0.20 mol dm -3
3% is very much negligible. An error of 5% is quiet acceptable in

this course.
The approximation method fails when K a is too large or when the

initial concentrations is too small ( the solution is too dilute). If that
is the case the quadratic equation has to solved using the formula
b  b 2  4ac
x
2a
The x positive value is the concentration of [H + ]
It is now time to check your understanding of the concepts that you
have covered in the above section. Do the following exercise. You
have 10 minutes to do this task.
68
Activity 2.5
What is the pH of a 0.10mol dm -3 solution of benzoic acid.
C6 H 5COOH? k a = 6.3 10 -3mol dm -3
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2.4.3 Calculating pH of weak bases.
Let us consider a base B, in aqueous solution of

concentration X mol dm-3 . (Don’t consider water)
B + H 2O  BH + + OH -
Since 1 mol of B must form one mole of BH + and 1 mole

of OH - , So the concentration of [BH + ] [OH - ] must be
equal.
[OH - ] [BH + ]
Kb = [BH + ] = [OH - ]
[B] - [OH - ]
[OH - ]2
Kb =
[B] - [OH]
69
But at equilibrium for weaker base will be very small

compared with [B]
[OH - ]2
[B] - [OH - ] = [B] thus K b =
[B]
[OH - ] = K b  [B]
[OH - ] = K 1 x (concentration of base)
pOH = - log K b x (concentration base)
Since for any aqueous solution at 25 0 C
[ H + ] x [OH - ] = 1.00 x 10- 4
Then pH + POH = 14
pH of a base = 14 - POH
Example 2.5
What is the pH of a solution of ammonium NH 3 of concentration
0.10 mol dm 3 , given that the K b = 1.7 x 10 -5 mol / dm 3 .
Solution:
NH 3 (l) + H 2 O(l)  NH 4+ (aq) + OH - (aq)
[NH 3 ] = 0.10 mol dm -3 K b = 1.7 x 10 -5 mol dm 3
70
[OH - ] = K b x [NH 3 ]
[OH - ] = (1.7 x 10 - 5 x 0.10)
 1.3 x 10 -3
mol dm -3
pOH  - log [OH - ]
= 2.89
pH = 14 – pOH
= 14 - 2.89
= 11. 1
Activity 2.6
The concentration of a base CH 3COO - in the solution is 0.015M.
(a) Using the ionic equilibrium equation for this base determine the
equilibrium concentrations of OH - ion and its conjugate base
(b) Calculate the pH of this base.
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71
2.5 Buffer solutions

A buffer solution is one that resist change in its or addition of small
amounts of acid or base.
Most commonly the buffer solution consists of a mixture of a weak

acid (HA) and its conjugate base ( A - ) . For example
H 2 CO3 and HCO3- or H 2 PO3- and HPO32- or NH 4 + and NH 3
When a strong acid  H +  is added to this buffer solution, it reacts
with a base A - present in the solution to form the conjugate acid
 HA 
A - + H +  HA
And when a base  OH -  is added to this buffer solution OH - reacts
almost indirectly with acid HA to form its conjugate base.
HA + OH -  A - +H 2O
The buffer solution contains a reservoir of a base that consumes the

added acid. (Converting it to weak acid HA ), and a reservoir of
acid to consume the added base (converting it to the weak base
A - ).
To make a buffer solution a weak acid, let say acetic acid

CH 3COOH , is mixed with it’s salt , sodium acetate CH 3COONa
Acetic acid is the main source of the weak acid ( CH 3COOH )

because it partially ionises
CH 3COOH  H +  CH 3COO-
72
Sodium acetate solution yields the conjugate base ( CH 3COO - )

acetate ion because it ionises completely
CH 3COONa  CH 3COO - + Na +
Thus the solution will be a mixture of the weak acid ( CH 3COOH )
and its conjugate base ( CH 3COO - ).
When a strong acid  H +  is added in small amounts to this solution
it reacts with the conjugate base ( CH 3COO - ) producing its
conjugate acid ( CH 3COOH )
CH 3COO -  H +  CH 3COOH
And when a strong base  OH -  is added in small amounts reacts
with the acid ( CH 3COOH ) producing water and its conjugate
base CH 3COO - )
CH 3COOH + OH -  H 2 O + CH 3COO-
This is how buffers resist the change in the pH of the solution
(buffer action).
73
Activity 2.7
The buffer solution can also be prepared by mixing a weak base,

lets NH 3 and its salt NH 4Cl . Explain the buffer action of this
solution?
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2.4.4 The Henderson-Hasselbalch Equation
The pH of a buffer solution depends on the ratio of the

concentrations of the conjugate acid and base. This dependence is
clear if the equilibrium condition is written in logarithm form.
HA  H+  A-
[H + ][A - ]
Ka =
[HA]
Taking the logarithms on both sides
 [H + ][A - ] 
log    logK a
 [HA] 
74
Using the properties of logarithms we get
[A - ]
log[H + ] + log  logK a
[HA]
Using the definition of pH and pK we get
[A- ]
-log[H + ] -log  logK a
[HA]
[A - ]
pH -log  pK a
[HA]
[A - ]
pH = pK a + log or
[HA]
[base]
pH = pK a + log
[acid]
This form of equilibrium condition called Henderson-

Hasselbalcah equation
Example 2.6
What is the pH of a buffer solution that is 0.20 M with respect to

ammonia, NH 3 , and 0.20 M with respect to ammonium chloride
NH 4Cl ?
Solution
The equation for the basic ionization of NH3 is
NH 3 + H 2O  NH 4 + + OH -
75
We check the initial, change and the equilibrium concentrations of

NH 3 , NH 4 + and OH -
NH 3 + H 2O  NH 4 + + OH -
Initial 0.20 0.20 0
Change -x +x +x
At equilibrium (0.20-x  0.20) (0.20 + x  0.20) x
We assume that the change in[ NH 3 ] and [ NH 4 + ] is negligible then
[NH 4 + ][OH - ]
Kb = = 1.77  10 5
[NH 3 ]
(0.20)(x)
= 1.77  10 5
0.20
x = 1.77 10 5 mol dm-3 = [OH - ]
We know that
pH = 14 - pOH
pOH = -log [OH - ]
= -log 1.77  10 5
= 4.75
pH = 14 - 4.75
= 9.25
Kw
We can also use this [H + ] = relationship to find pH
[OH - ]
76
Let us now use the Henderson-Hasselbalcah equation
[base]
pH = pK a + log
[acid]
[ NH 3 ]
pH = pK a + log
[NH 4 + ]
Here the pK a refers to NH 4 + ion (the acid in this conjugate pair)
pK a = -log K a = -log 5.64  1010 = 9.249
0.20
pH = 9.249 + log
0.20
= 9.25
Activity 2.8
Find the pH of a buffer solution containing 0.20 mole per litre

CH3COONa and 0.15 mole per litre CH3COOH.
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77
2.6 Acid – Base Titrations

