Unit P2 Equilibrium I Principles

UNIT
Equilibrium I:
Principles
1IIIIij'IIIIII~IIIJIUIIII
N27906
CEf\JTRE
© Inner London Education Authority 1983
First published 1983

by John Murray (Publishers) Ltd
50 Albemarle Street
London W1 X 4BD
Reprinted 1984, 1985, 1987, 1989, 1990
All rights reserved.

Unauthorised duplication
contravenes applicable laws
Printed and bound in Great Britain by

St Edmundsbury Press Ltd, Bury St Edmunds, Suffolk
British Library Cataloguing in Publication Data

Independent Learning Project for Advanced
Chemistry
Equilibrium I: Principles. - (ILPAC; Unit P2)
1. Science
I. Title II. Series
500 Q161.2
ISBN 0 7195 4040 2
ii
CONTENTS
PREFACE v
Acknowledgements vi
Key to activity symbols and hazard symbols vii
INTRODUCTION 1
Pre-knowledge 2
Pre-test 3
LEVEL ONE 5
EQUILIBRIUM SYSTEMS 5
Reversible reactions 5
Types of equilibrium system 6
Phase 7
Some examples of equilibrium systems 8
Equilibrium in homogen~ous and heterogeneous systems 9
General statements about equilibrium 9
CHARACTERISTICS OF THE EQUILIBRIUM STATE 9
Why equilibrium systems are 'closed' 11
How equilibrium systems are established 12
FACTORS AFFECTING THE POSITION OF EQUILIBRIUM 12
Position of equilibrium 13
Le Chatelier's principle 13
The effect on equilibrium of changing conoentrations 14
Experiment 1 - the effect of concentration changas on equ~libFia 15
Pure solids and pure liquids in equilibrium systems 17
The effect on equilibrium of changing temperature 19
The effect on equilibrium of changing pressure 21
The effect on equilibrium of catalysts 24
LEVEL ONE CHECKLIST 25
LEVEL ONE TEST 27
LEVEL TWO 29
THE EQUILIBRIUM LAW 29
Calculating the value of an equilibrium constant 31
When volume can be omitted from an equilibrium law expression 32
Experiment 2 - determining an equilibrium constant 33
Computer simulation of the ethyl ethanoate equilibrium 38
Various numerical problems involving equilibrium constants 38
Problems involving quadratic equations 42
THE EQUILIBRIUM CONSTANT, Kp 46
The effect on an equilibrium system of changing pressure 48
Computer simulation of sulphuric acid manufacture 51
Average molar mass of a gaseous mixture 51
THE VARIATION OF EQUILIBRIUM CONSTANT WITH TEMPERATURE 53
SOLUBILITY PRODUCTS FOR SLIGHTLY SOLUBLE SALTS 54
Calculating solubility product from solubility 55
Experiment 3 - determining a solubility product 56
Calculating solubility from solubility product 58
Limitations of solubility product theory 59
The common ion effect 59
Exp eri men t 4 - illustrating the corrmon ion effect 60
Will precipitation occur? 62
DISTFIBUTION EOUILIBRIUM 64
II/
Experiment 5 - distribution equilibrium 64
LEVEL TWO CHECKLIST 68
END-Of-UNIT TEST 69
APPENDIX ONE
Additional exercises 73
APPENDIX TWO
The relationship between the equilibrium constants, K and K 79
The relationship between K and ~G~ c p 80
The relationship between K and ~~ 82
ANSWERS TO EXERCISES 86
iv
PREFACE
This volume is one of twenty Units produced by ILPAC, the Independent Learning
Project for Advanced Chemistry, written for students preparing for the Advanced
Level examinations of the G.C.E. The Project has been sponsored by the Inner
London Educatio~ Authority and the materials have been extensively tested in
London schools and colleges. In its present revised form, however, it is
intended for a wider audience; the syllabuses of all the major Examination
Boards have been taken into account and questions set by these boards have been
included.
Although ILPAC was initially conceived as a way of overcoming some of the

difficulties presented by uneconomically small sixth forms, it has frequently
been adopted because its approach to learning has certain advantages over more
traditional teaching methods. Students assume a greater responsibility for
their own learning and can work, to some extent, at their own pace, while
teachers can devote more time to guiding individual students and to managing
resources.
By providing personal guidance, and detailed solutions to the many exercises,

supported by the optional use of video-cassettes, the Project allows students
to study A-level chemistry with less teacher-contact time than a conventional
course demands. The extent to which this is possible must be determined
locally; potentially hazardous practical work must, of course, be supervised.
Nevertheless, flexibility in time-tabling makes ILPAC an attractive propo-
sition in situations where classes are small or suitably-qualified teachers
are scarce.
In addition, ILPAC can provide at least a partial solution to other problems.

Students with only limited access to laboratories, for example, those studying
at evening classes, can concentrate upon ILPAC practical work in the laboratorYj
in the confidence that related theory can be systematically studied elsewhere.
Teachers of A-level chemistry who are inexperienced, or whose main discipline
is another science, will find ILPAC very supportive. The materials can be used
effectively where upper and lower sixth form classes are timetabled together.
ILPAC can provide 'remedial' material for students in higher education.
Schools operating sixth form consortia can benefit from the cohesion that ILPAC
can provide in a fragmented situation. The project can be adapted for use in
parts of the world where there is a severe shortage of qualified chemistry
teachers. And so on.
A more detailed introduction to ILPAC, with specific advice both to students

and to teachers, is included in the first volume only. Details of the Project
Team and Trial Schools appear inside the back cover.
LONDON 1983
v
ACKNOWLEDGEMENTS
Thanks are due to the following examination boards for permission to
reproduce questions from past A-level papers:
Southern Universities Joint Board;

Exercises 29(1979), 31(1975), 54(1980)
Oxford Oelegacy of Local Examinations

Exercise 48(1979)
End-of-Unit Test 12(1981)
The Associated Examining Board

Exercises 28(1974), 40(1976), 51(1979)
University of Cambridge Local Examinations Syndicate

End-of-Unit Test 14(1979)
University of London Entrance and School Examinations Council

Exercises 27(L1977), 86(N1975)
End-of-Unit Test 1(L1979), 1(L1978), 3(L1979), 4(N1978), 5(N1979)
6(N1978), 7(N1977), 8(N1977), 11(L1980), 13(L1982)
Exercises 39, 41, 42 and 49 are reproduced, by permission, from Nuffield

Advanced Science: Chemistry; Students' Book I, edited by B.J. Stokes
and published by Longman Group Limited for the Nuffield Foundation.
Photographs are included by permission as follows:

Henri Le Chatelier, p14 - The Macaulay Institute for Soil Research
Photographs of students - Tony Langham
vi
SYMBOLS USED IN ILPAC UNITS
&, Reading Revealing exercises
Exercise
~ Discussion
~
~\;l Test £: Computer programme
o 'A' Level question

~ Experiment
-
I[ 1) Video programme
'A' Level part question 00
[J:.2U
-
Film loop
'A' Level question
Special paper
Model-making
- Worked example
[] Teacher-marked exercise
INTERNATIONAL HAZARD SYMBOLS
IXI Harmful I~ Toxic Radioactive
181 Flammable g
~ Explosive
--
~
• ~ Corrosive I~ 1 Oxidising
vii
INTRODUCTION
This is the first of three Units on the subject of equilibrium. which is
an important concept in every branch of chemistry. In this Unit. we outline
the principles of equilibrium and show that they are applicable to a wide
variety of situations.
In Level One we deal with the qualitative aspects of equilibrium. and show
you how to apply a useful rule. known as Le Chatelier's principle. to
summarise the way equilibrium systems react to changes in conditions.
In Level Two we introduce the equilibrium law, a mathematical statement

which describes all equilibrium systems. We show you how to apply the
equilibrium law to a number of different systems, including the equilibrium
between a slightly soluble salt and its saturated solution. and the
distribution of a solute between two different solvents. Further
applications appear in Unit P3 (Equilibrium II: Acids and Bases) and
Unit P6 (Equilibrium III: Redox Reactions).
There are five experiments in this Unit. four of them in Level Two.
There is an ILPAC video-programme designed to accompany this Unit. It is

not essential, but you should try to see it at the appropriate time if it is
available.
Equilibrium
1
PRE-KNOWLEDGE
Before you start work on this Unit, you should be able to:
(1) state some examples of reversible reactions;

(2) write a thermochemical equation for a reaction, given the appropriate
data;
(3) write simple definitions of the following terms -
(a) amount of substance, (d) solubility,
(b) molar mass, (e) partial pressure,
(c) concentration, (f) catalyst;
(4) write equations, including state symbols, for the reactions between
(a) ethanol and ethanoic acid,
(b) iron and steam,
(c) calcium chloride and sodium carbonate;
(5) rearrange an equation of the type
3x
5= (1-x)(3-2x)
into a standard quadratic equation of the form ax2 + bx +. c o.
PRE-TEST
To find out whether you are ready to start Level One, try the
following test, which is based on the pre-knowledge items. You
should not spend more than 30 minutes on this test. Hand your
answers to your teacher for marking.
2
PRE-TEST
1. Write a thermochemical equation summarising the information given in
the energy level diagram below.
1367
(2)
2. What effect does a catalyst have on a chemical reaction? (1)
3. Define the following terms. stating the usual units.

(a) concentration. (2)
(b) molar mass. (2)
(c) solubility. (2)
(d) partial pressure. (2)
4. Write equations. including state symbols. for the reactions between:

(a) ethanol and ethanoic acid. (2)
(b) iron and steam. (2)
(c) calcium chloride and sodium carbonate. (2)
5. Rearrange into standard quadratic form the equation:

6x
4 = (1- 2x) (2 - x) (3)
(Total 20 marks)
3
LEVEL ONE
EQUILIBRIUM SYSTEMS
Objectives. When you have finished this section you should be able to:
(1) recognise that reversible changes are an essential feature of

equilibrium systems;
(2) quote examples of different types of equilibrium syste~;
(3) use the term phase to distinguish between homogeneous and heterogeneous
systems.
Reversible reactions
Most of the chemistry you have studied so far has been concerned with
reactions which appear to 'go to completion'. For example, when magnesium
burns in oxygen. all of the metal is converted to magnesium oxide. and when
a lump of calcium-carbonate is dropped into an excess of hydrochloric acid,
I
all of the solid reacts.
2Mg(s) + 02(g) ~ 2MgO(s)

CaC03(s) + 2HCI(aq) ~ CaCI2(aq) + H20(I) + CO2 (g)
In neither of these cases is there any indication that the reverse c~ange
occurs.
The idea of reversible change is very familiar in systems where no

chemical reaction occurs; for example. ice melting to water and water
freezing to ice. However, you have also met some reversible reactions; i.e.
chemical reactions which can be made to 'go both ways'.
For example, if iron is heated in a current of steam, it can be converted

completely to iron(II) diiron(III) oxide, Fe304•
3Fe(s) + 4H20(g) ~ Fe304(s) + 4H2(g)
But if the oxide is heated in a current of hydrogen the reverse reaction
occurs.
However, if the system is closed (no material can pass in or out) so that
reactants and products are always in contact, both reactions can occur at
the same time. Then the system achieves a state of equilibrium in which
the reversible changes 'cancel each other out'.
We can represent this state of equilibrium by a 'double-ended arrow', ~.

(In some books you may find the 'equals' sign, =, used ~or this purpose.)
We use this symbol to imply that two opposing processes are occurring at
the same time; e.g.
3Fe(s) + 4H20(g) ~ Fe304(s) + 4H2(g)
5
Does it make any difference if we write the equation the other way round?
Fe30~(s) + 4H2(g) ~ 3Fe(s) + 4H20(g)
We will answer this question shortly.
Other examples of equilibrium systems you may have studied in your pre-A-
level course are:
N2(g) + 3H2(g) ~~ 2NH3(g)
CaC03(s) + CO2 (g) + H2O(I) ~~ Ca(HC03)2(aq)
ICI(I) + CI2(g) ~~ ICI3(s)
(brown) (green) (yellow)
You may be surprised to learn that it is useful to consider all chemical

reactions as equilibrium systems even when the processes cannot be readily
l
reversed. We consider different types of equilibrium system in the next

section.
Types of equilibrium system
There are many situations in which opposing changes occur at~the same time.
leading to a state of equilibrium. The different types of equilibrium we
shall discuss in ILPAC Units can be classified as shown in Table 1.
Table 1
PHYSICAL PROCESSES
1. Pure solid/pure liquid.
2. Pure liquid/pure vapour.
3. Pure solid/pure vapour.
4. Pure solid in contact with a solution l dissolving and crystallizihg
occurring together.
5. Solute distributed (or partitioned) between two solvents which are
immiscible (i.e., do not mix - like oil and water).
CHEMICAL PROCESSES
6. Chemical equilibria with reactants and products in the same phase*.
7. Chemical equilibria with reactants and products in different phases.
Types 6 and 7 cover all chemical processes, but they may be further
subdivided:
8. A slightly soluble ionic solid in contact with a solution containing
its ions dissolving and crystallizing occurring together.
l
9. Acid-base systems (dealt with more fully in Unit P3).

10. Redox systems (dealt with more fully in Unit P6).
11. Complex ion formation (dealt with more fully in Unit 15).
*We explain the term 'phase' in the next section.
6
Phase
A phase is defined as any uniform (i.e. homogeneous) part of a system
which is different from the rest of the system and separated from it by a
distinct boundary. Here are some examples.
oil
~~I--- boundary
water
NaCI,Si02, CuO
Fig. 1. Fig. 2.
1. The contents of a tube 2. A mixture of salt, sand and

containing oil and water is a copper(II) oxide, even when
system with two phases (Fig. 1). finely ground, is a three-
phase system (Fig. 2).
_~ ~ _ -...•
.....-- alcohol and
water
Fig. 3. Fig. 4.
3. There can be only one gas phase 4. Miscible liquids form a one-
because gases always diffuse into phase system, because, like
one another to form a homogeneous gases, they form a homogeneous
mixture. Air is a one-phase mixture. An example is alcohol
system (Fig. 3). and water (Fig. 4).
Some of these different types of equilibrium system are illustrated in

Fig. 5(A) to (LJ. It will be useful for you later on if you can identify
the various types. So now do Exercise 1.
Exercise 1 Look at the list of different types of equilibrium syste~

in Table 1. For each type, choose one suitable example
from those illustrated in Fig. 5. ~~
(Answers on page 86 )
7
Some examples of equilibrium systems
bromine gas
water at saturated
ODC. sugar
solution
liquid bromine
surroundings at ODC. sugar crystals
A 8 c
iodine
crystals
result of mixing
iodine ethanoic acid
vapour and ethanol
D E F
mixture of
steam
and
hydrogen dilute
aqueous
,
aqueous
copper ammonia
sulphate
strong iron box
at steady 500DC.
G H I
result of mixing
aqueous
aqueous copper sulphate
iodine
with
result of aqueous ammonia
mixing solutions
iodine in of
trich loroethane calcium chloride
& sodium carbonate
deep blue solution
J K L
Fig. 5.
8
Equilibria in homogeneous and heterogeneous systems
Another way of classifying different equilibrium systems divides them into

two types - homogeneous and heterogeneous systems.
A homogeneous system consists of one phase only.
A heterogeneous system consists of more than one phase.
Exercise 2 Look again at the equilibrium systems illustrated in

Fig. 5 and decide whether they are homogeneous or
heterogeneous. Ignore the 'air space' inside the
containers and note that only in (G) is the container
part of the equilibrium system.
If you can identify a heterogeneous system, solving numerical problems will

be easier, because you can simplify the arithmetic by certain assumptions.
Of course, you can easily identify a heterogeneous system from the chemical
equation,provided state symbols are included.
General statements about equilibrium
Different types of equilibrium system are often dealt with in texts under
separate headings or even in separate chapters. In ILPAC Units, we want
to emphasise that the principles which apply to anyone equilibrium system
apply to all; we can make two general statements which apply throughout.
1. All equilibrium systems share the same general characteristics.

2. All equilibrium systems can be described quantitatively by the
equilibrium law.
We deal with the equilibrium law in Level Two. The next section will
enable you to learn what the characteristics of equilibrium are.
CHARACTERISTICS OF THE EQUILIBRIUM STATE

It can be demonstrated that all equilibrium systems share the same
characteristics. However, we will merely illustrate these characteristics
by reference to a few simple examples.
9
(4) list, in your own words, four characteristics of the equilibrium

state;
(5) illustrate and explain each characteristic by reference to a particular
equilibrium system.
Read about the characteristics of the equilibrium state in your text-

book(s). Make sure that you understand the difference between
0
macroscopic properties (bulk properties) and molecular properties.
If you are unable to watch the video-programme referred to below,
look for a detailed account of an experiment which demonstrates that
W
equilibrium is dynamic.
I[ II
If it is available, watch the first part of the ILPAC video-programme
'Equilibrium', in which we demonstrate by experiment that an
equilibrium system is dynamic.
00
Use the notes you have written to help you with the next exercise.
Teacher-marked Write an account of an experiment which shows

Exercise conclusively that equilibrium is dynamic.
The following exercise tests your understanding of the characteristics

of dynamic equilibrium.
Exercise 3 Make a full-page-size copy of Table 2.

