A Textbook of

Physical Chemistry
Volume III
A Textbook of Physical Chemistry

Volume I :
States of Matter and Ions in Solution
Volume II :
Thermodynamics and Chemical Equilibrium
Volume III :
Applications of Thermodynamics
Volume IV :
Quantum Chemistry and Molecular Spectroscopy
Volume V :
Dynamics of Chemical Reactions, Statistical Thermodynamics Macromolecules, and
Irreversible Processes
Volume VI : Computational Aspects in Physical Chemistry
 A Textbook of
Physical Chemistry
Volume III
(SI Units)

Applications of Thermodynamics

Fourth Edition

k l kAPoor
Former Associate Professor
Hindu College
University of Delhi
New Delhi

McGraw Hill Education (India) Private Limited

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A Textbook of Physical Chemistry, Vol III
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To the Memory of
My Parents
Preface
in recent years, the teaching curriculum of Physical Chemistry in many indian
universities has been restructured with a greater emphasis on a theoretical and
conceptual methodology and the applications of the underlying basic concepts and
principles. This shift in the emphasis, as i have observed, has unduly frightened
undergraduates whose performance in Physical Chemistry has been otherwise
generally far from satisfactory. This poor performance is partly because of the
non-availability of a comprehensive textbook which also lays adequate stress on
the logical deduction and solution of numericals and related problems. Naturally,
the students find themselves unduly constrained when they are forced to refer to
various books to collect the necessary reading material.

it is primarily to help these students that i have ventured to present a textbook

which provides a systematic and comprehensive coverage of the theory as well as
of the illustration of the applications thereof.
The present volumes grew out of more than a decade of classroom teaching
through lecture notes and assignments prepared for my students of BSc (General)
and BSc (honours). The schematic structure of the book is assigned to cover
the major topics of Physical Chemistry in six different volumes. Volume I
discusses the states of matter and ions in solutions. It comprises five chapters
on the gaseous state, physical properties of liquids, solid state, ionic equilibria
and conductance. Volume II describes the basic principles of thermodynamics
and chemical equilibrium in seven chapters, viz., introduction and mathematical
background, zeroth and first laws of thermodynamics, thermochemistry, second
law of thermodynamics, criteria for equilibrium and A and G functions, systems
of variable composition, and thermodynamics of chemical reactions. Volume III
seeks to present the applications of thermodynamics to the equilibria between
phases, colligative properties, phase rule, solutions, phase diagrams of one-,
two- and three-component systems, and electrochemical cells. Volume IV deals
with quantum chemistry, molecular spectroscopy and applications of molecular
symmetry. it focuses on atomic structure, chemical bonding, electrical and
magnetic properties, molecular spectroscopy and applications of molecular
symmetry. Volume V covers dynamics of chemical reactions, statistical and
irreversible thermodynamics, and macromolecules in six chapters, viz., adsorption,
chemical kinetics, photochemistry, statistical thermodynamics, macromolecules
and introduction to irreversible processes. Volume VI describes computational
aspects in physical chemistry in three chapters, viz., synopsis of commonly used
statements in BASiC language, list of programs, and projects.
The study of Physical Chemistry is incomplete if students confine themselves
to the ambit of theoretical discussions of the subject. They must grasp the practical
significance of the basic theory in all its ramifications and develop a clear
perspective to appreciate various problems and how they can be solved.
Preface viii

it is here that these volumes merit mention. Apart from having a lucid style
and simplicity of expression, each has a wealth of carefully selected examples and
solved illustrations. Further, three types of problems with different objectives in
view are listed at the end of each chapter: (1) Revisionary Problems, (2) Try Yourself
Problems, and (3) Numerical Problems. Under Revisionary Problems, only those
problems pertaining to the text are included which should afford an opportunity to
the students in self-evaluation. in Try Yourself Problems, the problems related to
the text but not highlighted therein are provided. Such problems will help students
extend their knowledge of the chapter to closely related problems. Finally, unsolved
Numerical Problems are pieced together for students to practice.
Though the volumes are written on the basis of the syllabi prescribed for
undergraduate courses of the University of Delhi, they will also prove useful to
students of other universities, since the content of physical chemistry remains the
same everywhere. in general, the Si units (Systeme International d’ unite’s), along
with some of the common non-Si units such as atm, mmhg, etc., have been used
in the books.

Salient Features

∑ Comprehensive coverage to applications of thermodynamics to the equilibria

between phases, colligative properties, phase rule, solutions, phase diagrams
of one-, two-and three-component systems and electrochemical cells
∑ emphasis given to applications and principles
∑ explanation of equations in the form of solved problems and numericals
∑ iUPAC recommendations and Si units have been adopted throughout
∑ Rich and illustrious pedagogy

Acknowledgements

i wish to acknowledge my greatest indebtedness to my teacher, late Prof. R P

Mitra, who instilled in me the spirit of scientific inquiry. I also record my sense
of appreciation to my students and colleagues at hindu College, University of
Delhi, for their comments, constructive criticism and valuable suggestions
towards improvement of the book. i am grateful to late Dr Mohan Katyal (St.
Stephen’s College), and late Prof. V R Shastri (Ujjain University) for the numerous
suggestions in improving the book. i would like to thank Sh. M M Jain, hans Raj
College, for his encouragement during the course of publication of the book.
i wish to extend my appreciation to the students and teachers of Delhi
University for the constructive suggestions in bringing out this edition of the book.
i also wish to thank my children, Saurabh-Urvashi and Surabhi-Jugnu, for many
useful suggestions in improving the presentation of the book.
Finally, my special thanks go to my wife, Pratima, for her encouragement,
patience and understanding.
Feedback Request

The author takes the entire responsibility for any error or ambiguity, in fact or
opinion, that may have found its way into this book. Comments and criticism
from readers will, therefore, be highly appreciated and incorporated in subsequent
editions.
K L Kapoor

Publisher’s Note

McGraw-hill education (india) invites suggestions and comments from you, all
of which can be sent to [email protected] (kindly mention the title and
author name in the subject line).
Piracy-related issues may also be reported.
 Contents

Preface vii
Acknowledgements viii

1. EquILIbrIuM bEtwEEN PHasEs 1

1.1 Thermodynamic Criterion of Phase equilibria 1
1.2 Chemical Potential Versus Temperature Graphs of a Pure Substance 3
1.3 effect of Pressure on the Chemical Potential Versus Temperature Graphs 4
1.4 Clapeyron equation 6
1.5 Application of Clapeyron equation 7
1.6 First- and Second-order Phase Transitions 23
1.7 effect of Pressure on the Vapour Pressure of a liquid 26

2. CoLLIGatIVE ProPErtIEs 34
2.1 Solution 34
2.2 Methods of expressing Concentration of a Solution 34
2.3 lowering of Vapour Pressure – experimental Observations 41
2.4 Relative lowering of Vapour Pressure 43
2.5 Chemical Potentials of Solute and Solvent in an ideal liquid Solution 45
2.6 Origin of Colligative Properties 47
2.7 elevation of Boiling Point 50
2.8 Depression of Freezing Point 57
2.9 Osmosis and Osmotic Pressure 64
2.10 Relations Between Different Colligative Properties 72
2.11 Colligative Properties of Strong and weak electrolytes 75
2.12 Solubility of a Solute in an ideal Solution 83

3. PHasE ruLE 95
3.1 Introduction and Definitions 95
3.2 Derivation of Phase Rule 98
3.3 Some Typical examples to Compute the Number of Components 104

4. soLutIoNs 112
4.1 ideal Solubility of Gases in liquids 112
4.2 effect of Pressure and Temperature on the Solubility of Gases 115
4.3 henry’s law and Raoult’s law 120
4.4 Raoult’s law for Solvent and henry’s law for Solute 124
4.5 Derivations of Raoult’s and henry’s laws from Kinetic-Molecular Theory 126
4.6 ideal and ideally Dilute Solutions 128
xii Contents

4.7 Variation of henry’s law Constant with Temperature 129

4.8 Thermodynamics of ideal Solutions of liquid in liquid 130
4.9 Vapour Pressure of an ideal Binary liquid Solution 134
4.10 Vapour Pressure-Composition Diagram of a Binary liquid Solution 139
4.11 isothermal Fractional Distillation of an ideal Binary Solution 144
4.12 Temperature-Composition Diagram of a Binary liquid Solution 152
4.13 isobaric Fractional Distillation of an ideal Binary Solution 157
4.14 Nonideal Solutions of liquid in liquid 162
4.15 The Duhem-Margules equation 167
4.16 Temperature-Composition Diagrams of Nonideal Solutions 172
4.17 Konowaloff’s Rule – Revisited 175
4.18 Partially Miscible liquids 179
4.19 Completely immiscible liquids (Steam Distillation) 192
4.20 Distribution of a Solute Between Two immiscible liquids – The Nernst
Distribution law 194

5. PHasE DIaGraMs of oNE-CoMPoNENt systEMs 217

5.1 Application of the Phase Rule 217
5.2 Qualitative Discussion of a Phase Diagram 217
5.3 Phase Diagram of water 220
5.4 Polymorphism 225

6. PHasE DIaGraMs of two-CoMPoNENt systEMs 245

6.1 Application of the Phase Rule 245
6.2 Classification of Diagrams 246
6.3 Thermal Analysis 246
6.4 Crystallization of Pure Components – Simple eutectic Phase Diagram 250
6.5 Crystallization of Pure Components and One of the Solids exists in More
than One Crystalline Form 261
6.6 Formation of a Compound Stable up to its Melting Point 266
6.7 Formation of a Compound which Decomposes Before Attaining
its Melting Point 272
6.8 Formation of a Complete Series of Solid Solutions 284
6.9 Formation of Partial Misciblity in the Solid State leading to Stable
Solid Solutions 296
6.10 Formation of Partial Misciblity in the Solid Phase leading to Solid
Solutions Stable up to a Transition Temperature 301
6.11 Formation of Partial Miscibility in the liquid Phase and
Crystallization of Pure Components 307
6.12 Phase Diagrams of Aqueous Solutions of Salts 311

7. PHasE DIaGraMs of tHrEE-CoMPoNENt systEMs 336

7.1 Application of the Phase Rule 336
7.2 Scheme of Triangular Plot 336
7.3 Systems of Three liquid Components exhibiting Partial Miscibility 345
 Contents xiii

7.4 Triangular Plots of a Ternary System Depicting Crystallization of its

Components at Various Temperatures 358
7.5 Ternary Systems of Two Solid Components and a liquid 373
7.6 Crystallization of Pure Components Only 373
7.7 Formation of Binary Compounds such as hydrates 379
7.8 Formation of a Double Salt 382
7.9 Formation of a Ternary Compound 389
7.10 Formation of Solid Solutions 392
7.11 Formation of Solid Solutions with Partial Miscibility 395
7.12 Salting out Phenomenon 396
7.13 experimental Methods employed for Obtaining Triangular Plots 397

8. ELECtroCHEMICaL CELLs 409

8.1 introduction 409
8.2 Reversible and irreversible Cells 413
8.3 electromotive Force and its Measurement 414
8.4 Formulation of a Galvanic Cell 417
8.5 electrical and electrochemical Potentials 418
8.6 Different Types of half-Cells and Their Reduction Potentials 419
8.7 The emf of a Cell and its Cell Reaction 426
8.8 Determination of Standard Potentials 434
8.9 Significance of Standard Half-Cell Potentials 436
8.10 Influence of Ionic Activity on Reduction Potential 450
8.11 effect of Complex Formation on Reduction Potential 452
8.12 Relation Between Metal-metal ion half-Cell and the Corresponding
Metal-insoluble Salt-Anion half-Cell 454
8.13 Cell Reaction and its Relation with Cell Potential 458
8.14 Calculation of Standard Potential for an Unknown half-Cell Reaction 460
8.15 Reference half-Cells 462
8.16 expression of Ecell in the Unit of Molality 464
8.17 Determination of Accurate Value of half-Cell Potential 467
8.18 Applications of electrochemical Cells 470
8.19 Construction of Potentiometric Titration Curves 495
8.20 Concentration Cells without liquid Junction Potential 514
8.21 Concentration Cells with liquid Junction Potential 519
8.22 Commercial Cells 528
8.23 Solved Problems 530
Annexure I: Concept of Activity 559
Annexure II: Derivation of Debye-hückel law 563
Annexure III: Operational Definition of pH 570
Appendix I: Units and Conversion Factors 571
Index 573
 1 Equilibrium Between Phases