Titration is a common method used to analyse a sample. A standard
solution, with accurately known concentration, is added to a sample
until a reaction is complete signalled by the colour change at the
end point. A typical example of acid – base titration is the analyses
of a sample of sulphuric acid, H 2SO 4 , by titrating it with a standard
solution of sodium hydroxide, NaOH . The reaction is
H 2SO 4 (aq) + 2NaOH(aq)  Na 2SO 4 (aq) + 2H 2O(l)
Or in ionic form with spectator ions omitted
2H + (aq) + 2OH - (aq)  2H 2O(l)
In a successful titration , the quantity of the standard solution that

has been added at the end point is chemically equivalent to the
quantity of the unknown. This means that the molar ratio of the
known added to unknown must conform to the molar ratio in the
chemical equation. In titrating H 2SO 4 with NaOH , 2 moles of
NaOH must be added for every mole of H 2SO 4 .
In titrations of acid and bases, advantage is taken of the observation

of that the pH of the solution being titrated changes rapidly as the
equivalence point is reached. The indicator changes colour when
just one drop of the standard solution is added after the equivalence
point has been reached.
When an acid and a base have been mixed in equivalent quantities

we say that they have neutralised each other. This is misleading,
because the resulting solution may actually be neutral, acidic or
basic. Take for instance, if we mix 1 mol of HCl and 1 mol of
NaOH, the reaction
78
HCl(aq) + NaOH(aq)  H 2O(l)
Or in ionic form
H + (aq) + OH - (aq)  H 2O(l)
goes practically to completion, the solution contains only water

and NaCl and there fore neutral ( pH = 7 at 250C )
But if we mix 1 mol of acetic acid, CH3COOH , with 1 mol of

NaOH and the reaction
CH3COOH(l) + NaOH(aq)  H 2O(l)  CH 3COONa(aq)
Or in ionic form
CH 3COOH(l) + OH - (aq)  H 2O(l)  CH 3COO - (aq)
goes practically to completion. , the only product is an aqueous

solution of sodium acetate. The same as if sodium acetate had been
added to water. The solution is moderately basic, since acetate ion
is a weak base:
CH 3COO- + H 2O  CH 3COOH + OH -
2.6.1 Determining the acid- base indicator
An indicator is a weak acid or base in which the dissociated form is

a different colour from the undissociated form.
HIn(aq)  H + (aq) + In - (aq)
(Colour A in acid solution) (Colour B in alkali solution)
[In - ]
K in = [H + ] 
[HIn]
Assuming that the colour changes when [In - ] = [HIn] then
The end point of the indicator will be when
79
[H + ]  K in that is when pH  pK in
Different indicators have different pK in values and so change

colour within different pH ranges.
Indicator pK in pH range use
methyl orange 3.7 3.1-4.4 titrating with strong acids
phenolphthalein 9.6 8.3 - 10.0 titrating with strong base
Methyl orange 5.6 4.8 – 6.0 titrating with strong acids
The pH of the solution at equivalent point determines what

indicator to use. The following steps are followed in determining
the indicator.
1. Determine what salt is present at the equivalence point
2. Estimates the salt’s concentration at the equivalence point
3. Calculate the pH of the solution at equivalence point
4. Select an indicator that changes about that pH
Example 2.7
2.500 mmol benzoic acid C6 H 4 COOH , is titrated with 2.500 mmol

NaOH. The volume of the solution at the equivalence point is
125mL.
(a) What solute is present in the solution at the equivalence point?
(b) What is the concentration of the solute?
(c) Calculate the pH at the equivalence point and select the
indicator suitable for this titration
80
Solution
(a) the reaction between benzoic acid and sodium hydroxide

produces
sodium benzoate.
C6 H 4 COOH + NaOH  C6 H 4COONa  H 2 O
Or in ionic form
C6 H 4 COOH + OH -  C6 H 4 COO -  H 2O
(b) The equation shows that when 2.500 mmol of C6 H 4 COOH
reacts (almost completely ) with OH - 2.500 mmol of

C6 H 4 COO- are produced. Since the final volume of the solution is
125mL, the concentration of the salt is
2.500 mmol
[C6 H 4 COO- ] = = 2.0×10-2 mol L-1
125 mL
(c) We expect the solution to be somewhat basic because of

benzoate ion is a conjugate base of a weak acid. The basic
ionization constant of C6 H 4 COO- is calculated from the
K a = 6.46  105 for the benzoic acid
We know that
Ka × Kb = Kw
Kw 1.00×10-14
Thus Kb = = = 1.55×10-10
Ka 6.46×10 -5
This constant corresponds to the reaction
C6 H 4 COO-  H 2O  C 6 H 4COOH + OH -
81
[C6 H 4 COOH][OH - ]
= 1.55×10-10
[C6 H 4 COO- ]
Since C6 H 4 COOH and OH - are produced in equal concentrations
[C6 H 4 COOH] = [OH - ] = x
x2
= 1.55×10-10 ( x is very small compared to 0.0200)
0.0200 - x
x2
= 1.55×10-10
0.0200
x = 1.55×10-10  0.0200 = 1.76 10-16
[OH - ] = 1.76×10-16 mol L-1
Kw 1.00×10-14
[H + ] = = = 5.68×10-9 mol L-1
[OH - ] 1.76×10-6
pH = -log 5.68×10-9 mol L-1
= 8.25
The indicator should change colour about pH 8.3 thus

phenolphthalein will be used for this reaction.
82
Activity 2.9
In a titration of NH 3 with HCl, 3.550 mmol NH 3 is titrated with
3.550 mmol HCl. The volume of the solution at the equivalence
point is 145mL.
(a) What solute is present at the equivalence point ?
(b) What is the pH of the solution?
(c ) Select an indicator to use in this titration.
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83
Unit summary
In this unit you learnt the three concepts of acids and bases that
are in current use, namely, Arrhenius concept, Bronsted-Lowry
concept and Lewis concepts. According to Arrhenius, an acid is
Summary
a compound that releases H + ions in water and a base as a
compound that releases OH- ions in water. As for Bronsted-
Lowry, we saw that an acid regarded as a molecule or ion that
can donate a proton (H+) and a base as any molecule or ion that
can accept a proton. We also noticed that Lewis defined an acid
an electron-pair and a base as an electron-pair donor. In
comparative terms, Lewis model was a more general than the
other two models. That is to say, All the Arrehenius and
Bronsted-Lowry reactions are covered by Lewis model. This is
due to the point that the transfer or gain of a proton is
accompanied by the loss or donation of an electron-pair in both
types of reaction. In this unit we also addressed the relative
strength of acids and bases. We noted that the concentration of a
weak acid and a weak base depends on the value of Ka and Kb
respectively. Next, we discussed the pH of solutions. pH was
defined as the negative log of [H+].
84
Assessment
Answer the following questions
Assessment
1. A student prepared 0.01 M NH 3 solution and determined that
NH 3 had undergone 4.2% of dissociation. Calculate the
K b for NH 3 .
2. What will be the pH of a buffer solution made from a mixture
of 0.1 mol dm-3 ethanoic acid and 0.3 mol dm-3 sodium
ethanoate?
Note that the answers to the above exercise are given at the end of
the module. However, you are encouraged to work through first
before referring to the answers.
Provide an extra answer sheet for (e) it requires a long solution

and the solution is not given at the end of this module.
85
Unit 3
Thermochemistry
3.0 Introduction
In this course we have learned how we use chemical formulas and
equations to represent chemical changes. The chemical changes are
accompanied by energy changes. Thus in this unit we discuss how
these energy changes are measured and how they are expressed in
balanced chemical equations. Then you will be able to predict the
energy changes of a reaction and relate these energy changes to
molecular composition.
 Calculate the heat involved in changing the temperature of

any substance. Calculate pH of strong acids and bases,
Outcomes
 Use Hess’s Law to calculate the enthalpy change of a
chemical cange
 Use standard heats of formation to calculate the enthalpy

change accompanying a chemical reaction
 Calculate the average bond energies
86
3.1 Measuring of Heat