(a) For each equilibrium system in Fig. 5 write, in the ~
first column of Table 2, an equation which identifies
the opposing changes which are occurring at equal ~~
rates. Two examples are given.
Note that since the changes are reversible, it is just as
correct to write the equations the other way round.
In some cases, there may be more than one equilibrium in
the same system; e.g. in all those involving aqueous
solutions, the equilibrium
H20(1) ~ H20(g)
is involved as well as the more important one required in
this exercise. If you cannot decide which is the
'important' equilibrium, then write down more than one
equation, as in Fig. 5 (I).
(b) In the second column of your copy of Table 2, for each
system write down at least three observable properties,
other than temperature, which have constant values despite
the continuous change on the atomic scale.
10
Table 2
Constant macroscopic
System Equation properties
volume of liquid bromine

A Br2 (1) ~ Br2(g) mass of bromine gas
colour of gas
mass of ethanol
F CH3C02HCl ) + CZH5OH(l) ~ CH3COzCzH5(1) + HzO(l) amount of water
volume of liquid phase
Why equilibrium systems are 'closed'
All the systems pictured in Fig. 5 are closed. and you have learned that
equilibrium can only be reached in a closed system. In the next Exercise
you decide just how necessary it is for an equilibrium system to be closed.
Exercise 4 Look again at Fig. 5.

(a) What would happen in systems A. D. E and G if the
system were made 'open' by removing the cover or
drilling a hole in the container? Why would
equilibrium not be maintained?
(b) In practice. it is not always so important to have a closed
system as it is in the examples discussed in part (al.
Look. for example. at system K and explain why it is not
very important that the tube should be stoppered.
11
How equilibrium systems are established
Once a system is at equilibrium, it is impossible to determine whether the

system was prepared by starting with reactants or products. In Fig. 5E,
for example, you could not tell whether the system was prepared by starting
with a mixture of hydrogen and iodine or by heating hydrogen iodide. To
see if you can work out how equilibrium might be established, try the next
Exercise.
Exercise 5 Choose any three systems, except E, from Fig. 5 and ~

state alternative practical ways of setting up each one
from different starting points. ~~
(Hint: A to G, and J, should be easy; the rest are
perhaps not quite so straightforward - try at least one of
these also. )
It can sometimes take quite a long time for a system to reach equilibrium
from a given starting point. For example, mixtures of ethyl ethanoate and
water need about three days to reach equilibrium at room temperature, even
with a catalyst present.
Therefore you should do Part A of Experiment 2 (page 33) as soon as

it is convenient, so that the mixtures you prepare will be ready for
examination in Part 6 in a few days time.
In the next section you study the ways in which equilibrium, once
established, can be disturbed.
FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

A system in chemical equilibrium is defined by an equation, as you have
seen in Exercise 3. However, one system can have many different states,
and change between one state and another can be brought about in various
ways.
(6) explain what is meant by the term position of equilibrium;

(7) list the factors which affect equilibria;
(B) state Le Chatelier's principle.
12
Position of equilibrium
We often use the term 'position of equilibrium' to refer to one particular

state of an equilibrium system. One state, or position, differs from
another in the concentrations of the substances present in the equilibrium
mixture.
When the conditions change so that the system is no longer in equilibrium,

the two opposing reactions no longer cancel each other out. The concent-
rations of all the substances change until a new position of equilibrium is
established.
For example, if a change in conditions in the system:

H2(g) + I2(g) ~ 2HI(g)
results in the reaction from the left to right becoming faster than the
reverse reaction, more HI will be formed until the rates of forward and
backward reaction are equal again and a new position of equilibrium
established. In this case, we can say that:
'the equilibrium has shifted towards more products',
or 'the position of equilibrium has shifted to the right'.
You should note that references to 'right' and 'left', or to 'reactants'

and 'products' in equilibrium systems, are quite useless unless an
equation is written down, because, of course, the equation can be written
either way round.
You are already familiar with the factors which affect the rates of
chemical reactions from your pre-A-level work. These are listed below.
1. Concentration 3. Pressure
2. Temperature 4. Catalysts
A system at equilibrium appears to consist of two reactions: a forward

reaction and its reverse. It seems reasonable to assume, therefore, that
the factors which affect rates might also affect equilibrium systems.
You will study the effect of each of these factors on different equilibrium
systems. In your study you will make use of a very important principle,
which can be applied to all changes in equilibrium position.
Le Chotelier's principle
A French chemist, Henri Le Chatelier, investigated changes in equilibrium

systems many years ago. His work, published in 1895, gives us a useful
'rule of thumb' to predict the direction in which the position of
equilibrium will shift under varying conditions of concentration, temper-
ature, pressure and with or without the presence of a catalyst.
13
A literal translation from the French of Le Chatelier's own form-
ulation of the principle follows. You should look for a simpler
wording in your text-book(s) for the next exercise!
"Every system in chemical equilibrium
submitted to the influence of an
exterior force which tends to cause
variation either in its temperature or
its condensation (pressur~~ concent-
ration, number of molecules in unit
volume) in its totality or only in
some one of its parts can undergo only
those interior modifications which, if
they occurred alone, would produce a
change of temperature, or of conden-
sation, of a sign contrary to that
resulting from the exterior force."
Exerc~se 6 Write, in your own words, a simple statement of

Le Chatelier's principle.
(Answer on page 87 J
The value of Le Chatelier's principle should become clearer to you when you
apply it to specific equilibrium systems in the following sections.
Remember that the principle allows you to predict the ?irection of any
change in equilibrium position but not the extent of the change.
The effect on equilibrium of changing concentrations
Objectives. When you have finished these sections you should be able to:
(9) use Le Chatelier's principle to predict the effect on equilibrium
tm
systems of changing concentrations.
We start this section with a simple experiment. You can consolidate

your understanding of the results by reading (after the experiment) ~
and by applying them to other systems. lL
In the experiment we introduce a convenient and widely used piece Df

shorthand. Square brackets enclosing the formula of a s~bstance mean
'concentration of', e.g. [Fe3+(aqJ] means 'the concentration of aqueous
iron(IIIJ ions'.
14
EXPERIMENT 1
The effect of concentration changes
on equilibria
Aim
The purpose of this experiment is to find
out how a system in equilibrium responds
to a change in concentration of components
in the mixture.
Introduction
Iron(III) ions and thiocyanate ions react in solution to produce
thiocyanatoiron(III), a complex ion, according to the equation:
fe(SCN)2+(aq)
pale colourless blood-red
yellow
The colour produced by the complex ion can indicate the post ion of
equilibrium.
Requirements
safety spectacles
4 test-tubes and test-tube rack
2 teat-pipettes
distilled water
potassium thiocyanate solution, 0.5 M KSCN
iron(III) chloride solution, 0.5 M FeCl3
ammonium chloride, NH4Cl
spatula
glass stirring rod
Procedure
1. Mix together one drop of 0.5 M iron(III) chloride solution and one
drop of 0.5 M potassium thiocyanate solution in a test-tube and add
about 5 cm3 of distilled water to form a pale orange-brown solution.
2. Divide this solution into four equal parts in four test-tubes.
3. Add one drop of 0.5 M iron(III) chloride to one test-tube.
Add one drop of 0.5 M potassium thiocyanate to a second.
4. Compare tHe colours of these solutions with the untouched samples.
Enter your observations in a copy of Results Table 1.
5. Add a spatula-full of solid ammonium chloride to a third test-tube
and stir well. Compare the colour of this solution with the
remaining tube and note your observation.
Ammonium chloride removes iron(III) ions from the equilibrium by forming

complex ions such as FeCI;. A possible reaction is:
Fe3+(aq) + 4CI-(aq) ~ FeCI;(aq)
The effect is to reduce the concentration r,f iron(III) ions.
15
Before you leave the laboratory, shake the tubes you prepared for Experiment
2.
Interpretation of results
Having made three observations, suggest a cause for each colour change (in
terms of the concentrations of the coloured species) and then suggest what
can be inferred about a shift in the position of equilibrium.
If a pattern has emerged, then you can make a prediction based on the
results of the experiment.
Results Table 1
Change Observation Cause Inference
[Fe3+] increased
[SCN -] increased
[Fe3+] decreased
(Specimen results on page 87 )
Questions
1. How would the position of equilibrium be affected by increasing the
concentration of FeSCN2+?
2. For each imposed change show how the shift in equilibrium position
conforms to Le Chatelier's principle.
To consolidate the work done in Experiment 1, read about the effect

o
W
of concentration changes on equilibrium. Look for the application
of Le Chatelier's principle to the direction of change in equilibrium
position, but leave till later any references to the extent of
change and the equilibrium law. This will help you with the
Revealing Exercise which follows.
Consider the following equilibrium system:

Mn2+(aq) + H2S(aq) ~ MnS(s) + 2H+(aq)
Q.1. What effect does the addition of more H2S have on the position of
equilibrium? (Assume the system is not saturated with H2S already.)
A.i. The position of equilibrium shifts to the right.
Q.2. Explain your answer to Q.1. using Le Chatelier's principle.
A.2. The change imposed on the system is an increase in the concentration

of H2S. The position of equilibrium will shift to use up some of
the added H2S. In doing so, more MnS(s) and H+(aq) will be formed.
Q.3. What effect does passing hydrogen chloride gEs into the mixture have
on the position of equilibrium?
16
A.3. The equilibrium shifts to the left.
0.4. Explain your answer to 0.3. using Le Chatelier's principle.
A.4. Hydrogen chloride gas dissolves to produce hydrogen ions in solution,

thus increasing their concentration. The system responds by shifting
to the left to reduce the concentration by producing more Mn2+Caq)
and H2SCF'lq).
0.5. What effect does the addition of alkali have on the position of
equilibrium?
A.S. The equilibrium shifts to the right.
A.6. The alkali reduces the concentration of hydrogen ions by neutraliza-

tion; therefore the forward reaction occurs to increase it again.
Both of the equilibrium systems we have used to study the effect of

concentration changes are homogeneous systems. The situation is usually
simpler in heterogeneous systems, as we now show.
Pure solids and pure liquids in equilibrium systems
One of the equilibrium systems you

have alrRady studied is shown again
in Fig. 6. This is a heterogeneous
system containing a pure solid. What
is the effect on the equilibrium
position of adding more solid sugar?
saturated
sugar
solution
sugar crystals
Fig.6.
Clearly the concentration of sugar in the solution cannot increase because

it is already saturated. If it takes five lumps of sugar to saturate
the solution in a cup of tea, six lumps will not make it any sweeter! So
the equilibrium position remains unchanged. How does this tie in with
Le Chatelier's principle?
To answer this question you must consider what we mean by 'the concentration
of a solid'. In a solution, and in a gas, the concentration changes as the
particles Cmolecules, atoms or ions) become closer together or further apart.
In a solid the particles are in fixed positions relative to each other; this
means that the concentration is also fixed. In effect, the concentration of
a solid is equivalent to its density.
17
Therefore, by adding more sugar to the system in Fig. 6 .• we change the
amount of solid present but not its concentration. Since an equilibrium
state, or position. is specified by the concentrations of substances
present, it follows that adding more solid sugar does not affect the
equilibrium position.
You can apply a very similar argument to pure liquids in equilibrium

systems; try this in the next exercise. You may find it useful to
0
....-.,
refer to your text-books. ~
Exercise 7 Fig. 7 shows another of the equilibrium systems you

have already considered.
bromine gas
liquid bromine
Fig. 7.
Explain why the addition of more liquid does not change

the cqncentration of bromine gas.
(Answer on page 87 )
Try one more exercise to make sure you have grasped this idea.
Exercise B Fig. B shows a copper strip in equilibrium with a

solution of copper(II) ions. What would happen to the
system if the copper strip were replaced by a fine
copper wire? Explain.
aqueous
copper
sulphate
Fig. 8.
Remember that although we have only discussed a few examples. the general
rules apply to all equilibrium systems.
The concentration of a pure solid. or a pure liquid. is constant.
Changing the amount of pure solid, or pure liquid, in an equilibrium

mixture does not disturb the equilibrium.
18
Now we consider the effect of temperature changes.
The effect on equilibrium of changing temperature
Objective. When you have finished this section you should be able to:
(10) apply Le Chatelier's principIa to the effect on equilibrium of

changing temperature.
For Simplicity we start by considering the effect of temperature change on

a physical process, but you can apply the principle to all equilibria, both
physical and chemical.
Consider again the system shown in Fig. 9.

Br2(IJ ~ Br2(g) bromine gas
liquid bromine
Fig. 9.
Common experience (usually of open systems) tells you that if a liquid is

warmed, it vaporizes. If this system is heated, more gaseous bromine is
formed.
To help you apply Le Chatelier's principle to this system, and to

generalise the effect of temperature on other equilibrium systems,
work through the following Revealing Exercise.
0.1. Using your data book, write a thermochemical equation for the
vaporization of bromine, and draw an energy level diagram.
+15.0 kJ mol-1
l?
/kJ mo l r+ +15.0 kJ mo 1 -1
Br2(1)
0.2. Is the vaporization of bromine exothermic or endothermic?
A.2. Endothermic.
0.3. If energy is supplied to the system, in what direction does the

equilibrium shift?
19
A.3. The position of equilibrium shifts to the right to produce more bromine
gas.
A.4. The system absorbs the added energy in an endothermic reactionl

i.e. by vaporizing some bromine.
0.5. Explain what happens when this systeml at equilibriuml is cooled.
A.5. When the system is cooledl it loses energy. The system responds by
releasing energy in an exothermic reactionl i.e. by condensing some
bromine.
Note that for equilibrium s ys t erns , l::J? values are quoted for the reaction e.s
written from left to right (the forward reaction). The reverse reaction has
the same numerical value of ~I but with the opposite sign.
If it is availablel watch the second section of the ILPAC video-

programme 'Equilibrium'l which deals with the effect of temperature
on another equilibrium system. Be ready to make notes summarising
the experiments. If necessary you could also watch the third
sectionl which deals with the effect of pressure but it would be
I
better to leave this till later.
To consolidate your understanding of the effect of temperature on

equilibrium systemsl read the appropriate section of your text- o
book(s). Look for a simple qualitative account; don't worry about
the extent of the shift in equilibrium position. If you have not
GJ
seen the video-programmel look for an account of the effect of
temperature on the equilibrium system~
~ = +57.2 kJ mol-1
You should now be able to do the following exercises in which you apply
what you have learned to chemical equilibria.
Exercise 9 A sealed syringel with a free-moving pistonl containing ~

an equilibrium mixture of nitrogen dioxidel N021 and
dinitrogen tetroxidel N2041 at room temperature is ~~
immersed first in hot water and then in cold water.
Describe the colour changes you would observe and
explain them in terms of Le Chatelier's principle.
20
Exerc ise 10 What effect does an increase in temperature have on the ~
position of equilibrium in the following examples:
(a) H20(g) + C(s) ~ CO(g) + H2(g); Afl& = +13 kJ mol-1 ~~
(b) H202(1) ~ H2(g) + 02(g); 6fl& +210 kJ mol-1

(c) C(s) + 02(g) ~ CO2(g); ~ = -393.5 kJ mol-1
(d) Hg IL) ~ Hg(g); ~ = +60.84· kJ mo l "?
(e) AgCI02(s) ~ Ag(s) + ~C12(g) + 02(g); 6fl& 0.0 kJ mol-1
Exercise 11 Write four sentences summarising the effect of:

(a) an increase of temperature on
(i) an exothermic reaction,
(ii) an endothermic reaction;
(b) a decrease of temperature on
(i) an exothermic reaction,
(ii) an endothermic reaction.
HaVing discussed what happens to equilibrium systems when the temperature

changes, we now consider changes in pressure.
The effect on equilibrium of changing pressure
(11) apply Le Chatelier's principle to the effect on equilibria of changing

Rressure.
The effect of changing pressure is illustrated for systems where gases are
involved. We choose gaseous systems to illustrate this because solid and
liquid components are virtually unaffected by pressure; their volumes, and
hence concentrations, are unaltered. However, in reactions involving gases,
an increase in pressure brings the molecules closer together and thus
increases the concentration of the gaseous components.
If you have not yet seen the third section of the ILPAC video-
programme 'Equilibrium', which illustrates by experiment the effect
on an equilibrium system of changing the pressure, do so now if this
is possible.
Read about the effects of pressure changes on equilibrium systems to

help you with the exercises which follow. Again, focus on a o
qualitative account; leave any calculations till later.
CO
21
After working through the following Revealing Exercise you should be
able to explain how a gaseous system in equilibrium responds to a
change in pressure which is imposed externally. The system we will
use is:
A mixture of PC15, PC13 and C12 was placed in a glass syringe, the nozzle
was sealed, and the system was allowed to reach equilibrium at 250 °c
(Fig. 10).
Fig. 10.
The pressure of the system was increased by moving the plunger in (Fig.11).
The temperature was kept at 250 °C.
Fig.11.
0.1. According to Le Chatelier's principle. how will this 5ystem react to

the increased pressure?
A.1. It will shift in such a way that the pressure will decrease
towards the original pressure.
0.2. How many moles appear on the right-hand side of the equation?
A.2. Two.
0.3. How many moles appear on the left-hand side of the equation?
A.3. One.
Q.4. At the same temperature and volume, which will exert less pressure:
one mole of gas or two moles of gas?
A.4. One mole of gas.
0.5. Which reaction (forward or reverse) lowers the pressure?
A.5. The reverse reaction lowers the pressure:

PC13(g) + CI2(g) ~ PCI5(g)
0.6. How would the system pictured in Fig. 11 respond to an increase in

volume caused by pulling the plunger out a short distance? Assume
that the temperature remains constant.
22
A.B. An increase in volume would cause a decrease in the pressure. The
system would tend to increase the pressure by shifting to the right,
thus producing a greater number of molecules.
The important idea to remember in connection with gaseous equilibria is that

the pressure of a gas is proportional to the number of molecules (or amount)
present. The reaction which results in fewer molecules being formed will
reduce the pressure of the system and so oppose an applied increase in
pressure.
Now try the following exercises. The first deals with homogeneous systems
and the second with heterogeneous systems.
Exercise 12 What is the effect on the position of equilibrium of

increasing the pressure in the following systems?
(a) N2(g) + 3H2(g) ~ 2NH3(g)
(b) 2So2(g) + o2(g) ~ 2So3(g)
(c) 2HI(g) ~ H2(g) + 12(g)
Exercise 13 What is the effect on the position of equilibrium of

decreasing the pressure in the following systems?
(a) 3Fe(s) + 4H2o(g) ~ Fe304(s) + 4H2(g)
(b) S(s) + 02(g) ~ S02(g)

(c) CaC03(s) ~ CaD(s) + CO2 (g)
Exercise 14 Copy the following statements in your notebook and

complete them.
Ca) The only components of an equilibrium system to be ~
affected by changes in pressure are those in the
.......... state.
(b) If pressure is applied to an equilibrium mixture
involving gases. the position of equilibrium shifts in
such a way as to cause a(n) in the number of
molecules.
(c) If the pressure on an equilibrium mixture involving
gases is reduc~d. the equilibrium shifts in such a way
as to cause a(n) in the number of molecules.
(d) If a system has numbers of gas molecules on
either side of the equation. increasing or decreasing
the pressure of this system has no effect on the
equilibrium position.
We now come to the last of the four factors affecting equilibrium.
23
The effect on equilibrium of catalysts
(12) state the effect of catalysts on equilibrium systems;

(13) discuss the factors affecting equilibrium in some industrial
processes.
Catalysts are often used in industrial processes which involve equilibrium

systems; you have met several examples in your pre-A-Ievel course, such es
the Haber process for manufacturing ammonia and the contact process for
manufacturing sulphuric acid.
Industrial chemists obviously want a high yield of product, and will

therefore consider all the factors which shift the equilibrium position to
the right. They must also consider the rate at which equilibrium is
achieved and the cost of shifting the equilibrium position.
Read about catalysts and equilibrium systems, distinguishing

carefully between the effect on the position of equilibrium and the o
effect on the rate of achieving equilibrium. You may find it help-
ful to look at sections covering the Haber process, the ,contact
process and the Bosch process, which are mentioned in the next
W
exercise.
Now you should be able to put together all the principles you have learned
so far in this Unit and apply them to some industrial processes.
Exercise 15 Consider the following equilibrium systems used in

industrial processes.
(a) Contact process:
2S02(g) + 02(g) ~ 2S03(g); ~ -97 kJ mol-1
(b) Haber process:
N2(g) + 3H2(g) ~ 2NH3(g); ~ -92 kJ mol-1
(c) Bosch process:
C(s) + H20(g) ~ CO(gJ + H2(g); ~ = +131 kJ mol-1
In each case state the effect of a catalyst (if one is used)
on the equilibrium system, and the conditions of temperature
and pressure (high or low) which give the highest yield of
product(s) in the equilibrium mixture.
You may have realised that the conditions which give the highest o
yield of product in an equilibrium mixture are not always those used
in practice. We ask you to explain this in the next exercise. Use \If
your text-book(s) again if necessary.
24
Exercise 16 (a) Both the contact and Haber processes are run at ~
moderately high temperatures despite the fact that ~
lower temperatures give more products in the
equilibrium mixtures. Explain.
(b) Why is the contact process not run at high pressure?
(c) Why is the Bosch process not run at a pressure lower than
atmospheric pressure?
LEVEL ONE CHECKLIST

You have now reached the end of Level One of this Unit. The following is a
summary of the objectives in Level One. Read carefully through it and check
that you have adequate notes.
At this stage you should be able to:
(1) recognise that reversible changes are an essential feature of

equilibrium systems;
(2) quote examples of different types of equilibrium system;
(3) use the term phase to distinguish between homogeneous and heterogeneous
systems;
(4) & (5) list and illustrate the four characteristics of the equilibrium
state;
(6) explain the term position of equilibrium;
(7 ) to ( 12) state Le Chatelier's principle and apply it to the effect on
equilibrium systems of:
(a) changing concentration,
(b) changing temperature,
(c) changing pressure,
(d) using catalysts.
( 13 ) discuss the factors affecting equilibrium in some industrial processes.
LEVEL ONE TEST

To find out how well you have learned the material in Level One, try ~.
the test which follows. Read the notes below before starting:
~\\\
1. You should spend about 40 minutes on this test.
2. Hand your answers to your teacher fo~ marking.
25
LEVEL ONE TEST
1. (a) Illustrate the four characteristics of the equilibrium state
by reference to the equilibrium system:
2HI(g) ~ H2(g) + I2(g) (4)
(b) It can be shown that, if some solid radioactive iodine is added
to the system:
I2(s) ~ I2(g)
the iodine vapour also becomes radioactive. Why is this? (2)
2. Consider the system:

Fe(s) + 4H20(g) ~ Fe304(s) + 4H2Cg); ~ = +151 kJ mol-1
With reference to Le Chatelier's principle, explain the effect (if any)
on the yield of hydrogen of:
Ca) increasing the temperature,
(b) increasing the total pressure,
(c) adding more iron,
Cd) increasing the partial pressure of the steam. (8 )
3. A solution of antimony trichloride, SbC13, is made by dissolving solid

antimony trichloride in 6 M hydrochloric acid; under these conditions
the following equilibrium lies far to the left:
SbC13(aq) + H20(lJ ~ SbCIO(s) + 2HCI(aq)
(a) Why is the solution prepared using 6 M HCl? (3)
(b) What would be observed if
(i) the solution were diluted,
(ii) solid sodium hydroxide were added? (4 )
4. How do catalysts affect equilibrium systems? (4)

(Total 25 marks)
27
LEVEL TWO
In this Unit so far you have met examples of several different equilibrium
systems and investigated the effect of changing the conditions at
equilibrium. These effects were described qualitatively by Le Chatelier's
principle; we now consider them quantitatively by using the equilibrium law.
THE EQUILIBRIUM LAW
The equilibrium law applies to all equilibrium systems and we shall use it
as a tool to make precise mathematical predictions and calculations. It was
put forward as a result of careful experimental work, but has a firm basis
in theoretical thermodynamics.
(14) state the equilibrium law:

(15) apply the law to any reversible reaction by writing an expression for
the equilibrium constant, Kc.
Scan the section of your text-book which covers the equilibrium law. 0
Look for a mathematical expression which relates the concentrations .--r-i,
of the components in a system at equilibrium. ~
We now show you, in a Worked Example. how to write an equilibrium law

expression for a particular equilibrium system. We illustrate the
conventions used in writing equilibrium law expressions and show you
how to work out the unit of K .
c
Worked Example (a) Write an expression for K for the reaction

c
Nz04(g) ~ 2NOz(g)
(b) What is the unit of K in this case? Assume the

c
unit of concentration is mol dm-3•
Solution
(a) By convention. the equilibrium law is written with the products in the
numerator and the reactants in the denominator; the index (exponent) of
the concentration term is the same as the stoichiometric coefficient in
the balanced equation:
[NO Z (g) ] Z
eqm
In future, we assume that the concentrations used in equilibrium law

expressions are equilibrium ones and we leave out the subscript 'eqm'.
This saves space and looks neater on the page. So the above expression
becomes:
K - [NOz(g)]Z
c - [NZ04(g)J
29
(b) To work out the unit, assume that
x mol dm- 3
and y mol dm-3
Substitution into the equilibrium law gives:
(x mol dm-3) 2 x2 (mol dm-3)2 x-
2
K mol dm-3
c y mol dm-3 y mol dm-3 y
The unit of Kc for this reaction is therefore mol dm-3•
Now try writing some equilibrium law expressions by doing the next
exercise.
Exercise 17 (a) For each of the following reactions write an

expression for K. Work out units for K and
include them in ~our answers, assuming tgat
concentrations are measured in mol dm-3•
IL) 2HBr(g) ..-
H2 (g) + Br2(g)
--"
(ii) 2S02(g) + °2(g) ~ 2S03(g) .-

(iii) Cu(NH )42+(aq)
3
~ Cu2+(aq) + 4NH3(aq)
(iv) 2NO(g) + °2(g) ~ 2N02(g)

(v) 4PF5(g) ..-
-->. P4(g) + 1OF 2 (g)
(vi) 2NO(g) ~..- N2(g) + °2(g)

(vii) C2H50H(1) + CH3C02H(1) ~ CH3C02C2H5(1) + H.20(1)
(b) Look at the examples in which K has no unit. What do
all these reactions have in com~on?
As soon as you come to consider numerical values of Kc' you must remember
two important points.
1. A particular value of Kc refers only to one particular temperature.
2. The form of the equilibrium law expression (and therefore the value
of K ) depends on the way the equation is written.
a
We illustrate these ideas in the following exercises.
Exercise 18 The same equilibrium system may be represented by two

different equations:
COC12(g) ~CO(g) + C12(g)
CO(g) + C12(g) ~ COC12
(a) Write expressions for two equilibrium constants, K and
K c '. c
(b) What is the mathematical relation between K and K '?

c c
30
Exercise 19 The equilibrium between dinitrogen tetroxide and ~
nitrogen dioxide may be represented equally well by two
different equations: ~~
~N204(g) ~ N02(g)
N204(g) ~ 2N02(g)
(a) Write expressions for two equilibrium constants, Xc and

X c '.
(b) At 100 oC, X'

c
0.490 mol dm-3 and
at 200 °C, Xc
, 18.6 mol dm-3
What are the values of Xc at these temperatures?
Calculating the value of an equilibrium constant
(16) calculate a value for an e~uilibrium constant by direct substitution

of equilibrium concentrations into the equilibrium law.
We illustrate the method of calculation by a Worked Example.
Worked Example. Equilibrium was established at 308 K for the system

CO(g) + Br2(g) ~ COBrz(g)
Analysis of the mixture gave the following values
of concentration:
[CO(gl] = 8.78 x 10-3 mol dm-3
[Br2(gl] = 4.90 x 10-3 mol dm-3
[COBr2(gl] = 3.40 x 10-3 mol dm-3
Calculate the value of the equilibrium constant.
Solution
1. Write the equilibrium law expression for this reaction in terms of
concentration:
2. Substitute the equilibrium concentrations:

3.40 x 10-3 mo 1 dm-3
X
c 8.78 X 10-3 mol dm 3 x 4.90 x 10 3 mol dm-3
3. Do the arithmetic; cancel units where appropriate.
Xc =179•0 dm3 mol-1 I
Now try a similar problem.
31
Exercise 20 The equilibrium
N204 ~ 2N02
can be established in an inert solvent at 298 K.

Analysis of an equilibrium mixture gave the concentratian
of N204 as 0.021 mol dm-3 and the concentration of N02 as
0.010 mol dm-3• Calculate the value of the equilibrium
constant at 298 K.
If you need more practice in this type of calcUlation, try some of the
problems in Appendix 1A on page 73 .
In some problems, you may have to calculate concentrations from amounts and
total volume before you apply the equilibrium law. Try this in the next
exercise.
Exercise 21 Some phosphorus pentachloride was heated at 250 °c in a ~

sealed container until equilibrium was reached according
to the equation. ~~
PC15(g) ~ PC13(g) + C12(g)
Analysis of the mixture showed that it contained 0.0042 mol of

PC15, 0.040 mol of PC13 and 0.040 mol of C12• The total
volume was 2.0 dm3•
(a) Calculate the concentration of each component and hence
determine the equilibrium constant, K •
c
(bJ The value of K for this system is much greater than the
one you calculgted in Exercise 20. What can you say about
the relative concentrations of reactants and products when
(i) K is very large,
c
(ii) K is very small?
c
(Answers on page 89
Sometimes you can simplify a calculation by omitting the volume from the
equilibrium law expression, as we now show.
When volume can be omitted from an equilibrium law expression
(17) recognise those systems for which the equilibrium law

expression is independent of the volume.
In the next exercise you show that, for an equilibrium system where the
equilibrium constant has no unit, amounts can be used directly in the
equilibrium law expression without using the total volume.
32
Exercise 22 The table below shows the composition of two eqUilibrium~
mixtures at 485 °C.
~\\\
Amount of Amount of Amount of
H2/mol I2/mol HI/mol
1 0.02265 0.'02840 0.1715

;2 0.01699 0.04057 0.1779
(a) Write the equation for the formation of hydrogen iodide

from hydrogen and iodine.
(b) Write an expression constant, K .
for the equilibrium
c
(c) Calculate a value of Kc for each mixture, assuming the
volume of the equilibrium mixture is 1.00 dm3• Include
units in your working.
(d) For mixture 1, calculate a value for the equilibrium
constant, assuming the volume is 2.00 dm3•
(e) For mixture 2, calculate a value for the equilibrium

constant, assuming the volume is V dm3• Show that the
volume cancels.
Exercise 22 should convince you that the volume of the reaction mixture
made no difference to the value of the equilibrium constant. We can
generalise this for gaseous reactions and reactions in solution: if the
equation shows equal numbers of molecules on both sides, then the
equilibrium law expression is independent of the volume, and K is unitless.
c
In these circumstances, to calculate an equilibrium constant you can use

equilibrium amounts rather than concentrations; or you can include V as an
unknown value which cancels as in Exercise 22(e).
In the next experiment you calculate an equilibrium constant, using

concentratiuns determined by titration. If you have already done
part A of the experiment, and at least 48 hours have elapsed since
you prepared the mixtures, read again the Aim and Introduction
sections and then proceed to part B.
EXPERIMENT 2
Determining an equilibrium constant
Aim
The purpose of this experiment is to
calculate the equilibrium constant for
the reaction:
CH3C02C2H5(lJ + H20(1)
ethyl ethanoate water
~ C2H50HCl) + CH3C02HCl)
ethanol ethanoic acid
33
Introduction
The reaction between ethyl ethanoate and water is very slow. However, by
using a catalyst, dilute hydrochloric acid, equilibrium can be attained in
about forty-eight hours.
In part A of the axperiment you prepare, in sealed containers, mixtures
containing different proportions of the two reactants. To each mixture you
add a fixed amount of dilute hydrochloric acid as a catalyst.
In part 8, after the mixtures have reached equilibrium at room temperature,

you analyse each one by titration with sodium hydroxide. Part of the added
sodium hydroxide reacts with the catalyst; the rest indicates the amount of
ethanoic acid in the equilibrium mixture.
Finally, from the starting amounts and the amount of ethanoic acid produced,
you calculate the equilibrium concentrations of all four components and USE
them to determine the equilibrium constant.
Requirements - Part A
safety spectacles
5 specimen tubes with well-fitting caps
labels for tubes and stoppers
access to a balance (sensitivity ± 0.01 g or better)
pipette, 5 cm3, and safety filler
dilute hydrochloric acid, 2 M HCl
2 measuring cylinders, 10 cm3 (one must be dry) I ~ I
ethyl ethanoate, CH3C02C2H5-------------------~-~
distilled water
Procedure - Part A
1. Label five specimen tubes with your name and the date. Number them 1A,
18, 2, 3 and 4. Number the stoppers too, so that they do not get
misplaced.
2. Weigh each tUbe, with its stopper, and record the masses in a copy of
Results Table 2.
3. Using a pipette and safety filler, carefully add 5.0 cm3 of 2 M
hydrochloric acid to each tube, replacing the stoppers as you go. The
volume of acid must be precisely the same in each tube; mea5ure it as
carefully as you can. If you think you have made a mistake, wash out the
tube, dry it and start again.
4. Weigh each stoppered tube in turn and record the masses.
5. Select a dry measuring cylinder, and use it to add to tubes 2, 3 and 4
the volumes-Capproximate) of ethyl ethanoate shown in Results Table 2,
again replacing the stoppers as you go.
6. Weigh the stoppered tubes 2, 3 and 4. Record the masses.
7. From a second measuring cylinder, add to tubes 3 and 4 the volumes
(approximate) of distilled water shown in Results Table 2, again
replacing the stoppers as you go.
B. Weigh the stoppered tubes 3 and 4. Record the masses.
9. Gently shake the tubes and set them aside for at least 4B hours. During
this time, arrange to shake the tubes occasionally.
34
Results Table 2
Tube number 1A 1B 2 3 4
Mass of empty tube/g