1.1 THERMODYNAMIC CRITERION OF PHASE EQUILIBRIA

An Example of Consider a system in which a pure substance B is present in two phases in

a Substance equilibrium with each other. Let mB( ) and mB( ) denote the chemical potentials
Distributed Between of the substance in phase and phase , respectively. The Gibbs function of the
Two Phases system is given by

G = f (T , p, nB(a ) , nB(b ) ) (1.1.1)†

where nB( ) and nB( ) are the amounts of the substance B in phases and ,
respectively. The change in Gibbs function of the system as a result of changes
in T, p, nB( ) and nB( ) is given by

Ê ∂G ˆ Ê ∂G ˆ
dG = Á
Ë ∂T ˜¯ p, n
dT + Á dp
B(a ) , nB(b )
Ë ∂p ˜¯ T , n
B(a ) , nB(b )

Ê ∂G ˆ Ê ∂G ˆ
+ Á ˜ dnB(a ) + Á ˜ dnB(b )
Ë ∂nB(a ) ¯ T , p, n Ë ∂nB(b ) ¯ T , p, n
B(b ) B(a )

Ê ∂G ˆ Ê ∂G ˆ
dG = Á
Ë ∂T ˜¯ p, n
or dT + Á dp
B(a ) , nB(b )
Ë ∂p ˜¯ T , n
B(a ) , nB(b )

+ m B(a ) dnB(a ) + m B(b ) dnB(b ) (1.1.2)

If the amount dnB of the substance is transferred from phase to phase
at constant temperature and pressure, then from Eq. (1.1.2), we have
dG = m B(a ) ( - dnB ) + m B(b ) (dnB )
= (m B(b ) - m B(a ) ) dnB (1.1.3)

If the above transfer takes place reversibly, then

dG = 0

†
Throughout this book, phase is written within brackets drawn immediately after the
substance.
2 A Textbook of Physical Chemistry

and Eq. (1.1.3) reduces to

(m B(b ) - m B(a ) ) dnB = 0 (1.1.4)
Since dnB 0, it follows that
m B(a ) = m B(b ) (1.1.5)

that is, if a substance is in equilibrium between two phases, its chemical potential
must have the same value in both the phases.
Generalized The above criterion of a substance present in two phases in equilibrium may be
Treatment generalized for a system containing more than one phase and each phase
containing more than one substance. Let us consider a closed system at a given
temperature and pressure containing the amounts n1, n2, n3, . . . of components
1, 2, 3, . . ., respectively. The differential of the Gibbs function of each phase at
constant temperature and pressure may be written as
dG(a ) = m1(a ) dn1(a ) + m2(a ) dn2(a ) + m3(a ) dn3(a ) + ◊◊◊
dG(b ) = m1(b ) dn1(b ) + m2(b ) dn2(b ) + m3(b ) dn3(b ) + ◊◊◊
dG(g ) = m1(g ) dn1(g ) + m2(g ) dn2(g ) + m3( g ) dn3(g ) + ◊◊◊
.................................................................................................. (1.1.6)
The total change of Gibbs function is given by
dG = dG(a ) + dG(b ) + dG(g ) + ◊◊◊ = 0 (1.1.7)
(This is zero because of equilibrium between the phases.)
Since the system over all is a closed system, the sum of changes of the
substances in various phases must be zero. Thus, we have
dn1(a ) + dn1(b ) + dn1(g ) + ◊◊◊ = 0
dn2(a ) + dn2(b ) + dn2(g ) + ◊◊◊ = 0
dn3(a ) + dn3(b ) + dn3(g ) + ◊◊◊ = 0
....................................................... (1.1.8)
Equation (1.1.8) can be rewritten as
dn1(a ) = – (dn1(b ) + dn1(g ) + ◊◊◊)
dn2(a ) = – (dn2(b) + dn2(g ) + ◊◊◊)
dn3(a ) = – (dn3(b ) + dn3(g ) + ◊◊◊)
.......................................................
Substituting these in Eq. (1.1.7) and rearranging, we get
(m1(b ) - m1(a ) ) dn1(b ) + (m1(g ) - m1(a ) ) dn1(g ) + ◊◊◊
+ (m2(b ) - m2(a ) ) dn2(b ) + (m2(g ) - m2(a ) ) dn2(g ) + ◊◊◊
+ (m3(b ) - m3(a ) ) dn3(b ) + (m3(g ) - m3(a ) ) dn1(g ) + ◊◊◊ = 0
 Equilibrium Between Phases 3

Since all dns are independent variables, we must have

m1(a ) = m1(b ) = m1(g ) = ◊◊◊
m2(a ) = m2(b ) = m2(g ) = ◊◊◊
m3(a ) = m3(b ) = m3(g ) = ◊◊◊
............................................ (1.1.9)
that is, if the system is in equilibrium, the chemical potential of any one
component must have the same value in each phase in which it exists.

1.2 CHEMICAL POTENTIAL VERSUS TEMPERATURE GRAPHS OF A PURE SUBSTANCE

Factor Determining For a pure substance, we have
the Slope of Graph dm = - Sm dT + Vm dp (1.2.1)
where Sm and Vm are its molar entropy and volume, respectively. The expression
for the slope of μ versus T curve at a constant pressure as obtained from
Eq. (1.2.1) is
Ê ∂m ˆ
ÁË ˜¯ = - Sm (1.2.2)
∂T p
Now Sm of a given substance in any phase, i.e. solid(s), liquid(1) or gas(g), is
always positive with the result that the slope of μ versus T curve at a constant
pressure is always negative
For the three phases of a given substance, we have
Ê ∂m s ˆ Ê ∂m1 ˆ Ê ∂m g ˆ
ÁË ˜ = - Sm,s ; ÁË ˜ = - Sm,1; ÁË dT ˜¯ = - Sm,g
∂T ¯ p ∂T ¯ p p

At any temperature, since

Sm,s < Sm,1 << Sm,g
it follows that
– Sm,s > – Sm,1 >> – Sm,g (1.2.3)
In other words, we have:
The slope of μ versus T curve for a substance in the solid phase has a small
negative value as Sm, s has a small value.
The slope of μ versus T curve for the liquid phase is slightly more negative
than that of the solid phase.
The slope of μ versus T curve for the gaseous phase has a large negative
value as Sm, g is very much larger than that of the liquid.
Diagrammatic The above characteristics are shown in Fig. 1.2.1.
Representation
Conclusion It will be seen from Fig. 1.2.1 that the curve for the solid and liquid phases
intersect each other at temperature Tm. At this temperature, the chemical potential
4 A Textbook of Physical Chemistry

Fig. 1.2.1 Chemical

potential versus
temperature graphs of
solid, liquid and gaseous
phases of a pure
substance

of the substance is same in both the phases and, consequently, it represents the
solid-liquid equilibrium. The temperature Tm is the melting point (m.pt.) of the
solid. Similarly, the curves for the liquid and gaseous phases intersect each other
at temperature Tb where μ1 = μg. At this point, the liquid and gaseous phases
coexist in equilibrium with each other. The temperature Tb is the boiling point
(b.pt.) of the liquid.
The state of the system at any temperature can be obtained from Fig.
1.2.1. Thus, we have:
(i) T < Τm : μs has the lowest value and thus the solid phase is stable.
(ii) T = Tm : μs = μ1; solid and liquid phases are in equilibrium.
(iii) Tb > T > Tm : μ1 has the lowest value and thus the liquid phase is stable.
(iv) T = Tb : μ1 = μg; liquid and gaseous phases are in equilibrium.
(v) T > Tb : μg has the lowest value and thus the gaseous phase is
stable.

1.3 EFFECT OF PRESSURE ON THE CHEMICAL POTENTIAL VERSUS

TEMPERATURE GRAPHS
Factor Determining It can be seen from Eq. (1.2.1) that at constant temperature
the Slope of Graph
Ê ∂m ˆ
ÁË ˜¯ = Vm (1.3.1)
∂p T
Since Vm is always positive, it follows that dm has the same sign as that of dp,
i.e. dm is positive if dp is positive and it is negative if dp is negative.
If the pressure is changed by an infinitesimal amount dp at constant
temperature, the change in the chemical potential is given by
dm = Vm dp (1.3.2)
Since for most substances
Vm,g >> Vm,1 > Vm,s
it follows that the order of change in chemical potential is
|dmg | >> |dm1 | > |dms | (1.3.3)
 Equilibrium Between Phases 5

Diagrammatic Figure 1.3.1 shows qualitatively the effects which are produced on the chemical
Representation potential (shown by dotted lines) of a substance in the three phases when pressure
of the system is reduced. The decrease at a given temperature is smallest for
the solid phase and largest for the gaseous phase (Eq. 1.3.3). For example, at a
temperature T, the decrease in chemical potential for solid is from a to a , for
liquid from b to b and that for gas from c to c . The decrease c to c is much
larger than from a to a and b to b .

Fig. 1.3.1 Effect of

pressure on the chemical
potential versus
temperature plots of a
substance having
Vm, 1 > Vm, s

Conclusion The following conclusions my be drawn from Fig. 1.3.1.

The melting point as well as the boiling point shifts to a lower value as
the pressure is decreased; the shift is relatively larger for boiling point.
Condition for The temperature difference between Tm and Tb decreases with decrease in pressure.
Sublimation of a This indicates that the temperature range over which the liquid phase can exist
Substance is decreased. If the pressure is decreased to a sufficiently low value, it may
happen that the liquid is not formed, the solid directly passes over to the gaseous
form. This happens when the boiling point of the liquid falls below the melting
point of the solid as shown in Fig. 1.3.2.
The temperature Ts is the sublimation temperature and is found to be very
sensitive to changes in pressure.
From Fig. 1.3.2, it may be concluded that if:
(i) T < Ts : μs has the lowest value and thus the solid phase is stable,
(ii) T = Ts : μs = μg, both solid and gaseous phases coexist in equilibrium,
(iii) T > Ts : μg has the lowest value and thus the gaseous phase is stable.
6 A Textbook of Physical Chemistry

Fig. 1.3.2 Effect of a

large decrease in
pressure on μ versus T
plots

The effects which are produced when the pressure is increased are exactly
opposite to those described above. There is an increase in melting point as well
as boiling point of the substance; the increase in boiling point is relatively larger,
and this enhances the stability of the liquid phase.
Effect on a The effect of pressure on the melting and boiling points of a substance which
Substance Involving shows a decrease in volume on melting can likewise be discussed. In this case,
a Decrease in the decrease of chemical potential of the solid will be larger than that of the liquid
Volume on Melting as shown in Fig. 1.3.3. It is obvious from Fig. 1.3.3 that there occurs an increase
instead of a decrease in the melting point of the solid as the pressure is decreased.
The increase in pressure will consequently decrease the melting point of such
type of substances. Examples include water, bismuth and antimony.