Energy changes accompany chemical reactions because there is
building and breaking of forces (chemical bonds) involved in
chemical changes. The net energy changes resulting from breaking
and making chemical bonds are known as heats of reaction.
They are called heats of reaction because heat is the common form
of energy that is absorbed or given out in chemical reactions. Thus
thermochemistry deals with the measurement and calculation of
heats of reaction. The heat of reaction is characteristic property of
the chemical reaction and a major factor in determining whether it
will occur.
Heat measurements always involve the flow of heat. Devices

known as calorimeters are used to measure the flow of heat using
the change in the temperature of a known mass of water to measure
the quantity of heat that is transferred. The SI unit of energy is the
Joule (J). Another unit which is commonly used is the calorie,
(cal), by conversion;
1 cal = 4.184 J
3.1.1 Specific Heat Capacity & Heat capacity
The specific heat capacity is the amount of heat required to raise

the temperature of 1gram of a substance by 10 C ( J g -1 0C -1 ). Or
the amount of heat required to raise the temperature of 1kilogram
of a substance by 1 Kelvin ( kJ kg -1 K -1 ). The specific heat
capacity of water is 1 cal g -1 0C -1 or 4.184 J g -1 0C -1 or 4.184
kJ kg -1 K -1
87
It means that 4.184 J is needed to raise the temperature of 1 gram

of water by 1 0 C . The some amount of heat is removed to cool 1
gram of 1 0 C .
The heat involved in changing the temperature of any substance

can be calculated from the equation:
Heat energy (q) = Specific heat capacity (c)  mass (g)

 temperature change ( t )
t = Final temperature minus – initial temperature.
( t = t final - t Initial )
Heat capacity is the amount of heat required to raise the

temperature of any substance by 1 0 C
Heat energy (q) q

Heat capacity = =
Change in temperature (Δt) Δt
Now let us now work out the following example
Example 3.1
An 19.5 g sample of a metal absorbs 1170 J as its temperature

increases from 25.0 to 92.5 0 C . What is the specific heta capacity
of the metal?
Solution
The sample absorbs heat q = 1170 J
q = specific heat capacity (c )  mass  t
q
c=
m × (t final -t Initial )
88
1170 J
=
18.5 g × (92.5 0 C- 25.0 0 C)
= 0. 937 J g -1 0C -1
You can now do the following activity
Activity 3.1
When 25.0 g of a metal at a temperature of 90.00 0 C is added to

50.0g of water at 25.00 0 C , the water rises to 29.80 0 C . The
specific heat capacity of water is 4.184 J g -1 0C -1 . (a) Find the
specific heat capacity of the metal. (b) The heat capacity of the
metal. (c) What is the difference between specific heat capacity and
heat capacity?
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89
3.1.2 Measuring Heats of reaction: Thermochemical

equations
Heats of reaction are measured by mixing known amounts of
reactants in a calorimeter at a known temperature and letting them
react. The heat evolved or absorbed by the reaction is equal to the
heat that is absorbed or evolved by the calorimeter shown below
Fig 3.1 A bomb calorimeter.
In an exothermic reaction, the chemical reaction gives off heat to

the surrounding, raising the temperature of the reaction products
above the temperature of the calorimeter. The hot products cool by
transferring heat to the calorimeter; as it absorbs this heat, the
calorimeter becomes warm. The calorimeter thus measures the
quantity of heat that must be removed from the calorimeter and the
products below the original temperature.
In an endothermic reaction, the chemical reaction absorbs heat

from the surroundings, lowering the temperature of the calorimeter
and the reaction products below the original temperature. The
calorimeter thus measures the quantity of heat that must be added
90
to the calorimeter and the products to restore them to the original

temperature.
The heat absorbed or evolved by a calorimeter depends on its heat

capacity and the temperature change:
q = Heat capacity  t
the measured change in the temperature of the calorimeter and its

known heat capacity allow us to calculate heats of reaction.
Example 3.2
A fuel with heat capacity 1732.5 J/°C is burned in the calorimeter, Its
temperature rises from 22. 3102 to 23.9863°C. Calculate the heat
absorbed by the calorimeter and evolved by the fuel?
Solution
The heat absorbed by the calorimeter depends on both the heat capacity
and the temperature change:
q = heat capacity  Δt
q = 1732.5J 0 C-1× (23.9863 0 C - 22.3102 0 C)
= 2903.8 J
The heat evolved by the fuel equals the heat absorbed by the calorimeter.
The fuel therefore emitted is 2903.8 J.
Recall that combustion is the process in which a substance burns in air.

The molar heat of combustion of a substance is the amount heat evolved
in the combustion of 1 mole of the substance; its units are kJ mol -1 .
91
Example 3.3
A 0.1000-g sample of liquid benzene, C6 H 6 , is burned
C6 H 6 (l) + 7
1
2
O 2 (g)  3H 2 O(l) + 6CO 2 (g)
In a closed calorimeter whose heat capacity is 1602 J 0C -1 . The

combustion of benzene causes a temperature rise of 2.609°C. Calculate
the molar heat of combustion for benzene.
Solution
First, we find the quantity of heat evolved;
q = heat capacity  Δt
q = 1602 J 0 C-1 × 2.609 0 C
= 4.180 × 103 J
Thus 4180 J is evolved during the combustion of 0.1000 g of C6 H 6 . We
want to calculate the heat evolved by the combustion of 1 mole of C6 H 6
(78.11 g mol-1 ).
mass of C6 H 6
Number of moles of C6 H 6 =
molar mass of C6 H 6
0.100g
=
78.11 g mol-1
= 0.0013 mol
Heat evolved by C6 H 6 in kJ
The Heat evolved per mol =
number of moles of C 6 H 6
1kJ
4.180×103J ×
= 103J
0.0013 mol
= 3215.38 kJ mol -1
The quantity of heat evolved by 1 mol C6 H 6 (l) is 3215.38 kJ mol -1
92
The combustion of C6 H 6 is a typical exothermic reaction. Combustion
of compounds containing C, H and O always produces CO 2 and H 2 O .
Calorimetric measurements of reactions involving gases are made in

containers of fixed volumes so that the chemical reactions occur at
constant volume. Because a volume cannot change under this condition,
expansion or contraction is impossible during the reaction. However,
reactions are frequently carried out in open vessels at constant barometric
pressure.
Data for heats of reaction are generally recorded for the quantity of heat
evolved or absorbed at constant pressure; this quantity is given the
symbol ΔH. This is, ΔH = q(p), measured at constant pressure (volume
may vary). The symbol ΔH is called the change in enthalpy of a
chemical reaction. The enthalpy change accompanying a chemical
reaction, is equal to enthalpy of the products, H products minus the enthalpy
of reactants, H reactants :
ΔH = H products - H reactants
For an exothermic reaction (heat is evolved), the enthalpy of the products,