Volume of HCl(aq) added/cm3 5.0 5.0 5.0 5.0 5.0
Mass of tube after addition/g
Volume of ethyl ethanoate added/cm3 - - 5.0 4.0 2.0
Volume of water added/cm3 - - - 1.0 3.0
Mass of ethyl ethanoate added/g
Mass of HCl(aq) added/g
Mass of water added/g
In addition to the two tubes containing only hydrochloric acid, you now have
three tubes containing different amounts of ethyl ethanoate and water (tube
2 has water from the acid). When these mixtures have reached equilibrium,
you can analyse them in part 8 of the experiment.
Before you begin part B, revise the technique of titration (Unit S1,
Experiment 3). You may find it helpful to have another look at the
I[ 11
ILPAC video-programme 'Performing a titration'. 00
Requirements - Part 8
safety spectacles
5 conical flasks, 250 cm3
wash bottle of distilled water
phenolphthalein indicator
burette, stand and white tile
small funnel ~
sodium hydroxide solution, 1 M NaOH (standardized) ----------~
Procedure - Part 8
1. Rinse and fill a burette with standardized sodium hydroxide solution.
2. Carefully pour the contents of tube 1A into a conical flask. Rinse the
tube into the flask three times with distilled water.
3. Add 2-3 drops of phenolphthalein indicator solution and titrate the
acid against sodium hydroxide solution. Record your burette readings
in a copy of Results Table 3.
4. Repeat steps 2 and 3 for each of the other tubes in turn. Remember that
tube 18 should require the same volume of alkali as tube 1A, but the
others should require a little more. Complete Results Table 3.
35
Results Table 3
Solution in flask Equilibrium mixture
Solution in burette Sodium hydroxide mol dm-3
Indicator Phenolphthalein
Tube number 1A 18 2 3 4
Final burette reading
Initial burette reading
Titre/ems
Calculations
The calculations seem complex, but consist of several very simple steps.
The flow scheme below summarises the procedure; refer to it as you work
through so that you can see the purpose of each step.
VOLUME of
HCl (eq ) "" amount mass
TITRE (HCl;---- of HCl - of HCl
only) ~ mass of H20
in HCl(aq)
MASS of ~
M:::(::l ~ ~
~total mass of initial
H20 at start -amount of H2~
EOM AMOUNT
of water
TITRE (eqm total amount of EOM AMOUNT OF

mixture) ----'acids at eqm ethanoic acid
MASS of ethyl initial amo~nt ~EOM AMOUNT

ethanoate added of ethyl of ethanol
ethanoate
EOM AMOUNT
of ethyl
ethanoate
1. From the average titre for tubes 1A and 18 (or the better titre if you
think one was inaccurate), calculate the amount of hydrochloric acid
catalyst you added to each of the five tubes. Remember that hydro-
chloric acid and sodium hydroxide react in equimolar amounts and that
amount = concentration x volume.
Record this amount in each column of a copy of Results Table 4.
2. From the titres for tubes 2, 3 and 4 in turn, calculate and record the
total amount of acid (hydrochloric and ethanoic) in each mixture.
3. Calculate, by SUbtraction, the amou~t of ethanoic acid in each

equilibrium mixture. This is the first of the four quantities you nee~
to substitute in the equilibrium law expression. Complete the third
row of Results Table 4.
4. The equation for the equilibrium system shows that the amount of
ethanol produced is equal to the amount of ethanoic acid produced. You
now have the second of the four quantities you need. Complete the
fourth row of your table.
36
5. From the data in Results Table 2~ calculate the amount of ethyl
ethanoate added to each tube.
amount of ethyl mass after addition - mass before addition
ethanoate molar mass
Complete the fifth row of your table.
6. Calculate and record the equilibrium amount of ethyl ethanoate in each
tube, using the relationship:
eqm amount of initial amount of eqm amount of
CH3C02C2H5 CH3C02C2H5 CH3C02H
You can see from the chemical equation that the amount of ethyl
ethanoate which reacts is equal to the amount of ethanoic acid produced.
You now have the third of the four quantities you need.
7. Calculate and record the mass of pure HCl in each mixture.
mass = amount x molar mass
8. Calculate and record the mass of water in the aqueous HCl added to each
tube. (You need to refer back to Results Table 2.)
mass of water = mass of HCl(aq) - mass of HCI
9. Calculate and record the total amount of water initially in each
mixture.
initial amount mass in HCI(aq) + mass added
of H2O molar mass
10. Calculate and record the equilibrium amount of water in each mixture
eqm amount initial amount
elf H20 of H20
11. Write an equilibrium law expression for the reaction and calculate three
values of the equilibrium constant~ Kc'
Results Table 4
Tube number 2 3 4
1. Amount of HCl/mol
2. Total amount of acid at eqm/mol
3. Eqm amount of ethanoic acid/mol
4. Eqm amount of ethanol/mol
5. Initiol amount of ethyl ethanoate/mol
6. Eqm amount of ethyl ethanoate/mol
7. Mass of pure HCl/g
8. Mass of water in HCl(aq)/g
9. Initial amount of water/mol
10. Eqm amount of water/mol
11 . Eqm constant. K
o
(Specimen results on page 89 )

Discuss the results of this experiment with other members of your
class and your teacher.
37
Computer simulation of the ethyl ethanoate equilibrium
The Schools Council 'Computers in the Curriculum Project' has ~
produced a computer program called 'Homogeneous equilibrium', parts
of which simulate an experiment similar to the one you have just
done. Ask your teacher if it is available. You do not need to know
anything about computing but, if you have not run a program before,
you will need a few minutes instruction on getting started and using the
keyboard.
Investigation 1 takes about 20-30 minutes. In this, you choose the initial
concentrations for the reaction between ethanoic acid and ethanol and
follow the progress of the reaction to equilibrium. Ask your teacher for
students' leaflets Band C.
Investigation 2 takes about 30 minutes and is a quantitative exercise in

which you find out whether the data from the above experiment fit in with
the equilibrium law. Ask your teacher for students' leaflets 0 and E.
You have done several direct calculations of equilibrium constants using

the equilibrium law. In the next section we show you how to use the
equilibrium law in a variety of other calculations.
Various numerical problems involving equilibrium constants
We describe different types of problem by means of objectives and illustrate

them by worked examples and exercises.
(18) calculate the equilibrium concentration of one substance in a mixture,

given the equilibrium concentrations of all other substances, the
balanced equation and the value of the equilibrium constant, K .
c
Worked Example For the equilibrium:

PC15(g) ~ PC13(g) + C12(g)
Kc = 0.19 mol dm-3 at 250 °c
One equilibrium mixture at this temperature contains PC15 at
a concentration of 0.20 mol dm-3 and PC13 at a concentration
of 0.010 mol dm-3•
Calculate the concentration of C12 in this mixture.
38
Solution
1. Start by writing the equation (even if it is given in the question).
Leave space where the equilibrium concentrations can be tabulated under
the formulae of the compounds:
PCI5(g) ~ PCI3(g) + CI2(g)
Equilibrium
concn/mo I dm-3
2. Indicate the equilibrium concentrations under the equation. Let the

concentration of chlorine, [C12(gJ], be x mol dm-3•
Equilibrium
concn/mol dm3
0.20 0.010 x
3. Write the equilibrium law expression in terms of concentration.

[PC13(g)][C12(g)]
K
c [PCI5(g)J
4. Substitute all values into the expression (remember to include units).
0.010 mol dm-3 x x mol dm-3
0.19 mol dm -3 = 0.20 mol dm 3
5. Solve the equation for x:
x = 0.19 x 0.20 = 3 8
0.010 .
Now do Exercises 23 and 24.
Exercise 23 Some N204 dissolved in trichloromethane was allowed to ~

reach equilibrium at a known temperature.
N20 ~ 2N02 ~\\
4
At this point the concentration of N02 was 1.85 x 10-3 mol dm-3•
What was the equilibrium concentration of N204?
K = 1.06 X 10-5 mol dm-3 at this temperature.
e
Exercise 24 At 1400 K, Kc = 2.25 X 10-4 mol dm-3 for the equilibrium: ~

2H2S(g) ~ 2H2(g) + S2(g) ~
In an equilibrium mixture, [H2S(g)] 4.84 x 10-3 mol dm-3
and [S2(g)] = 2.33 x 10-3 mol dm-3•
Calculate the equilibrium concentration of H2.
There are some more exercises of this type, for extra practice or for
revision, in Appendix 16 on page ~ .
The next exercise is similar, but requires an extra step at the start;
i.e. calculating concentrations from amounts and total volume.
39
Exercise 25 In another equilibrium mixture of the reaction
at 250 °c in a 2.0 dm3 vessel~ there is 0.15 mol of PC13

and 0.090 mol of C12.
K
c
0.19 mol dm-3 at 250 °c
(al Calculate the amount of PC15 present at equilibrium.
(b) Calculate the mass of PC15 present at equilibrium.
(Answers on page 90 1
Don't forget that if the total number of molecules does not change during
a homogeneous reaction~ the volume doesn't make any difference to the
calculation and you need not include it (see page 33 ).
Now we show you how to apply the equilibrium law to a slightly different
type of problem.
(19) calculate the equilibrium constant, K , given the balanced equation,

c
the initial concentrations (or amounts) and the equilibrium
BW
concentration (or amount) of at least one substance.
Worked Example. 6.75 g of SOzC12 was put into a 2.00 dm3 vessel,
the vessel was sealed and its temperature raised to
375 °C. At equilibrium, the vessel contained
0.0345 mol of C12. Calculate the equilibrium
constant for the reaction.
Solution
1. First~ note that the number of molecules does change, so you will have
to calculate concentrations from amounts.
2. Write the balanced equation, leaving room for initial concentrations
above and equilibrium concentrations below:
Initial
concn/mol dm-3
Equilibrium
concn/mol dm-3
3. Calculate the initial concentrations and put the values above the
appropriate formulae in the equation.
m 6.75 g
The amount, n, of S02C12 = M = 135 g mol-1 0.0500 mol
n
c = V
0.0500 mol
0.0250 mol dm-3
2.00 dm3
40
The initial concentrations of S02 and C12 are both zero. Write down
the initial concentrations:
Initial
eonen/mo 1 dm-3
0.025 o o
Equilibrium
eonen/mol dm-3
4. Now work out the equilibrium concentrations from the data and balanced
equation:
(a) There is 0.0345 mol of C12 present at equilibrium so there must
also be 0.0345 mol of S02 present. The concentrations are:
0.0345 mol
0.0173 mol dm-3
2.00 dm3
0.0345 mol
2.00 dm3
o . 01 73 mo 1 dm-3
(b) The amount of S02C12 left initial amount - amount reacted

(0.0500 - 0.0345) mol = 0.0155 mol
0.0155 mol
0.00775 mol dm-3
2.00 dm3
Write these equilibrium concentrations under the equation:
Initial
0.025 0 0
concn/mol dm-3
S02C12(g) ~ S02(g] + C12(g)
Equilibrium
0.00775 0.0173 0.0173
conen/mol dm-3
5. From here proceed as in the first Worked Example. Write the equilibrium
law expression and substitute the equilibrium concentrations:
K
[SO 2 (g) J [ C 12 (g ) J
c [S02C12(gJJ
0.0173 mol dm-3 x 0.0173 mol dm-3
0.00775 mol dm-3
I O.0386 mo 1 dm -3 I
Now try the following three exercises, two of which are A-level questions.
Exercise 26 Ethanoic acid, CH3C02H, and pentene, C5H10' react to ~

produce pentyl ethanoate in an inert solvent. A
solution was prepared containing 0.020 mol of pentene ~~
and 0.010 mol of ethanoic acid in 600 cm3 of solution.
At equilibrium there was 9.0 x 10-3 mol of pentyl
ethanoate. Calculate the value of K from these data.
c
CH3C02H + C5H10 ~ CH3C02C5Hll
41
Exercise 27 A mixture of 1 .90 mol of hydrogen and 1 .90 mol of iodine ~
was allowed to reach equilibrium at 710 K. The 1\
equilibrium mixture was found to contain 3.00 mol of ~
hydrogen iodide. Calculate the equilibrium constant at
710 K for the reaction
H2(g) + I2(g) 2HI(g)
(Answer on page 90)
Exercise 28 If a mixture of 6.0 g of ethanoic acid and 6.9 g of ~

ethanol is allowed to reach equilibrium. 7.0 g of ethyl 1\
ethanoate is formed. Ca lcu late K c. J';:t
CH3C02H + C2H50H ~ CH3C02C2H5 + H20
There are some more exercises of this sort. for more practice or for
revision. in Appendix 1C on page 74 .
The type of problem we present in the next section often requires the
solution of a quadratic equation. although it is not always possible to tell
just by reading the question. The chemistry is usually straightforward. but
if you find the mathematics difficult, remember that in an examination you
will secure a good proportion of the marks simply by applying the correct
principle without actually solving the equation at the last step. In any
case. som~ examining boards rarely set problems which require the solution
of quadratic equations.
Problems involving quadratic equations
The general form of a quadratic equation is
ax2 + bx + c 0
where a~ band c are constants. The solution of this equation is given by

the formula
-b ± Ibz - 4ac
x
2a
and it is easy to solve this using a calculator or tables of logarithms.
Objective. When you have finished this section. you should be able to:
(20) calculate the equilibrium concentrations (or amounts) of substances

given the initial concentrations and the value of the equilibrium
~-J
constant.
Worked Example Carbon monoxide and chlorine react to form phosgene, I

COC12• A mixture was prepared containing 0.20 mol
of CO and 0.10 mol of C12 in a 3.0 dm3 vessel. At
the temperature of the experiment Kc = 0.410 dm3 mol-1•
Calculate the concentration of COC12 at equilibrium.
42
Solution
1. As in almost all these calculations, write the equation, leaving space
above and below for initial and equilibrium conditions.
Initial
amount/mol
Equilibrium
amount/mol
2. In this case it is convenient to work first in terms of initial and

equilibrium amounts, and then divide them by the volume later when
substituting concentrations into the equilibrium law. Indicate the
initial amounts:
Initial
0.20 0.10
amount/mol
Equilibrium
amount/mol
3. Calculate the amounts at equilibrium in terms of one unknown amount.