1.4 CLAPEYRON EQUATION

Derivation of Let us consider a system in which a pure substance B is present in two phases
Clapeyron Equation and . The two phases may be either solid and liquid, or solid and vapour,
or liquid and vapour. At equilibrium, we will have
m B(a ) = m B(b ) (1.4.1)
Now let the temperature of the system be changed by an infinitesimal
amount. When the equilibrium is re-established, the pressure also undergoes
a change by an infinitesimal amount. Under these conditions, the chemical
potentials μB( ) and μB( ) also change by infinitesimal amounts dμB( ) and dμB( ),
respectively. Since the system is again in equilibrium, if follows that
m B(a ) + dm B(a ) = m B(b ) + dm B(b ) (1.4.2)
 Equilibrium Between Phases 7

Fig. 1.3.3 Effect of

pressure on chemical
potential versus
temperature plot of a
substance having
Vm, 1 < Vm, s

Making use of Eq. (1.4.1), this reduces to

dm B(a ) = dm B(b ) (1.4.3)

Writing dμs in the explicit form in terms of dT and dp, we get

dm B(a ) = - Sm, B(a ) dT + Vm, B(a ) dp
dm B(b ) = - Sm, B(b ) dT + Vm, B(b ) dp (1.4.4)
where Sm, B( ) and Vm, B( ) are molar entropy and molar volume of the substance
B in the phase , respectively, and Sm, B( ) and Vm, B( ) are those in the phase ,
Substituting Eq. (1.4.4) in Eq. (1.4.3), we get
– Sm, B(a ) dT + Vm, B(a ) dp = – Sm, B(b ) dT + Vm, B(b ) dp

Rearranging, we get
dp Sm, B(b ) - Sm, B(a ) D trs Sm, B
= = (1.4.5)
dT Vm, B(b ) - Vm, B(a ) D trsVm, B
where trsSm, B and trsVm, B are the respective changes in entropy and volume
of the system when 1 mol of pure substance B is transferred from the phase
to the phase .
Equation (1.4.5) is known as the Clapeyron equation.

1.5 APPLICATION OF CLAPEYRON EQUATION

In this section, we consider the application of Clapeyron equation to the two-
phase equilibria involving solid and liquid, solid and vapour, liquid and vapour,
and solid and solid.
8 A Textbook of Physical Chemistry

Solid-Liquid If one mole of the substance B is transformed from the solid phase to the liquid
Equilibrium phase, then we have
D trs Sm, B = Sm, B(1) - Sm, B(s) = D fus Sm, B (1.5.1)

D trsVm, B = Vm, B(1) - Vm, B(s) = D fusVm, B (1.5.2)

At the equilibrium temperature, the transformation of the substance from solid
to liquid is reversible, hence
D fus Sm, B = D fus H m, B /T (1.5.3)

Substituting Eq. (1.5.3) in Eq. (1.4.5), we get

dp D fus Sm, B D fus H m, B
= = (1.5.4)
dT D fusVm, B T D fusVm, B
The transformation of solid to liquid is always an endothermic process and
hence fusHm is a positive quantity. The term fusVm may be positive or negative
depending upon which one (whether solid or liquid) is more dense. For most
substances, ρs is greater than ρ1 and hence fusVm is positive. For substances
such as water, bismuth and antimony, fusVm is negative as the solid phase is
less dense than the liquid phase.
Magnitude of dp/dT The ordinary magnitudes of the quantities fusSm and fusVm are
for Fusion Process
D fus Sm = 8 to 25 J K -1 mol -1 and D fusVm = ± (1 to 10) cm 3 mol -1

Taking the typical values of

D fus Sm = 20 J K -1 mol -1 and D fusVm = ± 5 cm 3 mol -1

we get

dp 20 J K -1 mol -1
= -1
= ± 4 J K -1 cm -3 = ± 4(MPa cm 3 ) K -1 cm -3
dT ± 5 cm mol
3

Ê 1 ˆ
= ± 4 MPa K -1 = ± 4 ¥ 103 kPa K -1 = ± 4 ¥ 103 Á atm˜ K -1
Ë 101.325 ¯
= ± 39.5 atm K -1 (1.5.5)

That is, the slope of pressure versus temperature graph for solid-liquid equilibrium
has a large value. The graph is almost vertical. It is slightly tilted to the left
(negative slope) if fusVm is negative (Fig. 1.5.1).
Diagrammatic The line of Fig. 1.5.1 represents equilibrium temperatures of solid-liquid
Representation of equilibrium at various pressures, i.e. along the line solid and liquid phases
Pressure Variation coexist in a state of equilibrium with each other. A point lying anywhere on the
with Temperature left of the line corresponds to temperature below the melting point of the
substance, and thus in this region only the solid form exists. A point on the right
of the line corresponds to temperature above the melting point, and hence in
this region only the liquid form exists.
 Equilibrium Between Phases 9

Fig. 1.5.1 Plot of p

versus T for solid-liquid
equilibrium, when
(a) fusVm = +ve, and
(b) fusVm = –ve

Now inverting Eq. (1.5.5), we get

dT 1
=± K atm -1 = ± 0.025 K atm -1
dp 39.5
Thus, change in the melting point of a solid with variation of external
pressure is very small. The plus sign is meant for those substances which show
an increase in volume on melting whereas the negative sign is meant for those
substances where a decrease in volume on melting is observed. For most
substances, ρs > ρ1, and thus an increase in the melting point is observed with
increase in external pressure. In case of substances for which volume decreases
on melting (i.e. ρs < ρ1), a decr ease in the melting point occurs when the external
pressure increases. Examples include ice, bismuth and antimony.
Integrated Form of The Clapeyron equation (Eq. 1.5.4) can be written as
Clapeyron Equation D fus H m dT
dp = (1.5.6)
D fusVm T
Integrating Eq. (1.5.6), we get
p2 Tm¢ D fus H m dT
Úp1
dp = ÚT
m D fusVm T
where Tm and T m are the melting points at pressures pl and p2, respectively. If
fusHm and fusVm are considered independent of temperature and pressure, the
above equation becomes
D fus H m ÊT¢ ˆ
p2 - p1 = ln Á m ˜
D fusVm Ë Tm ¯

Since the difference T m – Tm is usually small, the logarithm term can be

approximated to
ÊT¢ ˆ Ê T + Tm¢ - Tm ˆ Ê Tm¢ - Tm ˆ
ln Á m ˜ = ln Á m ˜¯ = ln ÁË 1 +
Ë Tm ¯ Ë Tm Tm ˜¯
Tm¢ - Tm DT
=
Tm Tm
10 A Textbook of Physical Chemistry

Thus, we have
D fus H m DT
p2 - p1 = Dp = (1.5.7)
D fusVm Tm
Equation (1.5.7) describes variation in the melting point of a substance with
the change in external pressure. The form of Eq. (1.5.7) is identical to that of
Eq. (1.5.6) except that the infinitesimal changes dp and dT are replaced by finite
changes p and T, respectively.
Conclusion It may be pointed out once again here that for a given increase in external
pressure (i.e. p positive), the sign of T depends on the sign of fusVm. Thus,
we will have
T positive if fusVm is positive
T negative if fusVm is negative.

Example 1.5.1 The melting point of mercury is 234.5 K at 1.0132 5 bar pressure and it increases 5.033
× 10–3 K per bar increase in pressure. The densities of solid and liquid mercury are 14.19
and 13.70 g cm–3, respectively, (a) Determine the molar enthalpy of fusion, (b) Calculate
the pressure required to raise the melting point to 273 K.
Solution (a) Since D p = (D fus H m /D fusVm ) (DT/Tm ), we have
(D fusVm ) Tm
D fus H m =
(DT/Dp)
Ê 1 1ˆ
where D fusVm =Vm, 1 - Vm, s = M Á - ˜
Ë r1 rs ¯
From the given data, we get

Ê 1 1 ˆ
D fusVm = (200.59 g mol -1 ) Á -
Ë 13.70 g cm -3 14.19 g cm -3 ˜¯
= 0.51 cm3 mol -1 = 0.51 ¥ 10 -3 dm3 mol -1

(D fusVm )Tm (0.51 ¥ 10 -3 dm 3 mol -1 ) (234.5 K)

Hence, D fus H m = =
(DT/Dp) (5.033 ¥ 10 -3 K bar -1 )
= 23.30 dm 3 bar mol -1
Ê 100 kPa ˆ
= (23.30 dm3 bar mol -1 ) Á = 23.30 ¥ 102 J mol -1
Ë 1 bar ˜¯
= 2.33 kJ mol -1
(b) Substituting the given data in the expression
D fus H m DT
Dp =
D fusVm Tm

(23.30 dm 3 bar mol –1 ) (38.5 K)

we get Dp =
(0.51 ¥ 10 –3 dm 3 mol –1 ) ( 234.5 K)
= 7 501 bar
 Equilibrium Between Phases 11

Liquid-Vapour For the liquid-vapour equilibrium of the substance B, we have

Equilibrium D vap H m
D vap Sm, B = Sm, B(g) - Sm, B(1) = (1.5.8)
T
D vapVm, B = Vm, B(g) - Vm, B(1)

where vapSm, B and vapVm, B are the respective changes in entropy and volume
during the vaporization of one mole of liquid B at its boiling point T. Since
both vapSm and vapVm are positive, the quantity dp/dT is always positive, i.e.
the slope of p versus T is always positive.
For most substances, vapSm 90 J K–1 mol–1 (Trouton’s rule) and vapVm = 24.0
Illustration dm3 mol–1, the quantity dp/dT has a value of the order of 0.037 atm K–1 as
shown in the following.

dp 90 J K -1 mol -1
= = 3.75 kPa K -1
dT 24.0 dm 3 mol -1
Ê 1 atm ˆ
= (3.75 kPa K -1 ) Á = 0.037 atm K -1
Ë 101.325 kPa ˜¯

This value is much smaller than that of the solid-liquid equilibrium.

Solid-Vapour For the solid-vapour equilibrium of the substance B, we have
Equilibrium
D sub H m
D sub Sm, B = Sm, B(g) – Sm, B(s) = ; T is the sublimation temperature
T
D subVm, B = Vm, B(g) – Vm, B(s)

where the subscript ‘sub’ stands for the sublimation process. Since both subSm
and subVm are positive, the value of dp/dT is also positive.
Important At the triple point, where the three curves solid-liquid, solid-vapour and liquid
Conclusion vapour meet one another (Fig. 1.5.2), the slope of the solid-vapour curve is
steeper than that of the liquid-vapour curve. This can be seen from the following
analysis.
At the triple point
D sub H m = D fus H m + D vap H m

and the slopes of the two curves are

Ê dp ˆ D vap H m Ê dp ˆ D sub H m
ÁË ˜¯ = and ÁË ˜¯ =
dT 1 v T D vapVm dT s v T D subVm

Since subHm > vapHm, it follows that

Ê dp ˆ Ê dp ˆ
ÁË ˜¯ > Á ˜
Ë dT ¯ 1
(1.5.9)
dT s v v
12 A Textbook of Physical Chemistry

Fig. 1.5.2 Phase

diagrams (a) carbon
dioxide where Vm, 1 > Vm, s
and (b) water where
Vm, 1 < Vm, s
Depiction of Phase The three curves representing s 1, 1 v and s v are shown together in
Diagram Fig. 1.5.2. This diagram, known as the phase diagram, shows the region of
stability of different phases. It also depicts at a glance properties of the substance
such as melting point, boiling point, transition points, triple points, etc. The
melting point, boiling point and transition temperature (if any) are represented
by the intersection points of a line drawn horizontally from the given external
pressure with those of s 1, 1 v and s s curves, respectively. The state of
the system at various temperatures for a given pressure (say, 1 atm) can also be
predicted from the phase diagram. For example, in Fig. 1.5.2, we have
T < Tm ; only solid phase
T = Tm ; solid and liquid phases in equilibrium
Tb > T > Tm ; only liquid phase
T = Tb ; liquid and vapour phases in equilibrium
T > Tb ; only vapour phase.
The 1 v curve extends only up to a limit of critical pressure and temperature,
because above these conditions, it is not possible to distinguish the vapour phase
from the liquid phase.
We will show in Chapter 3 that the triple point of a given substance is
observed at definite values of temperature and pressure. At this point, all the
three phases are at equilibrium. For water, the triple point is observed at 4.58
Torr and 0.009 8 °C and that for CO2 at 5.11 atm and –56.6 °C.
Integrated Form of The Clapeyron equation is
Clapeyron Equation
dp D trs Sm, B
(Clausius-Clapeyron = (Eq. 1.4.5)
Equation) dT D trsVm, B
At the transformation temperature T, the above expression becomes
dp D trs H m, B
= (1.5.10)
dT T D trsVm, B
where trsHm, B is either the molar enthalpy of vaporization of the liquid or the
molar enthalpy of sublimation of the solid and trasVm, B is given by
D trasVm, B = Vm, B(g) - Vm, B(s or 1) (1.5.11)
 Equilibrium Between Phases 13

Clausius Clausius simplifies Eq. (1.5.11) by introducing the following two approximations.