H (products), must be less than enthalpy of the reactants, H (reactants).
This makes ΔH for exothermic reactions negative, and positive for
endothermic reactions (heat is absorbed), the enthalpy of the products is
more than the enthalpy of the reactant. Thus the enthalpy change for the
combustion of C6 H 6 is - 3215.38 kJ mol -1
93
C6 H 6 (l)+ 7 12 O 2 (g)  3H 2 O(l) + 6CO 2 (g) ΔH = - 3215.38 kJ mol-1
This equation is called a thermochemical equation because it describes

both a chemical reaction and its associated heat change (ΔH).
This means that the enthalpy of the 3 moles of H 2 O (l) and 6 moles of
CO 2 (g) is 3215.38 kJ less than the enthalpy of 1 mole of C6 H 6 (l) and
moles of O 2 (g), as illustrated.

1
7
2
Since ΔH = H products ― H reactants , ΔH is negative for the combustion of
C6 H 6 (l): ΔH = -3215.38 kJ. No attempt is made to define the separate
values of H products and H reactants because values cannot be determined
experimentally. We concern ourselves only with the difference, ΔH,

because this is the quantity measured.
The thermochemical equation for the formation of hydrogen iodide is
1
2 H 2 (g) + 12 I 2 (g)  HI(g) ΔH = +25.9kJmol-1
This means that when ½ mole of gaseous hydrogen reacts with ½ mole of
solid iodine, forming 1 mole of gaseous hydrogen iodide at constant
pressure, 25.9 kJ is absorbed from the surrounding. The enthalpy of the
products is larger than the enthalpy of reactants. Therefore, ΔH for the
reaction is positive as illustrated below
94
Endothermic reaction
The quantity of heat liberated or absorbed in a given reaction depends on

the mass or amount (moles) of reactants or products. Thus, if 2 moles of
C6 H 6 (l) are burnt instead of 1 mole, ΔH is doubled and 2  3215.38 kJ
is given out. It is important to indicate the state of each reactant and
product because ΔH is different for different states
When any substance is heated, it absorbs heat and its enthalpy must
increase. But heat capacities of substances change with temperature and
pressure. Thus, then magnitude of ΔH of a reaction depends on the
temperature and pressure. All data are given at 25°C and at 1 atmosphere
pressure (atm) pressure unless otherwise specified.
Example 3.4
50.0 cm3 of 1.00 mol dm -3 hydrochloric acid solution was added to
50.0 cm3 of 1.00 mol dm -3 sodium hydroxide solution in a polystyrene
beaker. The initial temperature of both solutions was 16.7 0 C . After

stirring and accounting for the heat loss the highest temperature reached
was 23.5 0 C . Calculate the enthalpy change for this reaction
95
Solution
Step 1 . write the equation for the reaction
HCl(aq) + NaOH(aq)  NaCl(aq) + H 2O(l) H = ?
Step2 . Calculate the molar quantities
Moles of HCl = Volume  molarity
= 0.05 dm -3  1.00 mol dm -3
= 0.05 mol
Moles of NaOH = Volume  Molarity
= 0.05 dm -3  1.00 mol dm -3
= 0.05 mol
Therefore the heat evolved will be for 0.05 mol
Step 3. Calculate the heat evolved
The total volume of the solution = 50.0 + 50.0 = 100 cm3
Assume the solution has the same density and specific heat capacity as
water then
Mass of the solution (m) = 100 cm3  1 g cm -3 = 100 g
Specific heat capacity (c ) = 4.184 J g -1 0C -1 .
Temperature change (Δt) = 23.5 – 16.7 = 6.8 0C
Heat evolved in the reaction (q) = c  m  Δt
= 4.184 J g -1 0C -1 .  100g  6.8 0C
= 2845 J
= 2.85k J (for 0.05 mol)
1
ΔH for the reaction = - 2.85 k J  = -57 .00 kJ mol-1
0.05 mol
96
Activity 3.2
When 1.00 L of 1.00 M Ba(NO3 )2 solution at 25.0_C is mixed
with 1.00 L of 1.00 M Na 2 SO 4 solution at 25.0 0C in a calorimeter,

the white solid BaSO4 forms, and the temperature of the mixture
increases to 28.1 0C. Assuming that the calorimeter absorbs only a
negligible quantity of heat, that the specific heat capacity of the
solution is 4.184 J g -1 0C -1 and that the density of the final solution
is 1.0 g cm -3 , calculate the enthalpy change per mole of Ba(NO3 )2

formed.
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3.2 Hess’s Law

Chemical reactions can be carried out in one step or in several
steps. Either way, the net chemical change is the same. For
example, we can burn carbon directly to carbon dioxide:
C(graphite) + O 2 (g)  CO 2 (g) ΔH = -393.509 kJ (1)
Or we can burn carbon to carbon monoxide and then burn the

carbon monoxide to carbon dioxide.
C(graphite) + 12 O 2 (g)  CO(g) ΔH = -110.524 kJ (2)
CO(g) + 12 O 2 (g)  CO 2 (g) ΔH = -282.985 k (3)
C(graphite) + O 2 (g)  CO 2 (g) ΔH = -393.509 kJ (1)
The sum of two steps, reaction 2 and 3, gives reaction 1. You also
notice that the sum of the ΔH values of reactions 2 and 3 is exactly
the same as the ΔH value of reaction 1.
This illustrates the Hess’s Law which states that; the enthalpy
change for reaction depends only on the difference between the
enthalpy of the products and the enthalpy of the reactant; it is
independent of the reaction pathway. In other ways the heat of a
reaction ( ΔH ) is independent of the number of steps involved in
going from the given reactants to the given product.
98
The ΔH for the heat of combustion of carbon is the same whether the reaction
occurs in one step or in two
Hess’s Law allows to predict heats of reactions. It is therefore

frequently used to calculate ΔH for reactions whose heats are
unknown or difficult to measure.
In applying Hess’s Law you keep in mind two properties of the

thermochemical equations:
1. They may be reversed. When we revserse an equation, the

value of ΔH remains the same but its sign is also reversed.
For example, when we reverse
H 2 (g) + 12 O 2 (g)  H 2 O(l) H = -286kJ (exothermic) (4)
We can reverse the equation
H 2 O(l)  H 2 (g) + 12 O 2 (g) H = +286kJ (endothermic) (5)
99
This means that the heat evolved in the formation of 1 mole liquid
water (equation 4) is equal to the heat that would be required to
decompose 1 mole of liquid water (equation 5).
2. They may be treated as algebraic equations. However, when