(a) Let the amount of COC12 formed be x mol.
(b) The balanced equation tells us that at equilibrium
amount of CO initial amount - amount reacted
(0.20 - x) mol
(c) By similar reasoning, at equilibrium
amount of C12 (0.10 - x) mol
4. Put these equilibrium amounts in the appropriate spaces under the
equation:
Initial
0.20 0.10 0
amount/mol
CO(g) + C12(g) ..-
-'" COC12(g)
Equilibrium
(0. 20-x) (0.1 O-x) x
amount/mol
5. Write the equilibrium law in terms of concentrations:
[COC12(g)]
[CO (g ) J [ C 12 (g ) J
6. Put the equilibrium amounts in terms of concentrations by dividing by
the volume; substitute these into the equilibrium law:
x 1 d -3
3.0 mo m
[CO( g) ]
0.20 - x 1 d -3
3.0 mo m
0.10 - x
-------- mol dm-3
3.0
x
mol dm-3
3.0
0.410 dm3 mol-1
0.20 - x 0.10 - x
mol dm-3 mol dm-3
3.0 3.0
43
7. The equation becomes:
X
3.0
0.410
0.20 - x 0.10 - x
x
3.0 3.0
Simplify this equation:

3x 3x
0.410
(0.20 - x) x (0.10 - x) 0.020 - 0.30x + XZ
or 0.0082 - 0.123x + 0.41Ox2 = 3x

Put this quadratic equation in the standard form
0.41Oxz - 3.123x + 0.0082 = 0
8. Solve this quadratic equation. The solutions of this equation are:
-h ± 1hZ - 4ac
a:
2a
for which a 0.410, h = -3.123, c = 0.0082.
3.123 ± 1(3.123)2 - (4 x 0.410 x 0.0082)

x
(2 x 0.410)
3.123 ± 19.7531 - 0.0134 3.123 ± 19.7397 3 .123 ± 3. 121

0.820 0.820 0.820
x 7.6 or x 2.4 x 10-3
Solving a quadratic equation produces two roots. Because the system

began with 0.20 mol of CO and 0.10 mol of C12, it is impossible to
produce 7.6 mol of COClz. Therefore, the correct root is x = 2.4 X 10-3•
9. The amount of COC12 at equilibrium is 2.4 x 10-3 mol.
amount
Now, concentratlon = vo 1ume
o
[ COCI ( ) 1
2 g J
= 2.4 x 10-
3.0 dm3
mol 3
I 8. 0 x 1 0 -4 mo 1 dm -3 I
Now try the following exercises, some of which require the solution of a
quadratic equation.
Exercise 29 Carbon monoxide will react with steam under the

appropriate conditions according to the following
reversible reaction:
~ = -40 kJ mol-1
Calculate the number of moles of hydrogen in the equilibrium
mixture when three moles of carbon monoxide and three moles
of steam are placed in a reaction vessel of constant volume
and maintained at a temperature at which the equilibrium
constant has a numerical value of 4.00.
44
Exercise 30 For the eqUilibrium:J
PC15(g) ~ PC13(g) + C12(g) ~
K 0.19 mol dm-3 at 250 °C. 2.085 g of PCl5 was heated
t8 250 °c in a sealed vessel of 500 cm3 capacity and
maintained at this temperature until equilibrium was
established. Calculate the concentrations of PC15, PC13 and
C12 at equilibrium.
Exercise 31 For the reaction:

2HI(g)
the equilibrium constant = 49.0 at 444 °C. If 2.00 mol
of hydrogen and 2.00 mol of iodine are heated in a
closed vessel at 444 °c until equilibrium is attained,
calculate the composition in moles of the equilibrium
mixture.
Exercise 32 For the equilibrium:

C2H50H(1) + C2H5C02HCIJ ? C2H5C02C2H5(1) +
propanoic acid ethyl propanoate
Kc = 7.5 at 50 °C. If 50.0 g of C2H50H is mixed with 50.0 g
of C2H5C02H, what mass of ethyl propanoate will be formed at
equilibrium?
For extra practice~ or for reV1Slon, there are some further exercises of
this type in Appendix 10 on page 75
So far in this Unit, we have expressed the equilibrium law only in terms
of the equilibrium concentrations of reactants and products. However, for
gaseous systems, it is often convenient to use partial pressures rather than
concentrations. The equilibrium law still applies, but gives a different
equilibrium constant, K , which we now consider.
p
45
THE EQUILIBRIUM CONSTANT) Kp
You know. from Unit P1 (The Gaseous State). that the partial pressure of a
gas is proportional to its concentration. Therefore. the equilibrium law
can be expressed in terms of partial pressures; the equilibrium constant is
then given the symbol K .
P
(21 ) write an expression for the equilibrium constant. Kp' for a gaseous
system;
(22) calculate the value of K for a reaction given
p
(a) partial pressures at equilibrium.
(b) equilibrium amounts and total pressure.
Read the section of your text-book(s) which shows you how to write the 0
equilibrium law in terms of partial pressures. If necessary. remind
yourself of the relationship between partial pressure and mole ~
fraction. '-l-J
Exercise 33 Write an expression for Kp for each of the following ~
equilibrium systems. Assume all pressures are measured
in atmospheres (atm). and include units for Kp' ~~
(a) 2NH3(g) ~ N2(g) + 3H2(g)
(b) 2S02(g) + 02(g) ~ 2S03(g)
(c) C(s) + CO2 (g) ..- 2CO(g)
(d) CaC03(s) ..-
-->.
CaO(s) + CO2 (g)
(e) NH4HS(s) ~ NH3(g) + H2S(g)

To calculate Kp. we simply substitute equilibrium partial pressures into

the equilibrium law expression. It is just like substituting equilibrium
concentrations to calculate Kc' To see if you can do thiS. try the
following exercise.
Exercise 34 In the equilibrium system

2S02(g) + 02(g) ~ 2S03(g)
at 700 K, the partial pressures of the gases in an
equilibrium mixture are:
PSO = 0.090 atm, Pso 4.5 atm. 0.083 atm.

2 3
Calculate K p for this system.

There are some similar exercises, for more practice or for revision, in
Appendix 1E on page 75 .
46
In the next exercise, you have to calculate the partial pressures before
substituting in the equilibrium law expression. Remember that
partial pressure mole fraction x total pressure

amount of one component
mole fraction
total amount of all components
Exercise 35 Analysis of the equilibrium system

N2(g) + 3H2(g) ~ 2NH3(g)
showed 25.1 g of NH3, 12.8 g of H2 and 59.6 g of N2.
(a) Calculate the mole fraction of each gas.
(b) The total pressure of the system was 10.0 atm. Calculate
the partial pressure of each gas.
(c) Calculate Kp for the system.
The following exercises are similar.
Exercise 36 Phosphorus pentachloride dissociates on heating

accordihg to the equation:
PC15(g) ~ PC13(g) + C12(g)
At a pressure of 10.0 atm and a temperature of 250 °c the
amount of each gas present at equilibrium was: 0.33 mol
of PC15, 0.67 mol of PC13 and 0.67 mol of C12• Calculate
the value of Kp.
(Answer on page 92)
Exer~ise 37 Ammonium aminomethanoate, NH2C02NH4, decomposes

according to the equation:
NH2C02NH4(s) ~ 2NH3(g) + CO2(g)
In a particular system at 293 K, there was 0.224 mol of
CO2 and 0.142 mol of NH3 at a total pressure of 1.83 atm.
Calculate K for this system.
p
If you had difficulty with the preceding exercises or you are revising the
topic, try some more from Appendix 1F on page 76.
Kp and Kc generally have different values and units (look, for example, at
Exercises 21 and 36), but the two quantities are related because partial
pressure is proportional to concentration. Ask you teacher if your syllabus
requires you to know this relationship; if so, turn to Appendix 2 on page 79 •
Now that you can write an expression for Kp, we show you how to use it to
consider the effect on a system of changing the total pressure.
47
The effect on an equilibrium system of changing pressure
In Level One, you applied Le Chatelier's principle to determine the

direction of any shift in equilibrium position caused by changing the total
pressure. Now you can apply the equilibrium law to show why Le Chatelier's
principle works in relation to pressure changes. You can also calculate the
pressure change required to alter the equilibrium concentrations to a given
extent.
(23) show how the equilibrium law determines the effect on an equilibrium
system of changing the total pressure;
(24) calculate the pressure change required to alter, to' a given extent,
the proportions of reactants and products in a particular equilibriu~
system.
We show you how to achieve these objectives by means of a Revealing

Exercise, followed by a Worked Example~ both of which concern the
equilibrium system
2S02(g) + 02(g) ~ 2S03(g)
0.1. Write the equilibrium law expression for the system.
A.1 • P~O
K --=--~--
P P~O 2 x Po 2
0.2. Write an expression for the partial pressure of each gas in terms of
its mole fraction X and the total pressure PT.
A.2. PSO = XSO PT

3 3
0.3. Substitute your answers to 0.2. into ths equilibrium law expression
for Kp and simplify the equation.
A.3.
K
P
0.4. If the pressure of the system is doubled (at constant temperature),

which mole fractions must increase and which must decrease? (The new
values must give the same value of K as before.)
p
A.4. The mole fraction of S03 must increase and the mole fractions of S02
and O2 must decrease.
0.5. In which direction must the equilibrium position shift in order to

change the mole fractions? Is this in accordance with Le Chatelier's
principle?
48
A.S. The equilibrium shifts to the right, as predicted by Le Chatelier's
principle.
The s.amemethod cou ld be applied to any gaseous equilibrium system. We now

show you, in a Worked Example, how to use the expression you derived in A.3.
of the Revealing Exercise.
Worked Examp.le. At 1100 K, K

p
= 0.13 atm-1 for the system
2S02(g) + 02(g) ~ 2S03(g)
If 2.00 mol of S02 and 2.00 mol of 02 are mixed and
allowed to react, what must the total pressure be to
give a 90% yield of S03?
Solution
1. Write the balanced equation, leaving room above and below to put in
initial amounts and equilibrium amounts:
Initial
amount/mol
Equilibrium
amount/mol
2. Put in the initial amounts:
Initial
amount/mol
2.00 2.00 o
Equilibrium
amount/mol
3. Calculate the amounts at equilibrium:
90
(a) The amount of S03 produced = 2.00 mol x 100 1.80 mol
(b) The amount of S02 left at equilibrium
initial amount - amount reacted
(2.00 - 1.80) mol = 0.20 mol
(c) Amount of oxygen reacting ! x amount of S02 reacting
!x 1 .80 mol = 0.900 mol
The amount of oxygen remaining at equilibrium
initial amount - amount reacting
(2.00 - 0.900) mol = 1.10 mol
4. Tabulate this equilibrium information.
Initial
2.0 2.LJ 0
amount/mol
....>.
2S02(g) + °2[g) ~ 2S03(g)
Equilibrium
amount/mol 0.20 1 .10 1.80
49
5. Write an expression for the partial pressure of each gas.
The total amount of gas present = (0.20 + 1.10 + 1.80) mol 3.10 mol
X 1.80
PS03 = S03 PT = 3.10 x PT
Similarly for the other two partial pressures:
0.20
P S02 = --3.10 x PT
6. Write an expression for K and substitute the partial pressures:

P
K
P
( 1 .80) 2 2
1
3.10 PT
0.13 atm-
7. Solve this equation for PT:

o 13 t -1 _ 0.337
. a m - 0.00416 x 0.355 PT
PT
0.337 3
0.13 atm-1 x 0.00416 x 0.355 = 1.76 x 10 atm
I I
The pressure calculated in the Worked Example is far too high for economic
production. In the next exercise, you calculate the pressure required for
a more modest conversion.
Exercise 38 For the system described in the Worked Example, ~

calculate the pressure necessary for 20~ conversion of
the S020 ~~
Now try two similar exercises.
Exercise 39 Sulphur dioxide and oxygen in the ratio 2 moles : 1 mole ~

were mixed at a constant temperature of 1110 K and a
constant pressure of 9 atmospheres in the presence of a ~~
catalyst. At equilibrium, one third of the sulphur
dioxide had been converted into sulphur trioxide:
2S02(g) + 02(g) ~ 2S03(g)
Calculate the equilibrium constant (K ) for this reaction
under these conditions. P
In the nex~ exercise you use a different unit of pressure, which you first
met in Unit P1.
50
Exercise 40 A sample of dinitrogen tetroxide is 66% dissociated at a ~
pressure of 98.3 kPa (747 mmHg) and a temperature of A
60 °C. (Standard pressure = 100 kPa (760 mmHg).) J;:t
Calculate the value of Kp for the equilibrium at 60 °C,
stating the units.
You have seen how the equilibrium yield of S03 varies with temperature,
with pressure, and with the ratio of S02 to 02 in the initial mixture. In
the industrial manufacture of sulphuric acid via S03 by the contact process,
it is important not only to achieve a good equilibrium yield but also to
maintain a high rate of production at reasonable cost. The conditions are
chosen to achieve a balance between these conflicting requirements, as you
can see in a computer simulation.
Computer simulation of sulphuric acid manufacture
The Schools Council 'Computers in the Curriculum Project' has C

produced a program called 'The manufacture of sulphuric acid', which
investigates the conflicting demands of best equilibrium yield, high
daily production and profitable manufacture. Ask your teacher if it
is available.
You do not need to know anything about computing but, if you have not used
a program before, you will need a few minutes instruction on getting
started and using the keyboard. You will need the students' notes which
accompany the program, and up to two hours of computing time.
When considering mixtures of gases, a useful concept is 'average molar mass'.

We deal with this in the next section.
Average molar mass of a gaseous mixture
You might be asked to calculate the average molar mass of a mixture of

gases from the amounts present or, alternatively, to calculate the relative
amounts present from the average molar mass of a mixture.
Objective. When you have finished this section, you should be able to:
(25) calculate the average molar mass of a gaseous mixture.
We show you how to do this calculation in a Worked Example. You may like
to try to solve the problem yourself before you look at our solution.
Worked Example. Calculate the average molar mass of a mixture

which contains 0.20 mol of S02' 1.10 mol of O2 and
1.80 mol of S03.
51
Solution
Each component of the mixture contributes to the average molar mass, M, in
proportion to its mole fraction, X.
-
M = XS02MS02 + X02M02 + XS03MS03
0.20 64 1 1 1 1.10 32 0 1-1 1.80 80 1 1 1

3.10 x . g mo - + 3.10 x . g mo + 3.10 x . g mo -
(4.1 + 11.4 + 46.5) g mol-l = 162.0 g mol-l
Now do the following exercises.
Exercise 41
For this system, a particular equilibrium mixture
has the composition 0.96 mol of N02Cg), 0.040 mol of
NOCg), 0.020 mol of 02(g) at 700 K and 0.20 atm.
(a) Calculate the equilibrium constant, Kp' for this reaction
under the stated conditions.
(b) Calculate the average molar mass of the mixture under the
stated conditions.
Exercise 42 0.20 mol of carbon dioxide was heated with excess carbon~
in a closed vessel until the following equilibrium w~s
attained: ~~
CO2 (g) + C(s) ~ 2CO(g)
It was found that the average molar mass of the gaseous
equilibrium mixture was 36 g mol-l•
Ca)· Calculate the mole fraction of carbon monoxide in the
equilibrium gaseous mixture.
(b) The pressure at equilibrium in the vessel was 12 atmo-
spheres. Calculate Kp for the equilibrium at the
temperature of the experiment.
(c) Calculate the mole fraction of carbon monoxide which would
be present in the equilibrium mixture if the pressure were
reduced to 2.0 atmospheres at the same temperature.
There are some more problems on average molar mass in Appendix 1G on page 77.
Now we consider again the effect on an equilibrium system of changing

temperature, this time in terms of the equilibrium law.
52
THE VARIATION OF EQUILIBRIUM CONSTANT WITH TEMPERATURE
You already know, from Level One, that the direction of a shift in equili-
brium brought about by a temperature change is determined by the sign of the
standard enthalpy change, 6B~. You should not be surprised to find that
the extent of the shift depends on the value of 6B~.
(26) describe how equilibrium constants vary with temperature.
Since a change in temperature does not, of itself, change the concentration

of a substance, it follows that any shift in equilibrium position must be
due to a change in the equilibrium constant. You explore this idea in the
next exercise.
Exercise 43 (a) Write expressions for K for the following

equilibrium systems~ p
(i) H2(g) + 12(g) 2HI (g); N? - 9.6 kJ mo 1 -1
(ii) N2(g) + 02(g) 2NO(g)j 6l? +180 kJ mo l."?
(iii) N~(g) + 3H2(g) 2NH3 (g) j N? -92 kJ mol-1

(b) According to Le Chatelier's principle, which way does the
equilibrium shift, in each case, with an increase in
temperature?
(c) Use your answers for (a) and (b) to decide whether K
increases or decreases with increasing temperature. P
[d) Which equilibrium constant do you think might change most
for a given change in temperature?
The effect on equilibrium of changing temperature is therefore different

from the effects of changing concentration and pressure. Remember that:
equilibrium constants vary with temperature; they do not vary with

pressure or concentrations;
--
if N?- is positive, K increases with temperature (more products);
if N? is negative, K decreases with temperature (more reactants·) .
You also know, from Unit S3 (Chemical Energetics), that the extent to
which a reaction 'goes' depends on the value of the standard free energy
change, 6f? You might therefore expect H? and K to be related. Ask
your teacher if your syllabus requires you to know the mathematical
relationship between ~ and K; if you 'do, you should work through Arpendix
2 on page 80. Appendix 2 also shows you how to calculate, from t:l?', the
change in equilibrium constant for a given temperature change.
53
Having considered some homogeneous equilibrium systems, we now apply the
equilibrium law to an important group of heterogeneous systems - sparingly
soluble salts in contact with their saturated solutions.
SOLUBILITY PRODUCTS FOR SLIGHTLY SOLUBLE SALTS

Equilibria involving sparingly soluble salts deserve special attention
because of their importance in chemical analysis. A simple application of
the equilibrium law helps us to understand how precipitation can be
controlled.
(27) write an expression for the solubility product of a slightly soluble

salt;
(28) calculate a solubility product from solubility data;
(29) calculate solubility from solubility product.
Find out from your text-book(s) how to apply the equilibrium law in
o
W
order to write an expression for the solubility product, Ks' of a
slightly soluble salt. We show you how to do the calculations after
the next exercise.
Exercise 44 Write expressions for the solubility products, Ks' for

the following systems; assume concentrations are
J
measured in mol dm-3 and include the unit of Ks.
~
(a) BaSO~(s) ..- ....->.
Ba2+(aq) + SO~2-(aq)
(b) CaF2(s) ..-

....->.
Ca 2 + (aq) + 2F-(aq)
(c) Ag3PO~(S) ~ 3Ag+(aq) + PO~3-(aq)
In Experiment 3, page 56, you determine the solubility product of

calcium hydroxide by titration. You need about 10-15 minutes to
prepare the solutibns (Procedure steps 1 and 2) now, or at least 24
hours before you do the titration. The next section will help you
to do the calculation at the end of the experiment.
54
Calculating solubility product from solubility
We show you how to do this type of calculation by means of a Worked Example.
Worked Example. The solubility of silver sulphide, Ag,S, is