1. Vm, B(g) – Vm, B(s or 1) Vm, B(g); since Vm, B(s or 1) << Vm, B(g).
2. If the gaseous phase is assumed to be ideal, the molar volume of the gaseous
phase may be replaced by RT/p.
With these approximations, the Clapeyron equation becomes

dp D H dp D H dT
= trs 2m p or = trs m 2 (1.5.12)
dT RT p R T
Equation (1.5.12) is known as the Clausius-Clapeyron equation. It relates the
vapour pressure of a condensed phase (solid or liquid) with its molar enthalpy
of phase transformation (sublimation or vaporization) and the temperature of
transformation.
Integrated Form of Integration of Eq. (1.5.12) gives
Clausius-Clapeyron
p2 dp T2 D trs H m dT
Equation
Úp1 p
= ÚT
1 R T2
where p1 and p2 are the vapour pressures of the condensed phase (solid or liquid)
at temperatures T1 and T2, respectively. If trsHm is assumed to be independent
of temperature, we get

Êp ˆ D H Ê 1 1ˆ
ln Á 2 ˜ = - trs m Á - ˜ (1.5.13)
Ë p1 ¯ R Ë T2 T1 ¯

If p1 = 1 bar, then T1 represents the normal sublimation (or boiling) point of

the solid (or liquid) phase. Representing this by T *, we get

Ê p ˆ D H Ê 1 1ˆ
ln Á 2 ˜ = - trs m Á - ˜
Ë 1 bar ¯ R Ë T2 T * ¯
Dropping the subscript 2, we get

Ê p ˆ D H Ê1 1ˆ
ln Á = - trs m Á - ˜
Ë 1 bar ˜¯
(1.5.14)
R ËT T*¯

Diagrammatic If we plot ln (p/bar) (or log p/bar) versus 1/T, we get a linear curve with slope
Depiction of equal to – trs Hm/R (or – trs Hm/2.303R) as shown in Fig. 1.5.3. The intercept at
Eq. (1.5.14) 1/T = 0 yields the value of trs Hm/RT * (or trs Hm/2.303RT *). From the
determined values of slope and intercept, we can determine both trs Hm and
T * of the substance under study.
Open Integration of Dividing the numerator and denominator of left side of Eq. (1.5.12) by the unit
Eq. (1.5.12) vapour pressure (represented by pº), we get
(1/p∞) dp D H dT
= trs m 2
(p/p∞) R T
14 A Textbook of Physical Chemistry

Fig. 1.5.3 Plot of

log (p/pº) versus 1/T
for the condensed
phase-vapour equilibria

The open integration of this expression gives

Ê pˆ D H 1
ln Á ˜ = - trs m +I (1.5.15)
Ë p∞ ¯ R T
where I is a integration constant. Its values may be determined if the value of
vapour pressure p at some known temperature T is known. In terms of common
logarithm, Eq. (1.5.15) becomes
Ê pˆ D H 1
log Á ˜ = - trs m + I¢ (1.5.16)
Ë p∞ ¯ 20.303 R T
Note that the value of slope of Eq. (1.5.16) is independent of the unit of pº.

Example 1.5.2 At 373.15 K and 1 bar, the specific volume of water vapour is 1 696 cm3 g–1 and the
value of dp/dT is 0.036 2 bar K–1. Calculate vapHm.
Solution The given data are
T = 373.15 K
Vg = 1 696 cm 3 g -1 ∫ (1 696 ¥ 18) cm3 mol -1 = 1.696 ¥ 18 dm 3 mol -1
p = 1 bar
dp
= 0.036 2 bar K -1
dT
From the expression

dp D vap H m D vap H m
=
dT T D vap Vm TVm,v

Ê dp ˆ
we get D vap H m = Á ˜ TVm,v
Ë dT ¯
= (0.036 2 bar K –1 ) (373.15 K) (1.696 ¥ 18 dm 3 mol –1 )
= 412.37 bar dm3 mol –1 ∫ 41 237 kPa dm 3 mol –1
= 41 237 J mol –1
 Equilibrium Between Phases 15

Example 1.5.3 The vapour pressure of toluene is 0.078 8 bar at 313.75 K and 0.398 bar at 353.15 K.
Calculate the molar enthalpy of vaporization.
Solution The given data are
T1 = 313.75 K T2 = 353.15 K
p1 = 0.078 8 bar p2 = 0.398 bar

Substituting these values in the expression

p2 D vap H m Ê 1 1ˆ
ln =- ÁË T - T ˜¯
p1 R 2 1

Ê 0.398 bar ˆ D vap H m Ê 1 1 ˆ

we get ln Á ˜ =- Á - ˜
Ë 0.078 8 bar ¯ (8.314 J K –1 mol –1 ) Ë 353.15 K 313.75 K ¯

(8.314 J K –1 mol –1 ) (353.15 K) (313.75 K) Ê 0.398 ˆ

D vap H m = ln Á
Thus
(353.15 K – 313.75 K) Ë 0.078 8 ˜¯
= 37 866 J mol –1

Example 1.5.4 A certain liquid has a boiling point of 338.15 K at 1.013 25 bar pressure. Using Trouton’s
rule (a) estimate the vapour pressure at 325.15 K, (b) estimate the boiling point at a
pressure of 0.267 bar, and (c) obtain an equation for the vapour pressure in bar of this
liquid as a function of temperature.
Solution (a) The given data are
T1 = 338.15 K p1 = 1.013 25 bar
T2 = 325.15 K p2 = ?
D vap H m 10.5 RT1 (Trouton’s rule)

Substituting the given data in the expression

p2 D vap H m Ê 1 1ˆ
ln =- -
p1 R ÁË T2 T1 ˜¯
p2 Ê 1 1ˆ ÊT ˆ
we get ln = - (10.5 T1 ) Á - ˜ = - (10.5) Á 1 - 1˜
p1 Ë T2 T1 ¯ Ë T2 ¯

Ê p2 ˆ Ê 338.15 K ˆ
ln Á = - (10.5) Á - 1˜
Ë 1.013 25 bar ˜¯
i.e.
Ë 325.15 K ¯
= - 0.42
-0.42
or p2 = (e ) (1.013 25 bar) = (0.657) (1.013 25 bar)
= 0.666 bar
(b) In this case, we have

Ê 0.267 bar ˆ Ê 338.15 K ˆ

ln Á = - (10.5) Á - 1˜
Ë 1.013 25 bar ˜¯ Ë T2 ¯
Ê 338.15 K ˆ
- 1.334 = - (10.5) Á - 1˜
Ë T2 ¯
16 A Textbook of Physical Chemistry

338.15 K 1.334 11.834

or = +1=
T2 10.5 10.5

Ê 10.5 ˆ
T2 = Á
Ë 11.834 ˜¯
or (338.15 K) = 300.00 K

(c) Substituting the values of T1 and p1 in the expression

p2 ÊT ˆ
ln = - (10.5) Á 1 - 1˜
p1 Ë T2 ¯

Ê p2 ˆ Ê 338.15 K ˆ
ln Á = - (10.5) Á - 1˜
Ë 1.013 25 bar ˜¯
we get
Ë T2 ¯

Ê p ˆ 3 550.58 K
or ln Á 2 ˜ = ln (1.013 25) – + 10.5
Ë bar ¯ T2
3 550.58 K 3 550.58 K
= 0.013 2 – + 10.5 = 10.51 –
T2 T2

Ê p ˆ 1 541.72 K
or log Á 2 ˜ = 4.564 –
Ë bar ¯ T2

Example 1.5.5 The vapour pressure of a liquid which obeys Trouton’s rule rises by 52 Torr between
temperatures 1 K below and 1 K above the normal boiling point. Determine the value
of the normal boiling point and the molar enthalpy of vaporization of the liquid.

Solution The given data are

dp = 52 Torr dT = 2 K
D vap H m
= 10.5 i.e. D vap H m = (10.5) RTb (Trouton’s rule)
RTb
The Clapeyron equation becomes
dp D vap H m (10.5) R (10.5) R (10.5) p
= = =
dT Tb D vapVm Vm, v (RTb / p) Tb
This gives
(10.5) p (10.5) (760 Torr)
Tb = = = 3066.9 K
dp/dT (52 Torr)/(2 K)

Also D vap H m = (10.5) RTb = (10.5) (8.314 J K -1 mol -1 ) (306.9 K)

= 26 791 J mol -1

Example 1.5.6 If the enthalpy of vaporization of water is assumed to be constant at 2 255 kJ g–1, calculate
the temperature at which water will boil under a pressure of 77.0 cmHg, the boiling point
of water being 373.15 K at 76.0 cmHg. The specific volume of water vapour at 373.15 K
and 76 cmHg is 1 644 cm3 g–1 and that of liquid water is 1 cm3 g–1.
 Equilibrium Between Phases 17

Solution The given data are

T1 = 373.15 K p1 = 76.0 cmHg
T2 = ? p2 = 77.0 cmHg

D vap H m = (2 255 J g -1 ) (18 g mol -1 ) = 40 590 J mol -1

Vm,v = (1 664 ¥ 18) cm3 mol -1 = 29 952 cm3 mol -1

= 29.952 dm 3 mol -1
Vm,1 = 1 ¥ 18 cm3 mol -1 = 0.018 dm 3 mol -1

Using the expression

Êp ˆ D vap H m Ê 1 1ˆ
ln Á 2 ˜ = - -
Ë p1 ¯ R ÁË T2 T1 ˜¯

Ê 77.0 cmHg ˆ (40 590 J mol -1 ) Ê 1 1 ˆ

we get 2.303 log Á ˜ =- Á - ˜
Ë 76.0 cmHg ¯ (8.314 J K -1 mol -1 ) Ë T2 373.15 K ¯
Ê 1 1 ˆ
0.013 07 = - (4 882.1 K) Á -
Ë T2 373.15 K ˜¯

1 0.013 07 1
= – + = ( – 2.677 ¥ 10 –6 + 2.680 × 10 –3 ) K –1
T2 4 882.1 K 373.15 K
= 2.677 ¥ 10 –3 K –1
1
T2 = = 373.5 K
(2.677 ¥ 10 –3 K –1 )

Example 1.5.7 The mean enthalpy of vaporization of water in the temperature range between 363.15 K
and 373.15 K is 2 268 J g–1. Calculate the vapour pressure of water at 363.15 K, its
value at 373.15 K is being 76.0 cmHg.
Solution The given data are
T1 = 373.15 K p1 = 76.0 cmHg
T2 = 363.15 K p2 = ?
D vap H m = 2 268 × 18 J mol –1
= 40 824 J mol –1