doing so,
remember that:
 If you multiply or divide an equation by a number,
you must also multiply or divide the ΔH
 If you add an equation as if it were an ordinary
algebraic equation, also add the ΔH values. For
example, addition of the two thermochemical
equations.
1
C2 H 4 (g)+H 2 (g)+3 O 2 (g)  2CO 2 (g) + 3H 2O(l) ΔH=-1696.6kJ 1
2
1
2CO 2 (g) + 3H 2O(l)  C 2 H 6 (g) + 3 O 2 (g) ΔH =+ 1559.8 kJ (2)
2
When we add equation 1 and 2 the like species of substances on

the opposite side of the two equations will cancel each other out;
1
2CO 2 (g) , 3H 2 O(l) and 3 O 2 (g) will cancel out and will remain
2
with C2 H 4 (g) + H 2 (g)  C 2 H 6 (g) as our final equation which is
the equation for the formation of ethane, C2 H 6 (g) . The heat of
reaction of H 2 (g) and C2 H 4 (g) to form ethane is predicted by

adding the ΔH of equation 1 and 2
C2 H 4 (g) + H 2 (g)  C 2 H 6 (g) ΔH = -1696.6 + 1559.8 = -136.8 kJ
10
0
We must only cancel the formula (like species of substances) when

they exist in the same physical state (l, g, s) on the both sides of the
arrow
Example 3.5
From the reactions
C3H8 (g) + 5O 2 (g)  3CO 2 (g) + 4H 2O(l) ΔH = - 2218.8 kJ (1)
C(s) + O 2 ( g )  CO 2 (g) ΔH = - 393.5 kJ (2)

1
H 2 O (l)  H 2 (g) + O 2 (g) ΔH = + 285.8 kJ (3)
2
Predict ΔH for the reaction
3C(s) + 4H 2 ( g )  C3H8 (g) ΔH = ? (4)
Which cannot be measured directly?
Solution
We want ΔH for equation 4.So we concentrate on its reactants and
product. The object is to manipulate the given equations 1, 2 and 3
so that after addition, all substances except those in equation 4 will
cancel. But we want 1 mole of product C3 H8 (g) , so reverse
equation 1 and change the sign of ΔH:
3CO 2 (g) + 4H 2 O(l)  C3H 8 (g) + 5O 2 (g) ΔH = +2218.8 kJ (5)
Since 3 moles of the reactant C(graphite) are needed, multiply

equation 2 by 3: this also multiplies ΔH by 3.
3C(s) + 3O 2 ( g )  3CO 2 (g) ΔH = 3  - 393.5 k J =-1180.5k J (6)

We also need 4 moles of reactant hydrogen: therefore we reverse
equation 3 and multiply it by 4: ΔH is also multiplied by 4 and its
sing is changed.
10
1
4H 2 (g) + 2O 2 (g)  4H 2O (l) ΔH = 4  -285.8 kJ =-1143.2 kJ (7)
Adding equation 5, 6 and 7 cancels the 5O 2 (g) , 4H 2 O(l) , and

3CO 2 (g) in the equation leaving equation 4
3C(s) + 4H 2 ( g )  C3H8 (g)

ΔH = +2218.8 kJ - 1143.2 kJ - 1180.5k J = - 104.9 kJ
Activity 3.3
Use the thermochemical equations:

4PCl5 (s)  P4 (s) + 10Cl2 (g) ΔH = +1774. 0 kJ
PCl3 (l)  P4 (s) + 6Cl 2 (g) ΔH = +1278.8 kJ
To find ΔH for the reaction

PCl5 (s)  PCl3 (l) + Cl 2 (g)
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3.3 Standards Heat of Formation

It would be impractical to list all the chemical reactions for which
ΔH values have been determined. Hess’s law however allows as
summarize these known enthalpy changes in terms of a limited
number of ΔH’s called Standard Heats of Formation. It’s
10
2
possible to calculate from these data the enthalpy changes of these

reactions including the reactions for which the ΔH’s have not been
measured. Before defining the standard heat of formation, however,
we define the term Standard state. The Standard state of any pure
substance is its stable form – solid, liquid or gas – at a pressure of
one atmosphere and a specified temperature, usually 25ºC. Then
the standard heat of formation ΔH 0f , of the substance is the
change in enthalpy when 1 mole of substance in its standard

state is formed from its elements in their standard states. The
superscript zero merely tells us that the reaction was carried out at
the standard condition of one atmosphere pressure. For example, at
25ºC, the standard heats of formation of ammonia, NH 3 and
sodium chlorate, NaClO3 , are the enthalpy changes for these

reactions;
1 1
N 2 (g) + 1 H 2 (g)  NH 3 (g) ΔH 0f = - 46.11 kJ
2 2
1 1
Na(s) + Cl 2 (g) + 1 O 2 (g)  NaClO3 (s) ΔH 0f = -361.1 kJ
2 2
From the definition of standard heat of formation, it follows that

the standard of formation of any element in its stable form at 25ºC
and 1 atm pressure is zero. This is another way of saying that there
is no enthalpy change in the reaction of formation the element from
itself, because there is actually no reaction;
O 2 (250 C,1atm)  O 2 (250C,1atm) ΔH 0f = 0
The stable form of Oxygen at 25ºC and 1 atm pressure is O 2 not O or

O3 (ozone). The addition of energy is required to convert O 2 to O or O3 ;
1
1 O 2 (g)(stable)  O3 (g)(unstable) ΔH 0f = + 142.7 kJ
2
10
3
Let us first study how standard heats of formation are obtained

from measured heats of combustion. Then, we shall study how
these heats of formation are used to calculate ΔHº for reactions.
The ΔH 0f ’s of most organic compounds (carbon-containing

compounds) cannot be measured directly from the one-step
reaction of the elements. Acetylene, C2 H 2 (g) , is typical; it is not
prepared from the reaction
2C(S) + H 2 (g)  C 2 H 2 (g) ΔH 0f = ?
Therefore, its ΔH 0f cannot be measured in such a direct manner.

Instead , ΔH 0f ’s are generally obtained from heats of combustion,
which can be measured with high accuracy.
The heat of combustion of acetylene, C2 H 2 (g) , is

1
C2 H 2 (g) + 1 O 2 (g)  2CO 2 (g) + H 2O(l) ΔHº = -1299.6 kJ 1
2
The ΔH 0f of the combustion products have also been measured;
1
C(s) + 1 O 2 (g)  CO 2 (g) ΔH 0f = -393.5 kJ 2
2
1
H 2 (g) + 1 O 2 (g)  H 2 O(l) ΔH 0f = -285.9 kJ 3
2
Hess’s law now permits us to calculate the ΔH 0f of C2 H 2 (g) . Reverse

equation 1, making C2 H 2 (g) a product, and change the sign of its ΔH.
Then multiply equation 2 and ΔH 0f by 2;
1
2CO 2 (g) + H 2 O(l)  C 2 H 2 (g) + 1 O 2 (g) ΔHº = +1299.6 kJ (4)
2
10
4
2C(s) + 2O 2 (g)  2CO 2 (g) ΔH 0f = 2  -393.5 = -787.0 kJ (5)