2.48 X 10-15 mol dm-3• Calculate its solubility
product.
Solution
1. Write the equation representing the dissolving of silver sulphide,
leaving space above and below the equation for initial and equilibrium
concentrations:
Initial
concn/mol dm-3
o o
Equilibrium
con cn/mo 1 dm-3
2. Calculate the concentrations of sulphide ion and silver ion.
The solubility indicates the amount of silver sulphide in a saturated
solution. The balanced equation shows that every mole of Ag2S which
dissolves produces one mole of S2- and two moles of Ag+. Hence, at
this temperature, in a saturated solution of Ag2S,
[S2-Caq) ] 2.48 x 10-15 mo 1 dm-3
and [Ag+(aq)] 2 x 2.48 X 10-15 mol dm-3 4.96 x 10-15 mo 1 dm-3

Put these values below the equation:
Initial
eonen/mol dm-3
o o
Equilibrium
4.96 X 10-15 2.48 X 10-15
con en/mo 1 dm-3
3. Write the expression for K , substitute the equilibrium concentrations
s
and do the arithmetic.
K [Ag·Caq)]2[S2-Caq)]
s
C4.96 X 10-15 mol dm-3)2 x C2.48 x 10-15 mol dm-3)
16.10 x 10-44 mo13 dm-91
In this type of calcUlation some students wonder why a concentration term

is both doubled and squared. The explanation is as follows: firstly, the
stoichiometry tells us that [Ag+Caq)] is twice the solubility; secondly,
the form of the equilibrium law tells us that the silver ion concentration
is squared.
Now try the following exercise.
55
Exercise 45 Calcu late the solubility products of the followin"g
sUbstances from their solubilities.
Substances Solubility/mol dm-s
(a) CdCOs 1 .58 x 10-7
(b) CaF2 2.15 x 10-4
(c) Cr(OH)s 1 .39 x 10-8
Now you can complete Experiment 3, provided

since you made up the solutions.
that 24 hours have elapsed t.u
LJJL\
EXPER I MENT 3
Determining a solubility product
Aim
determine the solubility and solubility
product of calcium hydroxide.
Introduction
The equilibrium between solid calcium hydroxide and its ions in an aqueous
so Lu t Lon is
Ca(OH)2(S) ~ Ca2+(aq) + 20H-(aq)

The concentration of hydroxide ions can be determined by titration with
hydrochloric acid; the concentration of calcium ions can be calculated
from the titration result.
Requirements
safety spectacles
4 stoppered bottles, 250 cm3
labels for bottles
spatula
calcium hydroxide, solid, Ca(OH)2
measuring cylinder, 100 cm3
distilled water
4 filter funnels, dry, with filter papers
thermometer 0-100 0c (± 1 °C)
pipette, 25 cm~ and safety filler
burette and stand, white tile
small funnel
hydrochloric acid solution, 0.1 M - standardized
phenolphthalein indicator solution
56
Procedure
1. Into each of four bottles put about 2 g of powdered calcium hydroxide
and about 100 cm3 of distilled water. Stopper securely.
2. Shake well for about a minute. Label each bottle with your name J
experiment and date and set aside for a day or more.

J
3. Rinse and fill the burette with standardized hydrochloric acid.

4. Filter the contents of one bottle. allowing the first 5 cm3 to run to
waste and collecting the rest in a dry conical flask. (The first few
cm3 are rejected because they are less concentrated in solute than the
rest. The filter paper adsorbs solute until it attains equilibrium with
the solution. Yet another equilibrium!)
To minimise absorption of carbon dioxide. steps 5 and 6 should be done quickly
(with due care!) and with only the minimum shaking that will ensure mixing.
5. Rinse the pipette with the calcium hydroxide solution and transfer
25.0 cm3 to a conical flask (this need not be dry).
6. Add two drops of phenolphthalein to the flask and titrate the solution
until the pink colour just disappears. Record your burette readings in
a copy of Results Table 5.
7. Repeat steps 4. 5 and 6 for the other three solutions.
S. Record the temperature.
Results Table 5
Solution in flask mol dm-3 cm3
Solution in burette mol dm-3
Indicator
Trial 1 2 3 4
Final
Burette readings
Initial
Volume used/cm3
Mean titre/cm3
Calculation
1. Calculate the concentration of hydroxide ions in a saturated solution of
calcium hydroxide.
2. From the equilibrium concentration of hydroxide ions calculate the
equilibrium concentration of calcium ions.
3. Calculate the solubility of calcium hydroxide at the temperature of
your experiment. Compare your result with the value listed in your
data book.
4. Calculate the solubility product from:
(a) your result.
(b) the solubility of calcium hydroxide given in your data book.
(Specimen results and calculations on page 95 )
57
Now that you know how to calculate solubility product from solubility, we
show you how to do the reverse process.
Calculating solubility from solubility product
Worked Example Calculate the solubility, in mol dm-3, of calcium

su Ipha t e .
K for calcium sulphate = 8.64 x 10-6 mol2 dm-6
s
Solution
1. Write the equation for the solution of the salt, leaving room above and
below for concentrations. Initially there is no Ca2+(aq) or S042-(aq).
Initial
o o
concn/mol dm-3
Equilibrium
concn/mol dm-3
2. From the balanced equation we know that the equilibrium concentration
of Ca2+ (eq l is equal to that of S04 2-(aq). Let this be X mol dm-3•
Initial
o o
concn/mol dm-3
Equilibrium
x x
concn/mol dm-3
3. Write the expression for K
s
Ks = [Ca2+(aq)][S042-(aqJ]
4. Substitute K and the equilibrium concentrations.
s
8.64 x 10-8 mo12 dm-6 = x mol dm-3 x x mol dm-3
x2 8.64 X 10-8
X 2.94 x 10-4
solubility = 12.94 x 10-4 mol dm-3
Try the next exercise, using a similar method.
Exercise 46 Calculate the solubilities of the following slightly

soluble substances from their solubility products.
Substance Solubility product
(a) CuS 6.3 x 10 -'3 6
mo12 dm-6
(b) Fe(oH)2 6.0 x 10-15 mol3 dm-9
(c) Ag3P04 1 .25 x 10 -2 0 mo I4 dm -12
58
Limitations of solubility product theory
Some data books do not list a value for the solubility product of calcium
hydroxide, and none list values for more soluble salts such as sodium
chloride. The idea of solubility product strictly applies only to slightly
soluble electrolytes, i.e. solutions in which the concentration of ions is
very low. Usually the total ion concentration is not more than 0.01 mol dm-3•
At higher concentrations, the ions interact with one another so that their
effective concentrations differ from their actual concentrations. In this
respect, very dilute solutions may be regarded as 'ideal solutions' which
obey simple laws. just as gases at low pressure observe the ideal gas law.
Calcium hydroxide is a border-line case; strictly, it is too soluble for

its solution to be regarded as ideal, but the error is small enough for us
to use calcium hydroxide as an example in a simple experiment. Obviously,
titration would not be a good method for determining solubility products
for less soluble salts; you will learn about another method in Unit P6
(Redox Reactions).
So far in this section we have considered only pure solutions. Now we deal
with mixtures of solutions with a common ion.
The common ion effect
(30) perform calculations involving solubility product and the common ion
effect;
(31) predict whether precipitation will occur given a solubility product
and the concentrations of the solutions to be mixed.
We illustrate the common ion effect by a short experiment involving a

fairly soluble salt. We then return to sparingly soluble salts for
calculations. The next exercise is a useful introduction to the experiment.
Exercise 47 You are given a saturated solution of sodium chloride. ~

NaCl(s) ~ Na+(aq) + Cl-(aq)
~\\
According to Le Chatelier's principle, what do you
expect to happen when
(a) the sodium ion concentration is increased.
(b) the chloride ion concentration is increased?
Now test your predictions by doing Experiment 4. It will take you

no more than ten minutes.
59
EXPERIMENT 4
Illustrating the common ion effect
Aim
demonstrate an example of the
ap~lication of Le Chatelier's principle.
Introduction
Although sodium chloride is quite soluble, we can use it to demonstrate the
common ion effect. In the preceding exercise, you made some predictions
based on Le Chatelier's principle; now you test them.
Requirements
safety spectacles
2 test-tubes with corks, in a rack
sodium chloride solution, saturated, NaCl
hydrochloric acid, concentrated, HCI - - - - - - - - - - - - - - --
teat-pipette
sodium hydroxide, pellets, NaOH - - - - - - - - - -- - - - - - - --
spatula or forceps
Procedure
1. Carefully pour about 10 cm3 of saturated sodium chloride solution into
each of two test-tubes. Do not transfer any solid.
2. To the first test-tube carefully add 4-5 drops of concentrated
hydrochloric acid. Cork the tube, shake gently and set aside.
3. To the second test-tube add one pellet of sodium hydroxide.
USE FORCEPS OR SPATULA TO HANDLE THE SODIUM HYDROXIDE.
Cork the tube, shake gently and set aside.
4. Note any observations.
Questions
1. What did you see happen in each test-tube?
2. Does this confirm your prediction in Exercise 47?
3. In the saturated solution of sodium chloride, what is the concentration
of each ion? (Use your data book.)
4. The concentration of concentrated hydrochloric acid is approximately
12 mol dm-3• Explain what happened to the sodium ions in solution when
the hydrochloric acid was added.
5. Explain what happened to the chloride ions in solution when the sodium
hydroxide pellet was added.
6. Why is no solubility product value given for sodium chloride in any
data book?
60
Experiment 4 showed you how Lncr-aes t ng the concentration
the ions in a saturated solution reduces the concentration
of one of
of the ~
0
other ion by causing precipitation. This is known as the common ion ~
effect; read about it further in your text-book(s). Look for
examples of calculations which help you to understand our Worked
Example and the following exercises.
Worked Example. Calculate the solubility of silver chloride. AgCl.

in~
(a) pure water. (b) 0.10 M KJaCl.
K (AgCl) = 2.0 x 10-10 mo12 dm-6
s
Solution
(a) This is not a new type of calculation but you need the result for
comparison. Refer to the last Worked Example if necessary.
Solubility of AgCl' = ~ = 12.0 X 10-10 mo12 dm-6

s
11.4 X 10-5 mol dm-31
(b) 1. Write the equation and indicate the concentrations present initially
and at equilibrium.
Initial
concn/mol dm-3
o 0.10
AgCl(s) ~ Ag+(aq) + Cl-(aq)
Equilibrium
x (x + 0.10)
concn/mol dm-3
If x mol dm-3 of AgCl dissolve. then x mol dm-3 of Ag+(aq) and x
mol dm-3 of Cl-(aq) are produced. The total concentration of
chloride ions equals that produced by the AgCl dissolving plus the
0.10 mol dm-3 initially present.
2. Write the equilibrium law expression.
K
s
3. Substitute th8 equilibrium concentrations and the solubility product.
2.0 X 10-10 mo12 dm-6 = x x (x + 0.10) rno l" dm-6
4. Now you can make a very useful approximation. In otherwise pure

water the concentration of Ag+(aq) from dissolved AgCl is
1.4 x 10-5 mol dm-3• Applying Le Chatelier's principle. addition
of Cl- will drive the equilibrium to the left thereby reducing the
silver ion concentration still further. So you can assume that the
concentration of chloride ions from the AgCl is negligible compared
to the 0.10 mol dm-3 solution of Cl - present initially.
Expressed mathematically. (x + 0.10) mol dm-3 ~ 0.10 moi dm-3
(You can test this approximation after the calculation.)
5. The equilibrium law expression now becomes
2.0 x 10 -10 x x 0.10
2.0 X 10-10
x 2.0 x 10-9
0.10
6. The solubility in 0.10 M NaCl [Ag+ (aq) J
x mol dm-3 =12.0 x 10-9 mol dm-31
61
Note the dramatic effect of the common ion; this solubility is less than
one thousandth of the solubility in water!
You can quite simply check that the approximation in Step 4 is valid:
x + 0.10 = (2.0 x 10-9) + 0.10 = 0.100000002 ~ 0.10
A better, but more tedious, check is to calculate x from the quadratic
equation in step 3:
2.0 x 10-10 = X x (x + 0.10)
. x2 + O. 10x - 2. 0 x 10 -10 = 0
-0.10 ± I 0.010 + 8.0 x 10-10

X = 2
= 2.0 x 10-9
You will find it very useful to make such approximations because they often
0A
make calculations much simpler, as you can see in the following exercises.
Exercise 48 At 20 °C, the solubility product of strontium sulphate

is 4.0 X 10-7 mol2 dm-6, and that of magnesium fluoride is
7.2 X 10-9 mo13 dm-9• Estimate, to two significant .
figures~ the solubility at 20 °c in mol dm-3 of
(a) strontium sulphate in a 0.1 M solution of sodium sulphate;
(b) magnesium fluoride in a 0.2 M solution of sodium fluoride.
Exercise 49 A saturated solution of strontium carbonate was filtered.~

When 50 cm3 of the filtrate was added to 50 cm3 of 1.0 M
sodium carbonate solution, some strontium carbonate was ~~
precipitated. Calculate the concentration of strontium
ions remaining in the solution. All the work was done
at 25 °C.
We now come to the last application of the solubility product principl~_

that we cover in this Unit.
Will precipitation occur?
To predict whether precipitation will occur when solutions are mixed, you
need to recognise that solubility product is a value which the product of
ion concentrations in solution can never exceed at equilibrium.
We show you how to apply this idea in a Worked Example.
62
Worked Example. If 50.0 cm3 of 0.050 M AgN03 is mixed with 50.0 cm3
of 0.010 M KBr03• will a precipitate of AgBr03 form?
K (AgBr03) = 6 x 10-5 mol2 dm-6•
s
B \AI
Solution
1. Work out what the concentrations of Ag+ and Br03- would be after mixing
but before any reaction:
(a) Amount of Ag+ = 0.050 dm3 x 0.050 mol dm-3
[Ag+ (eq )] 0.050 dm3 x 0.050 mol dm-3 -_ 0.025 mol dm-3
0.100 dm3
(The volume is doubled. so the concentration is halved.)
(bl Similarly. [Br03-(aq)] = ~ x 0.010 mol dm-3 = 0.0050 mol dm-3
2. Calculate the product of the ion concentrations (called the ion product I,
Ion product [Ag+(aq)][Br03-(aq)]
0.02~ mol dm-3 x 0.0050 mol dm-3 = 1.25 x 10-4 mo l" dm-6
3. Compare the value of the ion product with the solubility product.
If the ion product is greater than Ks. precipitation will occur.