Using the expression

Êp ˆ D vap H m Ê 1 1ˆ
log Á 2 ˜ = – –
Ë p1 ¯ 2.303 R ÁË T2 T1 ˜¯

Ê p2 ˆ 40 824 J mol –1 Ê 1 1 ˆ
we get log Á ˜ = – Á – ˜
Ë 76.0 cmHg ¯ (2.303) (8.314 J K –1 mol –1 ) Ë 363.15 K 373.15 K ¯
(40 824) (10)
= – = – 0.157 3
(2.303) (8.314) (363.15) (373.15)

p2
= 0.696 i.e. p2 = (0.696) (76.0 cmHg) = 52.9 cmHg
76.0 cmHg
18 A Textbook of Physical Chemistry

Example 1.5.8 Iodine boils at 456.15 K and the vapour pressure at 389.65 K is 100 Torr. The enthalpy
of fusion is 15.65 kJ mol–1 and the vapour pressure of the solid is 1 Torr at 311.85 K.
Calculate the triple point temperature and pressure.
Solution The given data are
Liquid-Vapour Equilibrium
T1 = 456.15 K p1 = 760 Torr
T2 = 389.65 K p2 = 100 Torr

Solid-Liquid Equilibrium
D fus H m =15.65 kJ mol -1
Solid-Vapour Equilibrium
T = 311.85 K p = l Torr
Calculation of vapHm: Using the Clausius-Clapeyron equation

Êp ˆ D vap H m Ê 1 1ˆ
log Á 2 ˜ = - -
Ë p1 ¯ 2.303 R ÁË T2 T1 ˜¯

Ê 100 ˆ D vap H m È 1 1 ˘
log Á =- -
Ë 760 ˜¯
we get
(2.303) (8.314 J K mol ) Î 389.65 K 456.15 K ˙˚
-1 -1 Í

(2.303) (8.314 J K -1 mol -1 ) (389.65 K) (456.15 K) Ê 760 ˆ

This gives D vap H m = log Á
(456.15 K - 389.65 K) Ë 100 ˜¯
= 45 076 J mol -1
Value of subHm: We have

D sub H m = D fus H m + D vap H m = 15.65 ¥ 103 J mol -1 + 45 076 J mol -1

= 60 726 J mol -1
Calculation of Triple Point Temperature and Triple Point Pressure
Let p and T be the pressure and temperature at the triple point, respectively. At this point,
the vapour pressure of liquid will be the same as that of solid. Hence, applying Clapeyron
equation at the triple point to liquid-vapour and solid-vapour equilibria, we get
Liquid-Vapour Equilibrium

Ê p ˆ Ê (45 076 J mol –1 ) ˆÊ1 1 ˆ

log Á ˜ = – Á –1 ˜ Á
– ˜¯ (1)
Ë 100 Torr ¯ Ë (2.303) (8.314 J K mol ) ¯
–1 Ë T 389.65 K
Ê1 1 ˆ
= – (2 354.2 K) Á – ˜
ËT 389.65 K ¯

Solid-Vapour Equilibrium

Ê p ˆ Ê (60 726 J mol -1 ) ˆ Ê1 1 ˆ

log Á ˜ =-Á Á - ˜ (2)
Ë 1 Torr ¯ Ë (2.303) (8.314 J K -1 mol -1 ) ˜¯ Ë T 311.85 K ¯
Ê1 1 ˆ
= - (3 171.5 K) Á -
Ë T 311.85 K ˜¯
 Equilibrium Between Phases 19

Subtracting Eq. (1) from Eq. (2), we get

3 171.5 K 3 171.5 2 354.5 K 2 354.2

log (100) = – + + –
T 311.85 T 389.65
1
2.00 = ( – 3 171.5 K + 2 354.2 K) + (10.170 – 6.042)
T
– 817.3 K
T = = 384.07 K
– 2.128

Substituting the value of T in Eq. (1), we get

Ê p ˆ Ê 1 1 ˆ
log Á = - (2 354.2 K) -
Ë 100 Torr ˜¯ ÁË ˜
384.07 K 389.65 K ¯
= - 0.0878

p = (0.817) (100 Torr) = 81.7 Torr

Example 1.5.9 The vapour pressures of solid and liquid white phosphorus are given by the expressions

Ê p ˆ (2 875 K) Ê p ˆ (2 740 K)
log Á 2 ˜ = - + 5.36 and log Á 1 ˜ = - + 4.95
Ë atm ¯ T Ë atm ¯ T

respectively. Calculate (a) the temperature and pressure of the triple point of phosphorus,
and (b) the molar enthalpy and molar entropy of fusion of phosphorus at the triple point.
Solution (a) At triple point, the vapour pressures of solid and liquid will be identical. Equating
the expressions of vapour pressure, we have

Ê p ˆ Ê p ˆ
log Á 2 ˜ = log Á 1 ˜
Ë atm ¯ Ë atm ¯

(2 875 K) (2 740 K)
or – + 5.36 = – + 4.95
T T

(2 875 K) (2 740 K)
or - = 5.36 - 4.95
T T

(135 K) (135 K)
or = 0.41 or T = = 329.3 K
T 0.41

The vapour pressure at the triple point can be obtained by substituting this temperature
in either of the vapour pressure expressions. Thus, we have

Ê p ˆ (2 875 K)
log Á 2 ˜ = - + 5.36 = - 8.732 + 5.36 = - 3.372
Ë atm ¯ (329.3 K)

Hence, p2 = 4.246 ¥ 10 -4 atm

(b) The expression of variation of vapour pressure with temperature is given by
Ê p ˆ DH m Ê p ˆ DH m
ln Á =- =- + I¢
Ë atm ˜¯
log Á
Ë atm ˜¯
+I i.e.
RT 2.303 RT
20 A Textbook of Physical Chemistry

Comparing this expression with the given expressions of vapour pressure, we get

D sub H m D vap H m
= 2 875 K and = 2 740 K
2.303 R 2.303 R

Thus D sub H m = (2.303) (8.314 J K -1 mol -1 ) (2 875 K) = 55 048 J mol -1

D vap H m = (2.303) (8.314 J K -1 mol -1 ) (2 740 K) = 52 463 J mol -1

Hence D fus H m = D sub H m - D vap H m = (55 048 - 52 463) J mol -1

= 2 585 J mol -1

Since G = 0 for the fusion at equilibrium temperature, therefore

D fus H m 2 585 J mol -1

D fus Sm = = = 7.85 J K -1 mol -1
T 329.3 K

Example 1.5.10 The vapour pressure of a liquid changes with temperature according to the expression

Ê p ˆ 273 K
log Á = 11.36 -
Ë mmHg ˜¯ T

Calculate the enthalpy of vaporization per mole of the liquid.

Solution The variation of vapour pressure with temperature is given by

Ê pˆ D vap H m Ê pˆ D vap H m
ln Á ˜ = - +I or log Á ˜ = - + I¢
Ë p∞ ¯ RT Ë p∞ ¯ 2.303 RT

Comparing this with the given expression, we get

D vap H m
= 273 K
2.303 R

or D vap H m = (2.303 R) (273 K) = (2.303 ¥ 8.314 J K -1 mol -1 ) (273 K)

= 5 227 J mol -1

Solid-Solid This type of equilibrium is observed if a substance exists in more than one
Equilibrium allotropic form. The typical example is that of sulphur, which exists in two
allotropic forms. At ordinary temperatures and under 1 atm pressure, its rhombic
form is stable. However, it passes over to the monoclinic form at 95.4 °C if heated
slowly. Above 95.4 °C, the monoclinic form is stable, until at 119 °C, where it melts
to give liquid sulphur. We can have the following equilibria in the sulphur system:
S(rhombic) S(monoclinic)
S(monoclinic) S(liquid)
S(liquid) S(vapour)
S(rhombic) S(vapour)
S(monoclinic) S(vapour)
 Equilibrium Between Phases 21

Besides the above equilibria, we can also have

S(rhombic) S(liquid)

This represents the metastable equilibrium and is observed only when the heating
of rhombic sulphur is done quickly. For 1 atm external pressure, the above
metastable equilibrium is observed at 114 °C.
The slope of the curve representing the allotropic transformation can be
obtained from the Clapeyron equation

dp D S D H
= trs m = trs m
dT D trsVm T D trsVm

The slope is usually quite large because of the small change in the molar volume
of transformation.

Phase Diagram of The phase diagram for the sulphur system is shown in Fig. 1.5.4. The metastable
Sulphur equilibria are shown by dotted lines.

Fig. 1.5.4 Schematic

Phase diagram of
sulphur

There are three stable and one metastable triple points:

(i) at 95.4 °C μrhomb = μmono = μv

(ii) at 119 °C μmono = μ1 = μv
(iii) at 151 °C μrhomb = μmono = μ1
(iv) at 114 °C μrhomb = μl = μv
22 A Textbook of Physical Chemistry

Example 1.5.11 The density of diamond is 3.52 g cm–3, while that of graphite is 2.25 g cm–3. At 298 K,
the free energy of formation of diamond from graphite is 2.866 kJ mol–1. At 298 K,
what pressure must be applied to bring diamond and graphite into equilibrium?

Solution The given data are

C(graphite) C(diamond) rG = 2 866 J mol–1
ρ (graphite) = 2.25 g cm–3
ρ(diamond) = 3.52 g cm–3
Since at equilibrium rG of the reaction is zero, it is obvious that we would have to
decrease rG of the reaction by 2 866 J mol–1 by increasing the external pressure. We
start with the relation
Ê ∂(D rG ) ˆ
ÁË ˜ = D trsVm
d p ¯T

or d(D rG ) = (D trsVm ) d p (T constant)

Ê 1 1 ˆ
= M carbon Á - ˜ ( p2 - p1 )
Ë rdiamond rgraphite ¯

Substituting the given data, we get

Ê 1 1 ˆ
( - 2 866 J mol -1 ) = (12 g mol -1 ) Á - ( p2 - 1 bar)
Ë 3.52 g cm -3 2.25 g cm -3 ˜¯

- 2 866 J mol -1
or ( p2 - 1 bar) = = 1 489.6 J cm -3
(3.409 - 5.333) (cm 3 mol -1 )

Now, since 1 J = 1 kPa dm3 = 10–2 bar dm3 = 10 bar cm3, we get
p2 - 1 bar = 14 896 bar
or p2 = 14 897 bar

Example 1.5.12 The density of ice II is 1.21 g cm–3, that of ice III is 1.10 g cm–3. Calculate trs Hm for
the conversion of 1 mol of ice II into ice III, if these two phases are in equilibrium at
3 260 atm and 298.15 K and at 2 450 atm and 242.15 K.
Solution The Clapeyron equation is
dp D S D H
= trs m = trs m
dT D trsVm T D trsVm
D trs H m
or dp = dT
T D trsVm

For a finite change, we have

D trs H m
Dp = DT
T D trsVm

(Dp) T D trsVm ( p2 - p1 )T1 [Vm, ice(III) - Vm, ice(II) ]

or D trs H m = =
DT (T2 - T1 )
 Equilibrium Between Phases 23

Substituting the given data, we get

Ê 18 g mol -1 18 g mol -1 ˆ
(3 260 atm - 2 450 atm) (242.15 K) Á -
Ë 1.1 g cm -3 1.21 g cm -3 ˜¯
D trs H m =
(6 K)
(810 atm) (242.15 K) (1.488 cm 3 mol -1 )
=
(6 K)
= 48 643 atm cm 3 mol -1 = 48.643 atm dm 3 mol -1
Ê 8.314 J ˆ
= (48.643 atm dm 3 mol -1 ) Á 3˜
Ë 0.082 atm dm ¯
= 4 932 J mol -1