1
H 2 (g) + 1 O 2 (g)  H 2 O(l) ΔH 0f = -285.9 kJ (6)
2
Addition of equation 4, 5 and 6 cancels the 2CO 2 (g) , H 2 O(l) , and the
1
1 O 2 (g) on both sides of the equation, yielding the standard heat of
2
formation of C2 H 2 (g) .
2C(S) + H 2 (g)  C2 H 2 (g) (7)
ΔH 0f = +1299.6kJ -787.0 kJ – 285.9 kJ = +226.7 k J

An examination of the table of standard heats of formation,
Appendix A, shows that most of the heats of formation are
negative. This tells us that most compounds require a heat input for
decomposition to the elements. Acetylene C2 H 2 (g) , on the other
hand, has a positive heat of formation and decomposes with large
output of heat.
Let us now calculate the heat of combustion of Carbon

disulfide, CS2 an excellent solvent for waxes, greases, and
cellulose,
CS2 (l) + 3O 2 (g)  2SO 2 (g) + CO 2 (g) ΔHº =? 1
From the following ΔH 0f ’s:
C (s) + 2S(s)  CS2 (l) ΔH 0f = +89.7 k J 2
S(s) + O 2 (g)  SO 2 (g) ΔH 0f = -296.8 kJ 3
C(S) + O 2 (g)  CO 2 (g) ΔH 0f = -393.5kJ 4
10
5
To obtain the heat of combustion of CS2 (l), reverse equation 2 to make
CS2 a reactant and change the sign of its ΔH 0f ; multiply equation 3 and
its ΔH 0f by 2 to get 2 moles of SO 2 ; then add the three equations;
CS2 (l)  C (s) + 2S(s) ΔHº = ΔH 0f = -89.7 k J (5
2S(s) + 2O 2 (g)  2SO 2 (g) ΔHº =2  ΔH 0f = -593.6 kJ (6
C(S) + O 2 (g)  CO 2 (g) ΔHº = ΔH 0f = -393.5kJ (7
CS2 (l) + 3O 2 (g)  2SO 2 (g) + CO 2 (g) ΔHº = - 1076.8 kJ (8
Let us examine what we have done;
 We added the heats of formation of the products, CO 2 and
SO 2 , after adjusting for the number of moles written in the

given chemical equation.
 But notice that the heat of formation of the reactants, CS2 ,

was not added. By reversing and changing the sign of the
ΔH 0f of CS2 , we subtracted the heats of formation of the
reactants.
The procedure may be summarized as follows; The enthalpy

change of reaction, ΔHº, equals the sum of the heats of formation
of the reactants, each multiplied by its coefficients in the chemical
equation, abbreviated as;
ΔH 0reaction = totalΔH 0products - totalΔH 0reactants
ΔH 0reaction =[2×ΔH 0f SO 2 (g)+ΔH f0CO 2 (g)]-[ΔH f0CS2 (l)+3×ΔH f0 O2 (g)]
= [(2× -296.8kJ)-393.5kJ]-[+89.7kJ + 0kJ]
= - 1076.8 kJ
10
6
Activity 3.4
The heat of combustion methane is

CH 4 (g) + 2O2 (g)  CO 2 (g) + 2H 2 O(l) ΔHº = -890.41 kJ
Use the heats of formation of CO 2 ( ΔH 0f =-393.509kJ) and H 2O
( ΔH 0f = -285.830 kJ) to find the value for the heat of formation of

methane, CH4.
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3.4 Bond Energy
Bond energy is the energy associated with breaking a chemical

bond between atoms in a gaseous molecule. The dissociation (bond
breaking) of 1 mole of HI (g) into gaseous atoms absorbs 298.3 kJ,
while the formation of1 mole of HI (g) from gaseous atoms evolves
298.3 kJ.
The higher a energy given weight (the longer the distance from the
earth), the larger the potential energy. Similarly, the longer the
10
7
distance of an H atom from an I atom, the larger is the potential

energy. Thus, when a molecules forms there is a reduction in
potential energy. In general, a molecule always has a lower energy
than the atoms from which it is formed. This is another way of
saying that energy is required to separate a molecule into its atoms.
The quantity of energy (ΔH) required to break one mole of a bond

in one mole of gaseous molecule in the gaseous state, forming
gaseous products, is called the bond dissociation energy, or
simply the Bonding energy, abbreviated BE. Bond Breaking in
gaseous molecules is always endothermic: thus, ΔH for bond
energy is always positive. On the other hand, bond formation
from gaseous atoms is always exothermic; and the ΔH negative.
For example, the bond energy for H―I (g) is 298.3 kJ. This means
that in the reaction
HI(g)  H(g) + I(g) (endothermic) ΔH = BE = + 298.3 kJ
Heat is absorbed in the breaking of bonds, while in the bond formation
H(g) + I(g)  HI(g) (exothermic) ΔH = BE = -298.3 kJ
The same quantity of heat is evolved.
For molecules with two or more identical atoms attached to another

atom, such as H 2 O , NH 3 and CH 4 , it is possible to assign a bond
10
8
energy to each of the bonds. To do so, first find the total quantity of
energy needed to break all the bonds in the molecule. Then, divide
that total by the total number of bonds in the molecule. This gives
average bond energy, as illustrated in the example below.
Average bond energy is also simply called a bond energy.
Example 3.6
Assign average bond energy to the C―H bond from the given
heats of reaction
There are 4 C―H in CH 4
CH 4  C(g) + 4H(g) ΔH = + 1663. 29 kJ (1)
Solution.
In all calculations involving bond energies, recall the three basic

rules;
1. Energy is always required to break chemical bonds in

gaseous molecules.
2. Energy is always given out when gaseous atoms combine.
3. Note the kind and number of bonds broken or formed.
Here, notice that the only reaction occurring is the breakage of four
moles of C―H bonds. Thus, 1663.29 kJ is the total quantity of
energy that is absorbed in breaking four moles of C―H bonds.
10
9
Division by four thus assigns an average bond energy to the C―H

bonds;
+1663.29kJ
C―H(g)  C(g) + H (g) ΔH = BE =
4mol(C-H)
kJ
= +416
mol(C-H)
This means that for the reaction
C―H(g)  C(g) + H (g) (bond breaking) ΔH = BE = +416 kJ
And for the reaction
C(g) + H (g)  C―H(g) (bond forming) ΔH = -BE = -416 kJ
Table 3.1 Bond energies
Reactions like reaction 1,in which a molecule is dissociated into

atoms, can seldom be carried out directly. Bond energies usually
have to be calculated by Hess’s law. In particular, bond energies
can be obtained from known heats of formation. Typical is the
calculation of the bond energies for the N―H bond from
ΔH 0f NH 3 .
Bond energies involve gaseous atoms as either reactants or

products
N(g) + 3H(g)  NH 3 (g) ΔH = ? 1
11
0
However the thermochemical equation for H 0f NH 3
( See Appendix B) involves only molecules
1 1
N 2 (g) + 1 H 2 (g)  NH 3 (g) H 0f = -46.11kJ 2
2 2
Therefore, first we should convert N 2 (g) and H 2 (g) ;
from table 3.1
N 2 (g)  2N(g) (bond breaking, endothermic) ΔH = +945.6 kJ 3
H 2 (g)  2H(g) (bond breaking, endothermic) ΔH = + 435.9 kJ 4
We need ΔH for equation 1.Therefore, reverse equations 2 and 3