If the ion product is less than Ks. precipitation will not occur.
a silver bromate precipitate will appear because the ion product

is greater than the solubility product.
To make sure that you can do this kind of problem. try the following two
exercises.
Exercise 50 Will a precipitate of BaF2 form if 150 cm3 of ~

0.1 M Ba(N03]2 is mixed with 50.0 cm3 of 0.05 M KF?
K = 1.7 X 10-6 mol3 dm-9• ~\\
s
Exercise 51 You are given the following numerical values only for ~
the solubility products of various salts at 25 °c. A
~
Ks [silver chloride] = 2 x 10-10
Ks [lead(II) bromide] = 3.9 x 10-5
Ks [silver bro~ate(V)J = 6.0 x 10-5
Ks [magnesium hydroxide] = 2.0 x 10-11
(al State the units for each of the above solubility products.
(b) Which of the following pairs of solutions (all of concent-
ration 1.0 x 10-3 mol dm-3) will form a precipitate when
equal volumes are mixed at 25 °C? Give reasons for your
answers.
(i) Silver nitrate and sodium chloride.
(ii) Lead(II) nitrate and sodium bromide.
(iii) Silver nitrate and potassium bromate(V).
(iv) Magnesium sulphate and sodium hydroxide.
(Answers on page 97)
63
We now deal with the last application of the equilibrium law in this Unit,
namely the distribution of a solute between two immiscible solvents.
DISTRIBUTION EQUILIBRIUM
You looked briefly at an example of
distribution equilibrium in Level One;
it is illustrated again in Fig. 12.
You now consider similar systems in
more detail.
aqueous
iodine
iodine in
trichloroethane
Fig. 12.
(30) calculate the equilibrium constant, Ko' for a distribution equilibrium

(the distribution coefficient) given the necessary data;
(31) apply the distribution equilibrium law to an extrac'tion process.
Read about distribution equilibria in your text-book(s).

how to write expressions for distribution coefficients
Find out
(sometimes ~
c=)
called partitition coefficients). You may find this application of ~
the equilibrium law referred to as the distribution law or partition
law.
Now you carry out an experiment to determine a distribution

coefficient.
EXPERIMENT 5
Distribution equilibrium
Aim
determine the value of the distribution
coefficient for the equilibrium that exists
when ammonia is distributed between water
and 1,1,1-trichloroethane.
64
Introduction
In this experiment you shake some ammonia solution with 1,1,1-trichloro-
ethane to e~tablish equilibrium, and then determine the concentration of
ammonia in each solvent by titration. This enables you to calculate the
distribution coefficient, KO.
NH3(tce).~ NH3(aq) (tce = 1.1.1-trichloroethane)
K - [NH 3 ( aq ) 1
o - [NH3(tce))
Requirements
safety spectacles
measuring cylinder, 50 cm3
ammonia solution, 1.0 M NH3
1.1.1~trichloroethane, CH3CCl3
separating funnel, 150 cm3
2 beakers. 100 cm3
pipette. 10 cm3• and safety filler
wash-bottle of distilled water
methyl orange indicator solution
white tile
burette. 50 cm3, and stand
hydrochloric acid, 0.010 M HCI (standardized)
hydrochloric acid, 0.50 M HCI (standardized)
Procedure
1. Pour about 50 cm3 of ammonia solution into a separating funnel.
2. Pour about 50 cm3 of 1,1.1-trichloroethane into the same separating
funnel.
3. Holding the tap firmly in position with one hand and the stopper with
the other. shake the separating funnel vigorously for about ten seconds.
Release the pressure inside by loosening the stopper fOr a momerrt.
4. Continue shaking f8r about half a minute. releasing the pressure every
ten seconds. Set aside until two layers separate.
5. Transfer the lower organic layer to a beaker. Using a dry pipette,
transfer 10.0 cm3 to a conical flask. Add about 20 cm30f distilled
water. a few drops of indicator and titrate the mixture with 0.010 M HCI
until the yellow solution just changes to red and remains red after
shaking. (It may take a few moments for all the ammonia to transfer
from the organic layer and react with the acid.)
6. Ti trate two more 10 cm3 samples and complete a copy. of Resul ts Table 6.
7. Transfer the aqueous layer to a beaker. Rinse the pipette thoroughly,
transfer 10.0 cm to a flask, add about 20 cm3 of water and a few
3
drops of indicator solution. and titrate to the endpoint with 0.50 M HCI.
8. Titrate two more 10 cm3 samples and complete a copy of Results Table 7.
65
Results Table 6
Solution in flask mol dm-3 ern"
Indicator
Trial 1 2 3 4
Final
Burette readings
Initial
Volume used/cm3
Mean titre/cm3
Results Table 7
Solution in flask mol dm-3 cm3
Indicator
Trial 1 2 3 4
Final
Burette readings
Initial
Volume used/cm3
Mean titre/cm3
Calculation
1. Calculate the average concentration of ammonia in the organic layer
from Results Table 6.
2. Calculate the average concentration of ammonia in the aqueous layer
from Results Table 7.
3. Calculate the distribution coefficient.
K - [NH3 (aq) ]
o - [NH3(tce)J
4. Compare your results with others in the class.
(Specimen results and calculations on page 98 )
The calculation in the next exercise is similar to the calculation in

Experiment 5; or you may choose to use a graphical method.
66
Exercise 52 Calculate the value of the distribution coefficient for ~
the distribution equilibrium of butanedioic acid between
water and ether from the following data. All experiments ~\\
were performed at the same temperature.
Concn of acid in water 0.0759 0.108 0.158 0.300

fmol dm-3
Concn of acid in ether 0.0114 0.0162 0.0237 0.0451

fmol dm-3
(Answer on page 97)
The distribution of a solute between two solvents is sometimes used in

extraction and purification procedures. For instance, you could remove
most of the ammonia from a solution in 1,1,1-trichloroethane by shaking it
with water in several portions, as you discover in the next exercise.
Exercise 53 This exercise concerns the removal of ammonia from a

solution in 1,1,1-trichloroethane (0.10 mol dm-3) by
shaking with water. KO = 290.
How much ammonia remains in the organic layer after shaking
100 cm3 of the solution with
(aJ 100 cm3 of water,
(b) four successive 25 cm3 portions of water?
In the distribution equilibria you have considered so far, the solute is in

the same molecular form in both solvents. For example, ammonia in
1,1,1-trichloroethane exists entirely as molecules of NH3, and in water
almost entirely as molecules of NH3. There is a slight reaction in water:
NH3Caq) + HzO(I) ~ NH4+(aq) + OH-Caq)
but K for this is about 10-7, so virtually all the ammonia remains as
c
molecules.
By contrast, ethanoic acid exists in aqueous solution almost entirely as

CH3COzH molecules and in 1,1.1-trichloroethane almost entirely as (CH3COzH)z
molecules, i.e. as dimers. You need not concern yourself with the
de~ivation of the expression for KO' but the simple result is that a
squared term appears:
[(CH3C02H) (tee)]
[CH3C02H(aq)]2
The next exercise concerns a similar equilibrium system.
67
Exercise 54 Trichloromethane was added to a series of aqueous ~
solutions of ethanoic acid (acetic acid) and the J\
~
mixtures shaken at laboratory temperature. By titra-
tion the following concentrations of ethanoic acid were
found in the two layers:
Trichloromethane/g dm-3 17.5 43.5 84.6
Water/g dm-3 292 479 642
By neglecting any dissociation of ethanoic acid in water,
deduce its molecular formula in trichloromethane.
You may use graph paper if you wish.
LEVEL TWO CHECKLIST

You have now reached the end of this Unit. Look again at the checklist at
the end of Level One. In addition, you should now be able to:
(14) & (15) state the equilibrium law by writing an expression for the
equilibrium constant, Kc' for a reversible reaction;
(17) recognise those systems for which the equilibrium law expression is
independent of the volume;
(16) to (20) perform calculations based oH expressions for the equilibrium
constant, Kc;
(21) & (22) calculate the equilibrium constant, KQ, for a gaseous reaction,
given either partial pressures or amounts and total pressure at
equilibrium;
(23) & (24) calculate the pressure change required to alter the proportions
of reactants and products in an equilibrium system;
(25) c9lculate the average molar mass of a gaseous mixture;
(26) describe how equilibrium constants vary' with temperature;
(27) to (29) apply the equilibrium law to the calculation of solubility
product from solubility, and vice versa;
(30) perform calculations illustrating the common ion effect;
(31) predict whether preCipitation will occur in given circumstances;
(32) & (33) calculate the distribution coefficient, KO' and apply it to an
extraction process.
END-Of-UNIT TEST
To find out how well you have learned the material in this Unit, try
the test which follows. Read the nctes below before starting.
1. You should spend about 1~ hours on this test.
2. Hand your answers to your teacher for marking.
68
END-O~-UNIT TEST
1. At a certain temperature, the equilibrium constant for the

r ee u t.Lun :
is 4.
If one mole of ethanoic acid (CH3C02H) is added to one mo Le of
ethanul and the mixture is allowed to reach equilibrium, how many moles
of ethanoic acid will be present in the equilibrium mixture?
A a
4
B 2
3 C 1
2 o 13 E 1
4
( 1)
2. At a certain temperature, for the reaction:

CO(g) + C12(g) ~ COC12(g)
the equilibrium partial pressures of carbon monoxide, chlorine and
carlJ~nyl chloride are 2, 4 and 48 atm, respectively. What is the
value of Kp?
o
A 54 atm B 42 atm C 12 atm o 8 atm-1 E 6 atm-1 ( 1)
3. If the solubility of bismuth trisulphide, Bi2S3, is x mol dm-3

what is the numerical value of its solubility product?
4.
A 2x5 B 4x5 o
The solubility product of silver chromate is 1 x 10-12 mo13 dm-9•

In a solution in which [Cr042-]
[A g + J, in mo 1 dm -3, is
is 1 x 10-4 mol dm-3, the maximum
54x5
0 (1)
A
A 0.5 x 10-8 C 1 x 10-6 E 1 x 10-4
o 0.5 X 10-4 (1)
In Questions 5 and 6, one or more of the suggested responses is correct.

Answer as follows.
A if only 1 , 2 and 3 are correct
B if only 1 and 3 are correct
C if only 2 and 4 are correct
0 if only 4 is correct
E if some other response, or combination is correct.
5. In the following reversible reaction:

CO(g) + 2H2(g) ~ CH30H(g)
~ (298 K) = -92.5 kJ mol-1
Which factor(s) will increase the yield of methanol at equilibrium?

1 increased pressure on the system
2 addition of an inert gas at constant pressure
3 increased partial pressure of hydrogen
4 increased temperature. (1)
69
6. If a solution which is 0.0001 M with respect to carbonate ions.
C032-. is mixed with an equal volume of a 0.0001 M solution of
ions of a ~roup II metal. which of the following carbonates
would be precipitated?
K (298 K)/mo12 dm-6
s
1 MgC03 1 .1 x 10-5
2 CaC03 5.0 x 10-9
3 SrC03 1 .1 x 10 -1 0
4 BaC03 5.5 x 10 -1 0 (1 )
For Questions 7 and 8, choose an answer from A to E as follows

A Both statements true: second explains first.
B Both statements true: second does n-ot explain first.
C First true: second false.
0 First false: second true.
E Both false.
First statement Second statement

7. Increase in pressure has no effect There are equal numbers of
on the position of equilibrium of molecules of reactants and
the system products in the system
H2(g) + I2(g) ~ 2HI(g) H2(gJ + I2(g) ~ 2HI(g) ( 1)
8. The term [Ag2S04(S)J is absent In a saturated solution of

from the expression eqm for the silver sUlphate at a given
solubility product of the sparingly temperature. the concent-
soluble silver sUlphate. ration of dissolved silver
sulphate is constant. ( 1)
9. The following equilibrium is involved in the industrial

production of sUlphuric acid.
2S02(g) + 02(g) ~ 2S03(g); 6fl& = -189 kJ mol-1
(a) Write down the equilibrium expression for K . (1)
P
(b) State the effect. if any. of each of the following on the
equilibrium concentration of S03 in a particular equilibrium
mixture. clearly giving the reasons.
(i) increase of pressure (3)
(ii) increase of temperature (2)
(iii) addition of a catalyst (2 )
(iv) addition of an inert gas to the system at equilibrium
while maintaining the pressure constant. (3)
70
10. (a) Of the metals Zn, Mg and Fe, which removes copper(II) ion
from solution most completely? The following equilibrium
constants are measured at room temperature:
Zn(s) + Cu2+(aq) ? Cu(s) + Zn2+(aq) Kc 2 x 1037
Mg(s) + Cu2+(aq) ? Cu(s) + Mg2+(aq) K 6 x 1090
c
Fe(s) + Cu2+(aq) ~ Cu(s) + Fe2+(aq) 3 x 1026
K (1)
c
(b) Explain your reasoning for your answer to part (a J. ( 1)
11 . (a) Write an expression for the solubility product of lead(II)

chloride. (1)
(b) The solubility product of lead(II) chloride is

1.6 x 10-5 mo13 dm-9 at a given temperature.
(i) What is the solubility in mol dm-3 of lead(II) chloride
in water at the same temperature?
(ii) How many moles of chloride ions must be added to a 1.0 M
solution of lead(II) nitrate at the same temperature in
order just to cause a precipitate of lead(II) chloride?
Assume that no change in volume occurs on adding the
chloride ions. (4)
12. In the vapour phase the following equilibrium exists between
dinitrogen tetroxide and nitrogen dioxide:
N204 ? 2N02
At atmospheric pressure and a given temperature T, 20.0 per cent

of the molecules in the vapour are N02.
CaJ Using the atmosphere as the unit of pressure, calculate the
equilibrium constant K at temperature T. (3)
p
(b) Calculate the percentage of N02 molecules in the vapour at
temperature T when the (total) pressure of the vapour is 0.50 (4)
atmosphere.
(Continued overleaf.)
71
13. When lead sulphate is added to an aqueous solution of sodium iodide,
the following equilibrium is obtained.
The equilibrium constant for this reaction may be determined by

adding an excess of lead sulphate to a known volume of a standard
solution of sodium iodide and allowing the mixture to equilibrate in
a water-bath thermostatically controlled at the desired temperature.
Cold water is then added to the reaction mixture to 'freeze' the
equilibrium and the mixture is then titrated with standard silver
nitrate solution. In a typical experiment using 50.0 cm3 of 0.1 M
sodium iodide, a titre of 31.0 cm3 of 0.1 M silver nitrate was
obtained.
(a) Give an expression for the equilibrium constant, X, of the
reaction. (1)
(b) Why is it not necessary to know the mass of lead sulphate used
ir the experiment?
(c) From the data given above, calculate
(i) the concentration of iodide ions present initially,
(ii) the concentration of iodide ions present at equilibrium,
(iii) the concentration of iodide ions which have reacted,
(iv) the concentration of sulphate ions formed,
(v) a value for X. (7 )
14. (a) State the partition law for the distribution of a solute
between two immiscible solvents. Under what conditions
~
does the law apply? ( 3)
(b) The following results were obtained in an experiment to
determine the partition coefficient of ammonia between water and
trichloromethane (CHCI3):
10.0 cm3 of the aqueous layer required 43.2 cm3 of 0.250 mol dm-3
hydrochloric acid for neutralization;
25.0 cm3 of the trichloromethane layer required 21.6 cm3 of
0.050 mol dm- hydrochloric acid for neutralization.
3
Calculate the partition coefficient at the laboratory

temperature. (5)
(Total 50 marks)
72
APPENDIX ONE
ADDITIONAL EXERCISES
Answers to these exercises, together with abbreviated methods, are on
pages 98 t0102.
A - Calculating Kc
Exercise 55
At 250 °C, equilibrium for the following system was established:
PC15(gJ ~ PC13(gJ + C12(gJ
Analysis of the mixture showed that
[PC13(gJ] 1.50 x 10-2 mol dm-3, [C12(gJ]
= 1.50 X 10-2 mol dm-3
and [PC15(g)] = 1.18 x 10-3 mol dm-3.
Calculate the value of K at this temperature.
c
Exercise 56
Analysis of the equilibrium system
2S02(g) + 02(g) ~ 2S03(g)
showed that
[S02(gJ] 1.37 mol dm-3
[S03(gJ] 0.92 mol dm-3
c
Exercise 57
At 700 K, analysis of the system
N2(g) + 3H2(gJ ~ 2NH3(g)
showed that
[N2(g)] = 13.6 mol dm-3, [H2(gJ] = 1.0 mol dm-3, [NH3(gJ] 1.5 mol dm-3
c
73
B - Calculating equilibrium concentrations
Exercise 58
In the following equilibrium:
H2(gJ + I2(gJ ~ 2HI(g)
K 54.1, at a particular temperature. The equilibrium mixture was found
tg contain H2 at a concentration of 0.48 x 10-3 mol dm-3, and HI at a
concentration of 3.53 x 10-3 mol dm-3•
What is the equilibrium concentration of I2?
Exercise 59
For the equilibrium
CSH10(1) + CH3C02H(1) ~ CH3C02C5Hll(lJ
(pentene) (ethanoic (pentyl ethanoate)
acid)
Kc = 540 mol-1 dm3 at a certain temperature.

An equilibrium mixture at this temperature contains 5.66 x 10-3 mol dm-3
of pentene and 2.55 x 10-3 mol dm-3 of ethanoic acid.
Calculate the concentration of pentyl ethanoate in the mixture.
Exercise 60
This question concerns the equilibrium system
In a particular experiment, 0.33 mol of CH3C02H, 0.66 mol of CH3C02C2Hs

and 0.66 mol of H20 are found to be present. What amount of C2HsOH is
present?
C - Calculating Kc from equilibrium amounts
Exercise 61
In the following equilibrium system:
H2(g) + I2(g) ~ 2HI(g)
20.57 mol of hydrogen and 5.22 mol of iodine were allowed to reach
equilibrium at 450 °C. At this point, the mixture contained 10.22 mol of
hydrogen iodide. Calculate the value of K at this temperature.
c
Exercise 62
The equilibrium
N204(1) ~ 2N02(1)
was established in a solvent at 10 °c starting with 0.1307 mol dm-3 of
N204; the equilibrium mixture was found to contain 0.0014 mol dm-3 of N02.
c
Exercise 63
C2H50HCl) + CH3C02HCl) ~ CH3C02C2H5Cl) + H20Cl)
2.0 mol of ethanol and 1.0 mol of ethanoic acid were allowed to react to
equilibrium at 25 °C. At equilibrium the mixture contained 0.845 mol of
ethyl ethanoate and the total volume was 30 cm3• Calculate the value of Kc
at this temperature.
D - Calculating equilibrium amounts from initial amounts

Exercise 64

CH3C02HCl) + C2~OHCl) ~ CH3C02C2H5Cl) + H20Cl)
8.0 mol of ethanoic acid, and 6.0 mol of ethanol were placed in a 2.00 dm3
vessel. What is the equilibrium amount of water? Kc at this temperature
::::
4.5.
Exercise 65
2HICg) ~ H2Cg) + 12(g)
1.0 mol of 12 and 2.0 mol of H2 are allowed to react in a 1.0 dm3 vessel
at 440 °C. What are the equilibrium concentrations of HI, H2 and 12 at this
temperature, given that K = 0.02 at 440 °C?
c
Exercise 66
4.0 g of phosphorus pentachloride is allowed to reach equilibrium at
250 °c in a 750 cm3 vessel. K 0.19 mol dm-3 for the following reaction
at 250 0c : o
PC15(g) ~ PC13(g) + C12(g)
Calculate the amount of phosphorus pentachloride at equilibrium.
E - Calculating Kp from partial pressures

Exercise 67
In the equilibrium system:

N204(g) ~ 2N02(g)
at 55 °C, the partial pressures of the gases are:
PN
2
° ::::0.33
4
atm and P
N02
= 0.67 atm
Calculate Kp for this system.
75
Exercise 68
In the following equilibrium system:
2S02(g) + 02(g) ~ 2S03(g)
at a certain temperature, the partial pressures of the gases are:
PSO = 2.3 atm, P = 4.5 atm, PSO = 2.3 atm

2
°2 3
Calculate K for this system.