Example 1.5.13 The specific volume of monoclinic sulphur which is stable above the transition temperature
is greater than that of rhombic sulphur by 0.0126 cm3 g–1. The transition point at one atm
pressure is 368.65 K and it increases at the rate of 0.035 K atm–1. Calculate the molar
enthalpy of transition.
Solution The given data are
p = 1 atm
Ti = 368.65 K

D trsVm = Vm, monoclinic – Vm, rhombic = 0.012 6 cm 3 g –1

= (0.012 6 × 32) cm 3 mol –1 = 0.012 6 × 32 × 10 –3 dm 3 mol –1
= 4.032 × 10 –4 dm 3 mol –1
dT/d p = 0.035 K atm –1 i.e. d p/dT = 28.57 atm K –1

Using the Clapeyron equation dp/dT = trsHm/(T trsVm), we get

D trs H m = Ti D trsVm (dp/dT )
= (368.65 K) (4.032 ¥ 10 -4 dm 3 mol -1 ) (28.57 atm K -1 )
= 4.247 dm 3 atm mol -1 = 4.247 dm 3 (101.325 kPa) mol -1
= 430.3 J mol -1

1.6 FIRST- AND SECOND-ORDER PHASE TRANSITIONS

First-Order Phase A given phase transition of a substance may be classified into first-order or
Transition second-order depending upon the following characteristics.
A first-order phase transition of a substance is accompanied with changes in the
values of enthalpy and volume of the substance, i.e. trsH and trsV are nonzero.
Examples include familiar phase transitions such as solid to liquid, solid to
vapour, and liquid to vapour.
For a substance B, we have
Ê ∂m B ˆ Ê ∂m B ˆ
ÁË ˜ = Vm,B and ÁË ˜ = - Sm,B
∂p ¯ T ∂T ¯ p
24 A Textbook of Physical Chemistry

If the substance B undergoes phase transition , we will have

Ê ∂Dm B ˆ Ê ∂m B(β ) ˆ Ê ∂m B(α ) ˆ

D trsVm,B = Á ˜ = Á -Á π0 (1.6.1)
Ë ∂p ¯ T Ë ∂p ¯ T Ë ∂p ˜¯ T
˜

Ê ∂D m B ˆ
D trs H m,B = T D trs Sm,B = - T Á
Ë ∂T ˜¯ p
and

ÔÏÊ ∂m B(b ) ˆ Ê ∂m B(a ) ˆ Ô¸

= - T ÌÁ ˜ -Á ˜ ˝ π 0 (1.6.2)
ÓÔË ∂T ¯ p Ë ∂T ¯ p ˛Ô
Equations (1.6.1) and (1.6.2) imply that the derivatives ( μB/ p) T and ( μB/ T ) p
have different values on either side of the transition or in other words, these
derivatives are discontinuous.
Main Characteristics Thus the main characteristics of first-order transitions are:
of First-Order
(1) The chemical potential is a continuous function of temperature.
Transitions
(2) The derivatives of chemical potential are discontinuous.
These characteristics are illustrated in Fig. 1.6.1.

Fig. 1.6.1 Typical

variations of
(a) Vm versus T,
(b) Hm versus T,
(c) – μ versus T,
(d) Sm versus T, and
(e) Cp versus T of first-
order transition

The fact that ( μ B/ T )p is discontinuous at the transition point leads to

another important characteristic that the first-order transition is accompanied by
an infinite heat capacity at the transition point. This may be understood from
the following analysis.
The heat capacity of the substance B is given by the relation

Ê ∂H ˆ
C p, B = Á B ˜
Ë ∂T ¯ p
Now since the transition takes place at constant temperature, the heat supplied
to the system is used in driving the transition (that is why H is discontinuous)
 Equilibrium Between Phases 25

rather than in raising the temperature of the system. Thus at the transition point,
we have
(∂H B ) p = positive
(∂T ) p = 0

(∂H B ) p positive
Hence C p,B = = =•
(∂T ) p 0

The variation of Cp of the system with temperature is also illustrated in

Fig. 1.6.1.
Second-Order Phase In a second-order phase transition of a substance B, the chemical potential and
Transition its derivatives ( μB/ T )p and ( μB/ p) T are continuous functions of temperature
whereas the second derivatives are discontinuous.
The fact that the first derivatives are continuous implies that changes in
the values of enthalpy and volume during transition are zero. In other words,
the entropy, the enthalpy and the volume of the system do not change when
the transition occurs.
Although the entropy of the substance changes in a continuous manner
with temperature, yet the rate of change in disorder (i.e. dSB) alters at the phase
transition point. Hence, the first derivative ( Sm,B/ T)p is a discontinuous function
of temperature. Since

Ê ∂2 mB ˆ Ê ∂Sm,B ˆ C p,m,B
-Á 2 ˜
= Á ˜ =
Ë ∂T ¯ p Ë ∂T ¯ p T

it follows that the second derivative of μB and Cp,m,B are discontinuous functions
of temperature.
Similarly, from the relations

Ê ∂2 mB ˆ Ê ∂Vm,B ˆ
-Á = -Á = k T Vm,B
Ë ∂p ˜¯ T
2 ˜
(κT is isothermal compressibility)
Ë ∂p ¯ p

∂2 mB Ê ∂Vm,B ˆ
= Á = a Vm,B
∂T ∂p Ë ∂T ˜¯ p
(α is cubic expansion coefficient)

and the fact that the rates of variation of Vm with T and p alter at the phase
transition, indicate that the second derivatives ( 2μB/ p2) and ( 2μB/ T p) are
discontinuous.
Diagrammatic The various characteristics of second-order transition discussed above are
Depiction of illustrated in Fig. 1.6.2. The heat capacity versus temperature curve often has
Characteristics the shape of Greek , and because of this reason the second-order transition is
frequently referred to as a -transition.
Examples of second-order transitions include order-disorder transitions in
alloys and the fluid-superfluid transition in helium (line AB in Fig. 1.6.3).
26 A Textbook of Physical Chemistry

Fig. 1.6.2 Typical

variations of
(a) Vm versus T,
(b) Hm versus T,
(c) – μ versus T,
(d) Sm versus T, and
(e) Cp,m versus T of
second-order transition

Fig. 1.6.3 -transition

of helium. Solid helium
is never in equilibrium
with the gas phase

1.7 EFFECT OF PRESSURE ON THE VAPOUR PRESSURE OF A LIQUID

Qualitative The variation in chemical potential of a liquid B (or solid B) with change in
Prediction the external pressure is given by

Ê ∂m B(1) ˆ
ÁË ∂p ˜¯ = Vm,B(1) (Eq. 1.3.1)
p

Since Vm,B(1) is positive, it follows that the chemical potential (or the escaping
tendency) of the liquid B is increased on increasing the external pressure.
For a liquid B in equilibrium with its vapour, we have
m B(1) = m B(v)
Moreover, the chemical potential of vapours of B is related to its pressure by
the relation
∞ + RT ln ( p/p∞)
m B(v) = m B(v)
 Equilibrium Between Phases 27

wher e pº represents the standard unit pressure. From the above expressions, it
follows that the increased value of μB(1) (or μB(v)) due to increase in the external
pressure is associated with increase in the vapour pressure of the liquid B(or
solid B).
Derivation of To determine the actual relation between the vapour pressure of the liquid and
Expression the total external pressure on the liquid phase, we proceed as follows. The
thermodynamic condition of equilibrium is
m B(v) (T , p) = m B(1) (T , P ) (1.7.1)

Equation (1.7.1) implies that at constant temperature, vapour pressure p is a

function of the external pressure P. To determine the relation between these,
we differentiate Eq. (1.7.1) with respect to P, such that

Ê ∂m B(v) ˆ Ê ∂p ˆ Ê ∂m B(1) ˆ
ÁË ∂p ˜¯ ÁË ∂P ˜¯ = ÁË ∂P ˜¯
T T T

Ê ∂p ˆ (∂m B(1) / ∂p)T Vm, B(1)

or ÁË ˜¯ = = (1.7.2)
∂P T (∂m B(v) / ∂p)T Vm, B( v )

where Vm, B(v) is the molar volume of vapour at pressure p. Since both Vm, B(1)
and Vm, B(v) are positive, it follows that the derivative ( p/ P)T is positive and
hence vapour pressure p increases with increase in external pressure P. However,
the rate of increase is small as Vm, B(1) << Vm, B(v).
If the vapour is assumed to be ideal, we have

Ê ∂p ˆ Vm,B(1)
ÁË ˜¯ =
∂P T RT/p

dp
or RT = Vm,B(1) dP (T constant) (1.7.3)
p

On integrating the above expression, we get

p2 dp P2
Úp1
RT
p
= ÚP
1
Vm,B(1) dP

If Vm, B(1) is assumed to be independent of pressure, we get

p2
RT ln = Vm,B(1) ( P2 - P1 ) (1.7.4)
p1
where p1 and p2 are the vapour pressures of the liquid under the external pressures
P1 and P2, respectively. If one of the external pressures on the liquid is its own
vapour pressure p*, then Eq. (1.7.4) reduces to
p2
RT ln = Vm, B(1) ( P2 - p*) (1.7.5)
p*
28 A Textbook of Physical Chemistry

Expressions for the variation of vapour pressure of a solid phase with the external
pressure can be derived similarly and is given by
p
RT ln 2 = Vm, B(s) ( P2 - P1 ) (1.7.6)
p1

Example 1.7.1 What is the vapour pressure of ice at 263.15 K due to the pressure of air at atmospheric
pressure? The density of ice is 0.920 g cm–3 and its vapour pressure at 263.15 K is
2.6 × 10–3 bar.
Solution The given data are

T = 263.15 K p* = 2.6 ¥ 10 3
bar
P2 = 1.01 325 bar p2 = ?
3
r(ice) = 0.920 g cm
The molar volume of solid ice is
M 18.0 g mol -1
Vm, s = = = 19.57 cm 3 mol -1 = 19.57 ¥ 10 -3 dm 3 mol -1
r 0.920 g cm -3
Substituting the given data in the expression
p2
RT ln = Vm,s (P2 - p*)
p*
Ê p2 ˆ
we get (0.083 14 dm 3 bar K -1 mol -1 ) (263.15 K) ln Á
Ë 2.6 ¥ 10 bar ˜¯
-3

= (19.57 ¥ 10 -3 dm 3 mol -1 ) (1.01325 bar - 2.6 ¥ 10 -3 bar)

Ê p2 ˆ (19.57 ¥ 10 -3 ) (1.010 65)
ln Á -3 ˜ = = 9.0 ¥ 10 -4
Ë 2.6 ¥ 10 bar ¯ (0.083 14) (263.15)
p2
= 1.000 9
(2.6 ¥ 10 -3 bar)
i.e. p2 = (1.000 9) (2.6 ¥ 10 -3 bar) = 2.602 ¥ 10 -3 bar

Example 1.7.2 Vapour pressure of water at 303.15 K is 0.042 4 bar when exposed to an insoluble gas at
1.013 25 bar pressure. What will be the vapour pressure if the gas pressure were increased to
101.325 bar? Density of water is 0.996 g cm–3 and it may be assumed to be incompressible.
Solution The given data are

P1 = 1.013 25 bar p1 = 0.042 4 bar

P2 = 101.325 bar p2 = ?
rwater = 0.996 g cm -3

The molar volume or liquid water is

M 18 g mol -1
Vm,1 = = = 18.07 cm 3 mol -1 = 18.07 ¥ 10 -3 dm 3 mol -1
r 0.996 g cm -3
 Equilibrium Between Phases 29