and multiply equation 1 by ½ and equation 3 by 1 ½:
1
N(g)  N 2 (g) (bond formation , exothermic) ΔH = ½  -945.6 kJ
2
= -472.8 kJ 5
1
3H(g)  1 H 2 (g) (bond forming, exothermic) ΔH = 1 ½  - 435.9 kJ
2
= -653.9 kJ 6
Then adding equations 2, 5, and 6 gives the desired equation 1:
1 1
N 2 (g) + 1 H 2 (g)  NH 3 (g) H 0f = -46.11kJ 2
2 2
1
N(g)  N 2 (g) ΔH = -472.8 kJ 5
2
1
3H(g)  1 H 2 (g) ΔH = -653.9 kJ 6
2
N(g) + 3H(g)  NH 3 (g) ΔH = - 1172.8 kJ 1
11
1
By definition, bond energy is the quantity of energy needed to

dissociate (break) a mole of the bond. Therefore reverse equation 1:
NH 3 (g)  N(g) + 3H(g) ΔH = + 1172.8 kJ 1
However, +1172.8 kJ is the total quantity of energy that is absorbed

in breaking three moles of N―H bonds. Division by three assigns
an average bond energy to the N―H bond.
+1172.8 kJ
N-H(g)  N(g) + H(g) ΔH = BE =
3mol(N-H)
kJ
= +391
mol(N-H)
This result agrees with the value in table 3. 1
The greater the bond energy is, the greater also the energy released
in forming the bond, the energy needed to break the bond and the
bond stability. Thus H―H (436 kJ/mol) is amore stable bond than
F―F (158 kJ/mol); more energy is need break the H―H bond.
Bond stability should not be confused with unreactivity, the
tendency not to react. Under given conditions, an uncreative
substance has little tendency to under go chemical changes with
itself or other substances. High bond stability does not necessarily
mean that the molecule is uncreative. For instance, Oxygen, O2 ,
has relatively high bond energy of 498 kJ/mol, but it is very
reactive. It reacts with other elements to form Oxides.
Some bond energies are given in table 3. 1. Those energies may be

used for any molecule in which the particular bonds appear,
because of the assumption that the bond energy of a given pair of
atoms is independent of the molecule in which it resides. However,
11
2
average bond energies vary somewhat in different compounds―

such as the C―H bond in CH 4 , C2 H 4 , and C2 H 2 ―but not enough
to prevent them from being useful. Consequently, bond energies
are used to determine the ΔH for the reactions in the phase whose
heats of reaction are unknown. Failure to keep track of signs and
coefficients must lead to a wrong answer. Remember; Bond
breaking is always endothermic and its ΔH is positive, as given in
table 3.1. Bond formation on the other hand, is always exothermic,
and its ΔH is negative. If the total energy input (bond breaking)
exceeds the total output (bond formation), the reaction is
endothermic (ΔH is positive); if the total output exceeds the total
input, the reaction is exothermic (ΔH is negative). So examples
follow.
Example 3.7
Use the bond energies in the table 4.3 to calculate the heat of the
reaction;
CH 4 (g) + 4Cl 2 (g)  CCl 4 + 4HCl(g)
Solution
List the kind and number of moles of bonds broken (endothermic)

and formed (exothermic) with their bond energies and ΔH values as
shown.
Moles of
Bond broken bonds broken BE- kJ/mol Reaction ΔH

C-H 4 416 CH 4  C + 4H +1664kJ
Cl – Cl 4 244 4Cl2  8Cl +976kJ
Moles of
Bond formed bonds formed BE- kJ/mol Reaction ΔH

C-Cl 4 326 C+ 4Cl  CCl 4 -1304kJ
H-Cl 4 431 4H + 4Cl  4HCl -1724 kJ
11
3
This can be illustrated:
Addition of the ΔH’s yields:
H reaction = +1664kJ + 976kJ - 1304kJ -1724 kJ = -388kJ
The experimental value is -395kJ/mol CH 4
Activity 3.5
Calculate ΔH for the reaction

CH 4 (g) + 4F2 (g)  CF4 (g) + 4HF (g) .
The experimental value is –1937 kJ/(mol CH 4 (g) ).
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11
4
Although agreement between the calculated ΔH and the

experimental ΔH is usually good, significant differences occur for
many reactions. These discrepancies compel us to re-examine our
assumptions that the properties of a bond are independent of its
molecular environment. The re-examination, in chapter 8, will lead
us to a better understanding of the nature of bonds holding atoms
together in molecules.
The term ‘bond energy’ may be misleading because it may imply a

bond full of vim and vigor, perhaps ready to explode. Such a notion
is incorrect. Bond energy is rather the energy that the bonded atoms
do not have, and which they will not get until some outside source
of energy comes along and breaks the bond. Thus, high bond
energy means that the bond requires a high energy input for
separation of the atoms. An explosive compound like TNT or
nitroglycerine can do its work because a reaction converts (weaker)
bonds of lower bond energy (high potential energy) to (stronger)
bonds of higher bond energy (lower potential energy}
11
5
Unit summary
In this unit we have learned that chemical reactions are

accompanied by energy changes, mainly in the for of heat
emitted or absorbed. When heat of reaction is measured at
Summary
constant temperature and constant volume is called enthalpy
change(ΔH) which is determined by
ΔH = H products ― H reactants ,
Most chemical reactions are exothermic they release energy to

the surrounding; others are endothermic, they absorb energy
from the surroundings. The ΔH in exothermic reactions is +ve
and –ve in endothermic reactions. According to Hess’s Law the
ΔH does not depend on the steps in chemical change
11
6
Assessment
Answer the following questions
Assessment
1. A student used a simple calorimeter to determine the enthalpy
change for the combustion of ethanol. When 0.690 g of ethanol was
burned, it produced a temperature rise of 13.2 K in 250 g of water.
Calculate ΔH for the reaction
C2 H 5OH(l) + 3O 2 (g)  2CO 2 (g) + 3H 2O(l)
2. 50.0 cm3 of 0.200 mol dm -3 copper(II) sulphate solution was

placed in a polystyrene cup. After 2minutes 1.20g of powdered zinc
was added. The temperature was then taken every 30 seconds for
about 10 minutes and the temperature change was found to be
10.40 C . Calculate the enthalpy change for the reaction
Note that the answers to the above exercise are given at the end of
the module. However, you are encouraged to work through first
before referring to the answers.
Provide an extra answer sheet for these questions
11
7
Answers to Activities
Unit 1
Activity 1.1
[HCl]2
(a) K c = [CO 2 ] (b) Kc =
[CH 2 Cl][Cl 2 ]3
[NO]4 [H 2 O]6
(c ) K c =
[NH]4 [O 2 ]5
Activity 1.2
K c = 7.8×10 4 The mixture consists mainly products, [NO 2 ] is much
larger than [N 2O 4 ]
Activity 1.3
Q = 5.0×10-4 , Q < K c Forward reaction will be favoured to make
Q lager and equal to Kc
Activity 1.4
[NO]=1.3×10-3 [O 2 ]  0.199  0.20 [N 2 ] = 0.799  0.80
Activity 1.5
(a) Adding Cl 2 shifts the equilibrium to the right; PCl3 is decreased
Cl2 is increased Kp is unchanged