P
Exercise 69
Consider the following reaction:
H2(g) + I2(g) ~ 2HI(g)
At a certain temperature, analysis of the equilibrium mixture of the gases
yielded the following results.
0.25 atm, PI = 0.16 atm, PHI = 0.40 atm
2
Calculate Kp for this reaction at the same temperature.
F - Calculating Kp from equilibrium amounts
Exercise 70
In the following reaction:
CO2 (g) + H2(g) ~ CO(g) + H20(g)
at a temperature of 100 0C and a pressure of 2.0 atm, the amounts of each
gas present at equilibrium were 6.2 x 10-3 mol of CO, 6.2 x 10-3 mol of
H20, 0.994 mol of CO2 and 0.994 mol of H2•
CalcuJate the value of Xp.
Exercise 71
An equilibrium mixture contained 0.40 mol of I atoms and 0.60 mol of 12
molecules. The total pressure was 1.0 atm. Calculate the value of X at
t-his temperature. P
I2(g) ~ 2I(g)
Exercise 72
H2(g) + I2(g) ~ 2HI(g)
at a temperature of 485 °C and a pressure of 2.00 atm, the amount of each
gas present at equilibrium was 0.56 mol of H2J 0.060 mol of 12 and 1.27 mol
of HI. Calculate K at this temperature.
P
76
G - Calculating pressure from Kpond equilibrium amounts
Exercise 73
2N02(g) ~ 2NO(g) + 02Cg)
at a temperature of 700 K. the amount of each gas present at equilibrium
is 0.96 mol of N02• 0.04 mol of NO. and 0.02 mol of O2,
If Kp = 6.8 X 10-6 atm what must the total pressure have been to achieve
this particular equilibrium mixture?
Exercise 74
Kp 3.72 atm at 1000 K for the system:
C(s) + H20Cg) ~ CO(g) + H2(g)
What pressure must be applied to obtain a mixture containing 2.0 mol of
CO. 1.0 mol of H2 and 4.0 mol of H20?
Exercise 75
At 1000 K. Kp = 1.9 atm for the system~
C(s) + CO2 (g) ~ 2CO(g)
What must the total pressure be to have an equilibrium mixture containing
0.013 mol of CO2 and 0.024 mol of CO?
H - Average molar mass
Exercise 76
For the equilibrium:
N2(g) + 3H2(g) ~ 2NH3(g)
at a particular temperature and total pressure of 2.0 atm, an equilibrium
mixture has the composition of 1.0 mol NH3, 3.6 mol H2 and 13.5 mol N2.
(a) Calculate the equilibrium constant, K , for this reaction under the
stated conditions. p
(b) Calculate the average molar mass of the mixture under the stated
conditions.
Exercise 77
PC15(g) ~ PC13(g) + C12(g)
a particular equilibrium mixture contains 0.20 mol PC15, 0.010 mol PC13
and 3.8 mol C12, at a particular temperature and a total pressure of 3.0 atm.
(a) Calculate the equilibrium constant, K , for this reaction under the
stated conditions. p
(b) Calculate the average molar mass of the mixture under the stated
conditions.
77
Exercise 78
N204(g) ~ 2N02(g)
1.00 mol of N204 was introduced into a vessel and allowed to attain
equilibrium at 308 K. It was found that the average molar mass of the
mixture was 72.4 g mol -1.
(a) Calculate the mole fraction of N02 in the equilibrium mixture.
(b) The pressure at equilibrium was 1.00 atm. Calculate Kp for the
system at the temperature of the experiment.
(c) Calculate the mole fraction of N02 which would be present in the
equilibrium mixture if the pressure were increased to 6.00 atm at the
same temperature.
78
APPENDIX TWO
This appendix contains some topics which are required only for certain
syllabuses. The first is fairly simple, but we consider the rest to be
rather advanced for A-level. We suggest you proceed only after discussion
with your teacher.
Objectives. When you have finished this appendix you should be able to:
(34) calculate Kp from Kc for a gaseous reaction, and vice versa;

(35) write an expression which relates equilibrium constant, standard free
energy change and temperature;
(36) sketch graphs showing minimum free energy at equilibrium for a range
of va lues of 6GB-;
(37) derive an expression which relates equilibrium constant, standard
enthalpy change and temperature;
(38) calculate 6HB- from a series of values of equilibrium constants at
different temperatures;
(39) calculate K at one temperature from 6HB- and K at another temperature.
We suggest that you work through the material in this appendix first
and then use your text-bookCs) afterwards for consolidation.
The relationship between Kp and Kc
You derive the relationship by means of a Revealing Exercise which

concerns the equilibrium system:
N204(g) ~ 2N02(g)
0.1. Write expressions for the amounts of the two gases, nNO and nN 0 ' in
terms of [N02(gJ], [N204(gJ] and the total volume, V. 2 2 4
0.2. Use the ideal gas law to relate the amounts, n and nN 0 ' to partial
pressures.
N02 2 4
A.2. PNO V = nNO RT PN 0 V = nN 0 RT

2 2 2 4 2 4
0.3. Combine A.1. and A.2. to write expressions for PNO and PN 0 in terms
of [N02(gJ] and [N204(gJ]. 2 2 4
A.3. PNO = [N02CgJ]RT

2
0.4. Write an expression for K and substitute partial pressures from A.3.
p
79
P~o a [N0~ (g )]2 (RT ) 2
A.4. K
P PN 0 [N 204 ( g) ]RT
2 4
0.5. Use A.4. to write an expression for K in terms of K •

P o
A.5. K K RT
P c
In general.
where 6n = number of moles of gaseous products - number of moles of gaseous

reactants.
Use this expression to do the following exercises. (Choose the value of R
which has the most appropriate unit.)
Exercise 78 For the equilibrium system:

PC15(g) ? PC13(g) + C12(g)
K = 0.811 atm at 523 K. Calculate K at this temperature.
p c
Exercise 80 In the equilibrium system:

N2(g) + 3H2(g) ? 2NH3(g)
~
K = 2.0 mol- 2 dm6 at 620 K. What is the value of K at this
c p
temperature?
Exercise 81 For the system:

H2(g) + I2(g) ? 2HI(g)
show that Kp = K c at any temperature.
Now we look at the relationship between equilibrium constant and standard

free energy change.
The relationship between K and LlG&
In Unit S3 (Chemical Energetics) you learned that it is the standard free

energy change. 6~. which determines whether a reaction can proceed. rather
than the standard enthalpy change. !:::l?'.
We were unable to explain fully at that stage why it is that although 6G

(not 6~) must be negative for a spontaneous change. reactions where 6c& has
a small positive value may proceed partially. towards an equilibrium
position.
80
The reason is that ~ and K are related mathematically by an equation,
which we now introduce without derivation.
6ae = -RT In K * or 6ae = -2.30 RT log K *
*We use 'In' to mean 'logarithm to the base e' and 'log' to mean 'logarithm
to the base 10'.
Note that for reactions involving a change in the amount of gas present,
K in the equation above must be Kp; in other cases we may use Kc.
The equation shows that

if 6ae is zero, log K is zero and K =
if 6ae is negative, log K is positive and K >
if 6ae is positive, log K is negative and K <
K = 1 for a simple reaction when there are Equal concentrations of reactants

and products. If K > 1 the products are favoured and if K < 1 the reactants
are favoured. The further away from zero the value of 6ae, the further the
equilibrium position lies to the right or left until,when ~ > 20 to
30 kJ mol -lor 6c& < -20 to -30 kJ mol-1, the reaction can be regarded as
virtually complete in one direction or the other. This is summed up in the
following diagrams.
Eqm
G G
100% 100% 100% 100%

reactants products reactants products
~Gesmall negative ~Ge large negative

(> - -30 kJ rnol rl] « - -30 kJ mol l)r
K>1 Kvery large
Equilibrium favours Virtually complete

products reaction
G Eqm
100% 100%
reactants products
Similar concentrations 'Eqm

Eqm
of reactants and products
G G
at equilibrium
100% 100% 100% 100%

reactants products reactants products
~Gesmall positive ~Ge large positive

« - +30kJ rnol l lr (> - +30 kJ mol r l)
K<1 Kvery small

Equilibrium favours Virtually no reaction
reactants
81
Notice that in every case G is at a mlnlmum at equilibrium so that 6G for
a partial reaction to an equilibrium mixture is always negative, even when
6c& (for complete reaction, under standard conditions) is positive.
In the next section we show you how the variation in equilibrium constant
with temperature is related to the standard enthalpy change of reaction.
The relationship between K and dHB-
To derive this relationship, you need only combine two equations which you
already know.
6I?" - T~
and -RT In K
Combining these two equations gives
-RT In K = 61? - T~
IV? 6E?
or In K = - RT + R
IV? and ~ vary a little with temperature but can be treated as constants
over a limited temperature range. A plot of In K against 1/T should
therefore be a straight line, because the equation is of the form
y=mx+c
t:J? ~
where the slope, m -R and the intercept, c = ~
We can therefore use a series of measurements of equilibrium constants at

different temperatures in two important ways.
1. We can calculate a value for t:J? This method is often applied when
calorimetry cannot be used.
2. We can obtain values of K for temperatures other than those at which
measurements were taken.
We illustrate these two uses in the following exercises.
82
Exercise 82 Use the information in the table below for the reaction: b.?
N204(g) ~ 2N02(g) ~
in answering the questions which follow .
TIK .l/K-~ Kp/atm 10gCK /atm)

T p
350 2.86 x 10-3 3.89 +0.59
400 2.50 x 10-3 4.79 x 1O~ +1.68
450 2.22 x 10-3 3.47 x 102 +2.54
500 2.00 x 10 -3 1.70 x 103 +3.23
(a) Plot a graph of log Kp (y-axis) against ~ (x-axis).

(b) Measure the slope of the graph and so calculate ~ for
this reaction. You may assume that ~ is constant over
this temperature range.
(c) What is the value of log Kp for this reaction at:

(l l 375 K, (ii) 475 K, (iii) 551J K?
What assumption must you make to determine
at 550 K? log K
P
(d) Use the graph to determine the effect of an increase in
temperature on the position of equilibrium for_ this reaction.
Exercise 83 Use the information in the table below for the reaction:~
N2Cg) + 3H2(g) ~ 2NH3(g)
~\\\
and answer the questions which follow.
3
TIK 10 !K-1 K latm-2 log (K latm-2)
T p P
345 2.9 1 x 103 +3.0
385 2.6 3.16 x 101 +1.5
500 2.0 3.55 x 10-2 -1.45
700 1.43 7.76 x 10-5 -4.11
(a) Calculate ~ for the reaction.

(b) Use the graph to determine the effect of an increase in
temperature on the position of equilibrium for this reaction.
(c) (i) What do you notice about the gradients of the graphs
drawn in this exercise and in the last?
(ii) What determines whether the gradient will be positive
or negative?
83
It is not always necessary to plot a graph of log K against; in order to
estimate K at some other temperature. We can derive an expression which
enables you to calculate K directly.
equilibrium constant at temperature Tl

equilibrium constant at temperature T2•
6l? 6se
Then In Kl + --
RTl R
6l? ~
and In K2 = + --
RT2 R
6l? 6l?
Subtracti.ng, In K2 - In Kl -- +
RT2 RTl
6l? 1 1
or In (K2 ) = - (- --)
Kl R Tl T2
If we use logarithms to the base 10, the expression becomes
log (K2) = 6l? 1 __ 1_)
(__
Kl 2.30 R Tl T2
Thus, if four of the quantities 6l?~ Kl~ K2~ Tl~ and T2 are known, the
fifth may be calculated.
Use the expression derived above in the following exercises.
Exercise 84 At 1065 °C, K 0.0118 atm for the reaction:

p
2H2S(g) ~ 2H2(g) + S2(g); 6l? = 177.3 kJ mO~ll
Calculate the equilibrium constant for the reaction at
1200 °C. ~~
Exercise 85 A particular reaction has a value of K = 2.44 atm at ~

1000 K and 3.74 atm at 1200 K. Calcul~te 6l? for this
reaction. ~~
84
Exercise 86 The table below gives information about the values at
different temperatures of the equilibrium constant for
the reaction:
N2(g) + o2(g) ~ 2No(g)
It also gives the partial pressures of NO in equilibrium with
two different mixtures of nitrogen and oxygen at the given
temperatures.
Partial pressure of NO/atm x 102
Temperature 104K PN = 0.8 atm PN2 = 0.8 atm

/K P 2
Po 2 = 0.2 atm Po 2 = 0.05 atm
1800 1.21 0.44 0.22
2000 4.08 0.81 0.40
2200 11.00 1.33 0.67
2400 25.10 2.00 1 .00
2600 50.30 2.84 1.42
(a) Write an expression for the equilibrium constant K for

the given reaction. P
(b) Use the expression you have written to explain why the
values in the fourth column are half those in the third.
(c) What condition of temperature and pressure should be used
to obtain the best yield of NO? Justify your answer.
(d) Is the reaction exothermic or endothermic? Justify your
answer.
Exercise 87 Calculate tifi& from the data given in Exercise 86.

(Answer on page 104
85
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104

Unit P2 Equilibrium I Principles

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UNIT

© Inner London Education Authority 1983

First published 1983

Reprinted 1984, 1985, 1987, 1989, 1990

All rights reserved.

Printed and bound in Great Britain by

British Library Cataloguing in Publication Data

Although ILPAC was initially conceived as a way of overcoming some of the

By providing personal guidance, and detailed solutions to the many exercises,

In addition, ILPAC can provide at least a partial solution to other problems.

A more detailed introduction to ILPAC, with specific advice both to students

Southern Universities Joint Board;

Oxford Oelegacy of Local Examinations

The Associated Examining Board

University of Cambridge Local Examinations Syndicate

University of London Entrance and School Examinations Council

Exercises 39, 41, 42 and 49 are reproduced, by permission, from Nuffield

Photographs are included by permission as follows:

&, Reading Revealing exercises

~\;l Test £: Computer programme

o 'A' Level question

INTERNATIONAL HAZARD SYMBOLS

IXI Harmful I~ Toxic Radioactive

In Level Two we introduce the equilibrium law, a mathematical statement

There is an ILPAC video-programme designed to accompany this Unit. It is

(1) state some examples of reversible reactions;

into a standard quadratic equation of the form ax2 + bx +. c o.

2. What effect does a catalyst have on a chemical reaction? (1)

3. Define the following terms. stating the usual units.

4. Write equations. including state symbols. for the reactions between:

5. Rearrange into standard quadratic form the equation:

(1) recognise that reversible changes are an essential feature of

2Mg(s) + 02(g) ~ 2MgO(s)

The idea of reversible change is very familiar in systems where no

For example, if iron is heated in a current of steam, it can be converted

We can represent this state of equilibrium by a 'double-ended arrow', ~.

You may be surprised to learn that it is useful to consider all chemical

reversed. We consider different types of equilibrium system in the next

Types of equilibrium system

9. Acid-base systems (dealt with more fully in Unit P3).

*We explain the term 'phase' in the next section.

1. The contents of a tube 2. A mixture of salt, sand and

Some of these different types of equilibrium system are illustrated in

Exercise 1 Look at the list of different types of equilibrium syste~

surroundings at ODC. sugar crystals

Another way of classifying different equilibrium systems divides them into

Exercise 2 Look again at the equilibrium systems illustrated in

If you can identify a heterogeneous system, solving numerical problems will

General statements about equilibrium

1. All equilibrium systems share the same general characteristics.

CHARACTERISTICS OF THE EQUILIBRIUM STATE

(4) list, in your own words, four characteristics of the equilibrium

Read about the characteristics of the equilibrium state in your text-

Teacher-marked Write an account of an experiment which shows

The following exercise tests your understanding of the characteristics

Exercise 3 Make a full-page-size copy of Table 2.

volume of liquid bromine

Why equilibrium systems are 'closed'

Exercise 4 Look again at Fig. 5.

Once a system is at equilibrium, it is impossible to determine whether the

Exercise 5 Choose any three systems, except E, from Fig. 5 and ~

Therefore you should do Part A of Experiment 2 (page 33) as soon as

FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

(6) explain what is meant by the term position of equilibrium;