Substituting the given data in the expression

p2
RT ln = Vm,water (P2 - P1 )
p1

Ê p2 ˆ
we get (0.083 14 dm 3 bar K –1 mol –1 ) (303.15 K) ln Á
Ë 0.042 4 bar ˜¯
= (18.07 × 10 –3 dm3 mol –1 ) (101.325 bar - 1.013 25 bar)
-3
Ê p2 ˆ (18.07 ¥ 10 ) (100.312)
or ln Á ˜ = = 0.071 92
Ë 0.042 4 bar ¯ (0.083 14) (303.15)
p2
or = 1.075 or p2 = (1.075) (0.042 4 bar) = 0.045 6 bar
0.042 4 bar

REVISIONARY PROBLEMS

1.1 Show that the chemical potential of a substance present in more than one phase in
equilibrium with each other has the same value in all the phases.
1.2 (a) Show that the slope of μ versus T curve for a pure substance is equal to – Sm and
hence show that this slope is always negative.
(b) Show that the slope of μ versus T curve of a pure substance B follows the order
Ê ∂m B(s) ˆ Ê ∂m B(1) ˆ Ê ∂m B(v) ˆ
ÁË ∂T ˜¯ > ÁË ∂T ˜¯ >> ÁË ∂T ˜¯
p p p

and hence draw a schematic diagram of μ versus T curves for the above-mentioned
three phases. Locate the melting point and the boiling point of the substance on the
diagram.
(c) What is the effect of pressure on the μ versus T curves? Show that the shift in
the curves due to the change in pressure follows the order
dμB(v) >> dμB(1) > dμB(s)
and hence show the shift in the melting point and the boiling point with increase in
the external pressure.
(d) Show qualitatively that on increasing the external pressure the melting point of
a substance increases when melting results in an increase in volume, but a decrease
is observed when melting results in a decrease in volume.
1.3 (a) Derive the Clapeyron equation
dp D S
= trs m
dT D trsVm
as applicable to the phase transformation , where trs Sm and trsVm are the
respective changes in molar entropy and molar volume accompanying the phase
transformation.
(b) Show that:
(i) The slope d p/dT of solid to liquid transformation has a very high positive
(or negative) value.
(ii) At the triple point, the slope dp/dT of solid to vapour transformation is
steeper than that of liquid to vapour transformation.
(c) On what factors does the sign of the slope dp/dT of solid to liquid transformation
depend?
30 A Textbook of Physical Chemistry

(d) Show that the integrated form of Clapeyron equation as applicable to solid-solid
and solid-liquid transformations is
Dp 1 D trs H m
=
DT Ttrs D trsVm

1.4 (a) Discuss the Clausius simplifications to the Clapeyron equation and hence derive
the Clausius-Clapeyron equation as applicable to the condensed phase-gas equilibrium.
Does this relation hold good for the solid-liquid equilibrium?
(b) Draw a schematic plot of log ( p/p°) versus l /T. What will be its slope and intercept?
Do the values of slope and intercept depend upon the units in which pressure is
expressed?
(c) Is the relation
D sub H m = D fus H m + D vap H m
for a substance true at all conditions of temperature and pressure?
(d) Show qualitatively that the shift in the boiling point due to the given pressure
change is relatively larger than that of the melting point.
(e) Under what circumstances can the solid pass directly to the gaseous form without
the formation of liquid state?
1.5 What do you understand by the first-order and second-order phase transitions? What
are their main characteristics?
1.6 Derive the relation
p
RT ln = Vm, cond.phase (P - p*)
p*
where p is the vapour pressure under a pressure of P and p* is the vapour pressure
when the condensed phase and vapour are under the same pressure. From this relation,
show that the vapour pressure of the condensed phase increases on increasing the
total external pressure.
1.7 (a) For the liquid-vapour transformation, derive the following form of Clausius-
Clapeyron equation:
Ê pˆ D vap H m Ê 1 1 ˆ
ln Á =- Á - ˜
Ë p * ˜¯ R Ë T T *¯

where T* is the normal boiling of the liquid where p* = 1 atm; p is the vapour
pressure at temperature T and vapHm is the temperature-independent molar enthalpy
change of the transformation.
(b) Draw a schematic plot of log ( p/atm) versus 1/T. What do the slope and intercept
of such a graph represent? How are the slope and intercept affected if p is expressed
in cmHg?

TRY YOURSELF PROBLEMS

1.1 Trouton’s rule says that the molar entropy of vaporization of liquids is about
87.86 J K–1 mol–1 at the normal boiling point T *. From this show that the boiling
point at pressure p can be corrected to 760 mmHg by the relation

DTb = 0.000 125 T * (760 - p/mmHg).

Ï Dp D S D trs Sm D S D S Ê 760 mmHg ˆ ¸

ÌHint. = trs m = trs m = trs m Á ˜¯ ˝
Ó DT D trsVm Vm RT/p T* Ë R ˛
 Equilibrium Between Phases 31

1.2 (a) In deriving Eq. (1.5.13), it has been assumed that Hm of the system is independent
of temperature. Suppose Hm depends upon the temperature and is given by

Ê D b ˆ 2 (Dc)T
3
DH m = DH 0 + (Da)T + Á ˜ T + + ◊◊◊
Ë 2 ¯ 3
where H0, ( a), ( b), . . . , etc., are constants. Show that with this expression of
Hm, the Clausius-Clapeyron equation is given by

Êp ˆ DH 0 (T2 - T1 ) T
R ln Á 2 ˜ = + ( Da) ln 2
Ë p1 ¯ T2T1 T1
( Db) Dc
+ (T2 - T1 ) + (T22 - T12 ) + ◊◊◊
2 6
(b) Show that with the expression of Hm given in part (a), the open integration of
Clausius-Clapeyron equation yields

Ê pˆ DH 0 Db Dc 2
R ln Á ˜ = - + Da ln (T/K) + T + T + ◊◊◊ + I
Ë p∞ ¯ T 2 6

where I is the constant of integration.

1.3 For the condensed phase-vapour equilibrium, it is known that Keq = p, where p is
the pressure of the vapour. Show that on substituting this relation in the Clausius-
Clapeyron equation, we get

K2 DH m È 1 1˘
ln = -
K1 R ÍÎ T1 T2 ˙˚

1.4 The vapour pressure of a particular liquid varies with temperature as follows:

Ê p ˆ ( 4 849 K) ÊTˆ
log Á =- - 14.70 log Á ˜ + 50.24
Ë atm ˜¯ T Ë K¯

How does the enthalpy of vaporization vary with temperature?

1.5 The melting points of mercury at external pressures of 10 atm and 3 540 atm are
234.3 K and 257.2 K, respectively. Predict whether the transformation
solid Hg liquid Hg involves an increase or a decrease of volume.
(Ans. Increase)
1.6 (a) A solid substance directly passes to the gaseous form at STP conditions. State
the conditions under which the liquid form of the substance can be obtained.
(b) For a given substance, ρs = ρ1. Predict the nature of solid to liquid equilibrium
line in its phase diagram.
1.7 (a) The rate of change of chemical potential with temperature [i.e. ( μ/ T)p] is an
important quantity in the discussion of phase transitions. What is the difference in
slope on either side of (i) the freezing point of water, and (ii) the normal boiling
point of water? Given: vapHm = 40.59 kJ mol–1 and fusHm = 6.008 kJ mol–1.
(Ans. 22 J K–1 mol–1, 109 J K–1 mol–1)
(b) The gradient ( μ/ p)T is also an important quantity in order to decide the nature
of transition. What is the difference of this quantity on either side of the two
transitions referred to in part (a)? Given: ρ (ice) = 0.917 g cm–3, ρ(liquid water) =
1.0 g cm–3 at 0 °C and ρ(liquid water) = 0.958 g cm–3 and ρ(steam) = 0.598 kg
m–3 at 100 ºC.
32 A Textbook of Physical Chemistry

1.8 Combine the barometric formula for the dependence of pressure on altitude with the
Clausius-Clapeyron equation, and predict how the boiling point of a liquid depends
on altitude.
È 1 1 Ê Mgh ˆ ˘
Í Ans. = +Á ˜˙
ÍÎ T T * Ë T *D vap H m ¯ ˙˚

1.9 Why is the following relation not applicable for graphite-diamond transformation?

p2 D H Ê1 1ˆ
ln = trs m Á - ˜
p1 R Ë T1 T2 ¯
1.10 How do the slopes of Gm versus p curves for a liquid and its vapour vary as the
temperature of the liquid is increased towards its critical temperature?

NUMERICAL PROBLEMS

1.1 The melting point of benzene increases by about 0.03 K/atm. If the specific gravities
of solid and liquid benzene are 1.02 and 0.89 at the melting point of 278.65 K at
1 atm, what is the molar enthalpy of fusion of benzene? (Ans. 10.52 kJ mol–1)
1.2 For uranium hexafluoride the vapour pressures for the solid and liquid are given by

log ( ps / Torr) = 10.648 - 2 559.5/(T / K)

log ( p1/ Torr) = 7.540 - 1 511.3/(T / K)

Calculate (i) the temperature and pressure of the triple point and (ii) the molar
enthalpy of fusion of UF6.
(Ans. 337.2 K, 1 122 Torr, 20.08 kJ mol–1)
1.3 What is the boiling point of water on a mountain where the barometric reading is
500 Torr? The enthalpy of vaporization of water may be taken as 2.259 kJ g–1.
(Ans. 362 K)
1.4 The densities of - and -sulphur are 2.00 and 1.95 g cm–3, respectively, at their
transition temperature 369 K. The transition temperature changes by 0.036 K for
every atmosphere rise in pressure. Determine the molar enthalpy of transition.
(Ans. 426.4 J mol–1)
1.5 A particular liquid obeys both Clausius-Clapeyron equation and Trouton’s rule. With
this information calculate the vapour pressure of the liquid in atm, at a temperature
equal to one-third of the normal boiling point.
(Ans. 6.4 × 10–10 atm)
1.6 NH4NO3 undergoes a transition from one solid modification to another at 398.65 K
and 1 atm, and at 408.15 K and 1 000 atm pressure. The form stable at higher
temperatures has an average volume of 0.012 6 cm3 g–1 greater than the other
modification over the pressure range studied. From these data, calculate the molar
enthalpy of transition. (Ans. 4.284 kJ mol–1)
1.7 AgI exists in two forms, and , which are in equilibrium at 419.65 K at 1 atm pressure.
For the change of to , trsHm = 6.40 kJ mol–1, while trsVm = –2.2 cm3 mol–1.
Find the pressure at which the transition temperature will be 418.15 K.
(Ans. 67.37 atm)
1.8 Propene has the following vapour pressures:
T/K 150 200 250 300
p/Torr 3.82 198.0 2 074 10 040
 Equilibrium Between Phases 33

From these data calculate (a) the molar enthalpy of vaporization, (b) the normal
boiling point, and (c) the vapour pressure at 225 K
(Ans. (a) 19.54 kJ mol–1, (b) 741 Torr)
1.9 (a) The boiling point of n-butyl chloride is 77.96 °C. Without using any other data,
determine the boiling point at vapour pressure 650 Torr. (Ans. 72.8 ºC)
(b) The variation of vapour pressure of n-butyl chloride is also given by the empirical
equation

Ê p ˆ (1763 K)
log Á =-
Ë Torr ˜¯
+ 7.912
T
Calculate the molar enthalpy of vaporization from this equation.
(Ans. 33.76 kJ mol–1)
1.10 The vapour pressure of a given liquid varies with temperature according to the
following expression

Ê p ˆ (4 849.3 K) ÊTˆ ÊTˆ

log Á =- - 14.701 log
Ë Torr ˜¯ T
ÁË ˜¯ + 53.118 ÁË ˜¯
K K
Determine the molar enthalpy of vaporization at 298 K and at 423 K.
(Ans. 39.23 kJ mol–1, 79.04 kJ mol–1)
1.11 Find out the difference in the freezing points of ice at 1 atm pressure and under
its own vapour pressure. The vapour pressure of ice at 273 K is 4.579 mmHg. The
densities of ice and water at 273 K are 1.000 and 0.916 8 g cm–3, respectively, and
the enthalpy of fusion of ice is 6.009 kJ mol–1. (Ans. 0.007 5 K)
1.12 From the following data at 298 K, determine (i) the free energy change of transition
from graphite to diamond at 1 atm and 298 K, (ii) direction of spontaneous process
of graphite to diamond conversion, (iii) the pressure at which the two forms would
be in equilibrium at 298 K and at 1 273 K. Assume densities to be independent of
pressure.