(b) Shifts the equilibrium to the right PCl3 is decreased, PCl5 is
increased.
(c) The reaction shifts to the left; Cl 2 and PCl3 are increased Kp
decreases.
11
8
Unit 2
Activity 2.1
(a) HNO3 +H 2 O  H 3 O + + NO-3

acid base
(b) H 3O + + F+  H2 O + H F
base acid
Activity 2.2
(a) NH 4  / NH 3 , H 2 O/OH - , OH  / O 2 , H 2 /H -
(b) NH 4  / NH 3 , HNO3 / NO3- , H 2 PO4 / HPO42  , HSO4  / SO4

Activity 2.3
NH 3 is a Lewis base it donates its lone pair of electron to form a
coordinate covalent bond with H  a Lewis acid
Activity 2.4
(a) pH = 12.3 (b) pH = 1.4
Activity 2.5
pH = 1.6
Activity 2.6
pH = 11.1
Activity 2.7
NH 3  H 2 O  NH 4   OH -
The solution has a reservoir of the base ( NH 3 ) and the acid ( NH 4  )

when a small amounts of the acid H  is added to this solution it reacts
with the base NH 3 to produce a weak acid ( NH 4  ) NH 3 +H +  NH 4 +
And addition of a base OH - wil react with an acid NH 4  to produce a

base NH3 and water NH 4 +  OH -  NH 3  H 2 O
Activity 2.8
pH = 4.9
Activity 2.9
(a) NH 4 Cl (b) pH = 5.43
( c) Methyl red would a good choice
11
9
Unit 3
Activity 3.1
(a) 0.666J g -1 0 C -1 (b) 16.66 J 0 C-1
(c) Heat capacity is the amount heat needed to raise the
temperature of a substance by 1 0 C . While Specific heat
capacity is the amount heat required to raise the temperature
of 1 g of a substance by 1 0 C
Activity 3.2
(1) q = 90.83 kJ (2) ΔH = -26 kJ mol-
Activity 3.3
ΔH = +123.8 kJ
Activity 3. 4
ΔH 0f = - 74.73 kJ
Activity 3.5
ΔH = -1940 kJ mol-
12
0
Answers to Assessments
Unit 1
1. [ SO2 ] = 0.075 mol [O 2 ] = 0.537 mol and [ SO3 ] = 0. 925 mol
K c = 2.8 x 10 2
2. (a) The mass of NO will decrease because of a forward reaction
(b) Mass of NO will increase
(c) The mass of will increase
(d) No change on the mass of NO
(e) The mass of NO will increase
Unit 2
1. K b  1.76  10 5
2 . pH = 5.3
Unit 3
1. ΔH = -920 kJ mol -1
2. ΔH = -217 kJ mol-1
12
1
Readings
There are a number of excellent resources on the web. A few suggested links
are:
 http://www.how-to-study.com/
The “How to study” web site is dedicated to study skills resources. You
will find links to study preparation (a list of nine essentials for a good
study place), taking notes, strategies for reading text books, using
reference sources, test anxiety.
 http://www.ucc.vt.edu/stdysk/stdyhlp.html
This is the web site of the Virginia Tech, Division of Student Affairs.
You will find links to time scheduling (including a “where does time go?”
link), a study skill checklist, basic concentration techniques, control of the
study environment, note taking, how to read essays for analysis, memory
skills (“remembering”).
 http://www.howtostudy.org/resources.php
Another “How to study” web site with useful links to time management,
efficient reading, questioning/listening/observing skills, getting the most
out of doing (“hands-on” learning), memory building, tips for staying
motivated, developing a learning plan.
The above links are our suggestions to start you on your way. At the time of
writing these web links were active. If you want to look for more go to
www.google.com and type “self-study basics”, “self-study tips”, “self-study
skills” or similar.
Important 1. P. Mathews (1992). Advanced Chemistry, , Cambridge

note : If you University Press,
have not yet
done so,
please 2. Brescia F., Arent J.,Meislich H., and Turk A (1987).General
review the Chemistry, 5th Ed Academic press; New York
3. Geofrffrey N (2001) Chemistry for the IB Diploma
Oxford University Press, Great Britain
12
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MUKUBA UNIVERSITY

CHE110: INTRODUCTION TO CHEMISTRY

© Copperbelt University College 2013.

No part of this module may be reproduced or transmitted in any form or by any

Directorate of Distance Education (DODE)-

Mweshi E : Lecturer CBUC

Muma E : Lecturer CBUC

Mukonde B: Lecturer CBUC

Changwe P: Lecturer CBUC

About Content iii

About this Module 1

Getting around this Module 7

Unit summary ................................................................................................................. 84

About this Module

How this module is structured

The module overview

Welcome to the module on

This module is part of Introduction to Chemistry Courses in the

We strongly recommend that you read the overview carefully

The module content

 Course content and structure.

 Course reading materials and resources.

 Course support (assigned tutors, technical help, etc.)

Your constructive feedback will help us to improve and enhance

 Explain chemical equilibrium, and apply le chaterlier’s

 Calculate the pH of weak and strong and weak acids and

Essentially you will be taking control of your learning

We recommend that you take time now—before starting your self-

Mr Muma E Cell: 0977-185244 / 0969735302

The assignments should be handed in to course tutors during the

You will be required to submit the assignments in the order in

Getting around this Module

A complete icon set is shown below. We suggest that you

Activity Assessment Outcomes Note it!

 Use the law of mass action to express the law of equilibrium.

 Calculate the equilibrium constant for an equilibrium mixture.

Outcomes  Calculate the equilibrium concentrations of reactants and

 Compare the value of the reaction quotient and the equilibrium

 Use the Le chatelier’s principle to determine the shift in the

1.1 The Equilibrium Constant

Reversible reactions are shown by double arrows between reactants

Action mass is the molar concentrations of the reacting substances,

Let as consider this law using a general form of a balanced

Rate of combination of A and B product of the action

Ratef [A]a [B]b

Rateforward = Kf [A]a [B]b _ _ _ (1)

forward velocity constant

Ratereverse [C]c [D]d

Ratereverse = Kr [C]c [D]d _ _ _ _ (2)

Reverse velocity constant

At equilibrium, the two rates are equal

Kfoward [A]a [B]b = Kreverse [C]c[D]d -------------- (3)

To find the equilibrium constant we make we divide both sides by

K forward [C]c [D]d

If the system is NOT at equilibrium, the ratio is different from the

For gases equilibria, the equilibration constant can be expressed in

For ideal gases, KC and KP conversions are done by applying the

1.1.1 Rules for writing the equilibrium expression

 The equilibrium expression contains the concentration

 The concentration term [solid] or [liquid] for pure solid or

At a particular temperature each reaction has a unique equilibrium

Write the equilibrium expression for the following equilibrium

(a) The equilibrium constant expression for a equilibrium mixture

(b) The equilibrium expression for silver chloride solution.