Dc Hm Density
Form Sm/J K–1 mol–1
(kJ mol -1 ) (g cm -3 )
diamond – 395.32 2.439 3.513
graphite – 393.42 5.694 2.260
 2 Colligative Properties

2.1 SOLUTION
A solution may be defined as a homogeneous mixture of a single phase
containing one or more of the chemical species dispersed on a molecular scale.
The characteristics of any one section of the homogeneous solution will be
completely identical to those of any other section of the solution. Depending
upon the total constituents present in the solution, it is called the binary solution
(two constituents), ternary solution (three constituents), quarternary solution (four
constituents), and so on.
By convention, the constituent present in the largest amount is called the solvent
and the constituents present in relatively small amounts are called the solutes.
However, this classification is completely arbitrary, since it is not possible to
classify the two constituents of a binary solution into solute and solvent when
both of them are present in equal amounts. Any one of the two constituents may
be classified as the solute or the solvent. Thus this classification is a matter of
convenience only.
In this chapter, we shall consider only those properties which result because of
the dissolution of a nonvolatile solute in a volatile liquid solvent. These are,
the relative lowering of vapour pressure, elevation of boiling point, depression
of freezing point and the osmotic pressure. These are collectively known as the
colligative† properties as they depend only on the number of species present
in the solution and not on their nature. Before considering these properties, it
is worth reviewing the units in which the composition of the solution can be
expressed.

2.2 METHODS OF EXPRESSING CONCENTRATION OF A SOLUTION

There are many ways of expressing the concentration of a solution which are
used for different purposes. Some of these are:
Mass percentage.
Volume percentage.
Mass of a solute in a definite mass of solvent.
Mass of a solute per definite mass of solution.
†
Colligative, a latin word; co, together; ligare, to bind.
 Colligative Properties 35

Molarity; amount (in moles) of solute per dm3 of solution.

Normality; amount (in equivalents) of solute per dm3 of solution.
Molality; amount (in moles) of solute per kg of solvent.
Amount (or mole) fraction; amount (in moles) of a given substance divided
by the total amount (in moles) of all constituents of a solution.
Since the density of a solution varies with temperature, presumably due
to the variation of volume, it is obvious that the concentration c2, which is
expressed as mol dm–3 of the solution, varies with temperature. On the other
hand, molality and amount fraction are independent of temperature.

Example 2.2.1 Calculate the amount fraction, molal and molar concentrations of a solution containing
20 per cent acetic acid by mass in water, if the density of the solution at 20 °C is
1.026 g cm–3.
Solution In 100 g of the solution, we have
Mass of acetic acid, m2 = 20 g
Mass of water, m1 = 80 g
Molar mass of acetic acid, M 2 = 60 g mol -1
m2 20 g
Amount of acetic acid, n2 = = = 0.333 mol
M2 60 g mol -1
m1 80 g
Amount of water, n1 = = = 4.444 mol
M1 18 g mol -1
n2 0.333 mol
Amount fraction of acetic acid, x2 = =
n2 + n1 0.333 mol + 4.444 mol
0.333
= = 0..069 7
4.777
n 0.333 mol
Molality of acetic acid solution, m = 2 = = 4.163 mol kg -1
m1 (80/1 000) kg
Volume of the solution containing 20 per cent acetic acid by mass is
mass 100 g
V = = = 97.45 cm 3
density 1.026 g cm -3
n2 0.333 mol
Molarity of acetic acid solution, M = = = 3.417 mol dm -3
V (97.45/1 000) dm 3

Of the various units, molality, molarity and amount fraction are commonly employed
to express the composition of a solution. Quite often, we require the interconversion
of these concentration units.† These can be carried out as shown in the following.

†
Throughout this chapter, solvent is represented by the subscript 1, solute is represented
by the subscript 2. To avoid any confusion between the symbol m used simultaneously
for mass and molality, we use subscripted m for mass whereas unsubscripted m for
molality of the solution. To be specific, m1 and m2 represent masses of solvent and solute,
respectively, whereas m represents molality of the solution.
As per IUPAC recommendations, the symbol b may be used for molality to avoid
the confusion of notation.
36 A Textbook of Physical Chemistry

By definition, we have

n1 n2 n2
x1 = ; x2 = and M =
n1 + n2 n1 + n2 V

We will have

n2 n n2
M = = 2 =
V m/r (n1 M1 + n2 M 2 ) /r

Dividing numerator and denominator by n1 + n2 we get

x2 r
M = (2.2.1)
x1 M1 + x2 M 2

For a dilute solution x2M2 << x1M1, x1 1 and ρsolution ρsolvent. Under
these approrimations, Eq. (2.2.1) may be written as

x2 r
M i.e. M μ x2 (2.2.2)
M1

that is, molarity of the solution is directly proportional to the amount fraction
of solute in the solution.

Example 2.2.2 The amount fraction of methanol in aqueous solution is 0.02 and its density is
0.994 g mL–1. Determine the molarity of the solution.

Solution Let there be 1 mol of total amount of solvent and solute in the solution. We will have
Amount of solute, n2 = 0.02 mol
Amount of solvent, n1 = 0.98 mol

Mass of solution, m = mass of (solvent + solute) = n1 M1 + n2 M 2

= (0.98 ¥ 18 + 0.02 ¥ 32) g = 18.28 g

m 18.28 g
Volume of solution, V = = = 18.39 cm 3
r 0.994 g cm -3

Finally, the molarity of solution would be

n2 0.02 mol
M = = = 1.088 mol dm -3 (V expressed in dm3)
V 18.39 ¥ 10 -3 dm 3

Alternatively, using the conversion formula directly, we get

x2 r (0.02) (0.994 g cm -3 )
M = =
x1 M1 + x2 M 2 (0.98) (18 g mol -1 ) + (0.02) (32 g mol -1 )
 Colligative Properties 37

= 1.088 ¥ 10 -3 mol cm -3 = 1.088 ¥ 10 -3 mol (10 -1 dm)-3

= 1.088 mol dm -3

The expression relating molarity (M) with amount fractions (x1 and x2) is

x2 r
M =
x1 M1 + x2 M 2

where M1 and M2 are molar masses of solvent and solute, respectively.

Since x2 = 1 – x1, we get
x2 r
M =
(1 - x2 ) M1 + x2 M 2

which on rearranging gives

MM1
x2 = (2.2.3)
r + M ( M1 - M 2 )

Example 2.2.3 The molarity of NH3 in aqueous solution is 11.8 mol dm–3. Calculate the amount fraction
of NH3 in solution. The density of solution is 0.916 g cm–3.
Solution Let the volume of solution be 1 dm3. We will have
Amount of NH3, n2 = 11.8 mol
Volume of solution, V = 1 dm 3
Mass of 1 dm3 solution, m = V r = (103 cm3 ) (0.916 g cm -3 ) = 916 g
-1
Mass of NH3 in 1 dm3 solution, m2 = n2 M 2 = (11.8 mol) (17 g mol )
= 200.6 g
Mass of solvent in 1 dm3 solution, m1 = mass of (solution - solute)
= 916 g - 200.6 g = 715.4 g
m1 715.4 g
Amount of solvent in 1 dm3 solution, n1 = = = 39.74 mol
M1 18 g mol -1

n2 11.8
Amount fraction of NH3 in solution, x2 = = = 0.229
n1 + n2 39.74 + 11.8

Alternatively, using the conversion formula, we get

MM1
x2 =
r + M (M1 - M 2 )
(11.8 mol dm –3 ) (18 g mol –1 )
=
(0.916 ¥ 10 g dm –3 ) + (11.8 mol dm –3 ) {(18 – 17) g mol –1}
3

212.4 212.4
= = = 0.229
916 + 11.8 927.8
38 A Textbook of Physical Chemistry

By definition
n1 x2 n2
x1 = ; x2 = ; m=
n1 + n2 n1 + n2 m1
We will have
n2 n2
m= =
m1 n1 M1
Dividing numerator and denominator by n1 + n2, we get
x2
m= (2.2.4)
x1 M1
For a dilute solution x1 1. With this approximation, Eq. (2.2.4) may
be written as
x2
m or m μ x2 (2.2.5)
M1
that is, molality of solution is directly proportional to the amount fraction of
solute in the solution.

Example 2.2.4 The amount fraction of methanol in aqueous solution is 0.02. Determine the molality of
methanol in solution.
Solution Let there be 1 mol of total amount of solvent and solute. Then
Amount of solute, n2 = 0.02 mol
Amount of solvent, n1 = 0.98 mol
Mass of solvent, m1 = n1 M1 = (0.98 mol) (18 g mol -1 ) = 17.64 g
Finally, the molality of solution is
n2 0.02 mol
m= = = 1.134 mol kg -1 (m1 expressed in kg)
m1 17.64 ¥ 10 -3 kg
Alternatively, using the conversion expression directly, we get
x2 0.02
m= =
x1 M1 (0.98) (18 g mol -1 )
= 1.134 ¥ 10 -3 mol g -1 = 1.134 ¥ 10 -3 mol (10 -3 kg)-1
= 1.134 mol kg -1

The expression relating amount fractions (x1 and x2) and molality (m) is

x2
m= (M1 is the molar mass of solvent)
x1 M1

Replacing x1 = 1 - x2 and rearranging, we get

mM1
x2 = (2.2.6)
1 + mM1
 Colligative Properties 39

Example 2.2.5 An aqueous solution is 1.133 molal in methanol. Determine the amount fractions of
methanol and water.

Solution Let the mass of solvent be 1 kg. We will have

Amount of solute, n2 = 1.133 mol
Mass of solvent, m1 = 1 kg = 1 000 g
m1 1 000 g
Amount of solvent, n1 = = = 55.56 mol
M1 18 g mol -1

Amount fraction of solute (i.e. methanol) is

n2 1.133
x2 = = = 0.02
n1 + n2 55.56 + 1.133

Amount fraction of solvent (i.e. water) is

x1 = 1 - x2 = 1 - 0.02 = 0.98

Alternatively, using the formula directly, we get

mM1 (1.133 mol kg -1 ) (18 ¥ 10 -3 kg mol -1 )

x2 = =
1 + mM1 1 + (1.133 mol kg -1 ) (18 ¥ 10 -3 kg mol -1 )
0.020 394
= = 0.02
1 + 0.020 394
x1 = 1 - x2 = 1 - 0.02 = 0.98

Since molarity is given as M = n2/V, we assume that

Amount of solute = n2
Volume of solution = V
Mass of solute, m2 = n2M2 (M2 is molar mass of solute)
If ρ is the density of solution, then
Mass of solution = Vρ
Now Mass of solvent, m1 = mass of (solution – solute) = Vρ – n2M2
Finally, molality of solution is
amount of solute
molality =
mass of solvent expressed in kg
n2
i.e. m=
V r - n2 M 2

Dividing numerator and denominator of the right side by V, we get

(n2 /V ) M
m= = (2.2.7)
r - (n2 /V ) M 2 r - MM 2
40 A Textbook of Physical Chemistry

Example 2.2.6 The density of 1.35 M solution of acetic acid is 1.012 g cm–3. Calculate its molality.

Solution Let the volume of solution be 1 dm3. We have

Amount of solute, n2 = 1.35 mol
Volume of solution, V = 1 dm3
Mass of solute, m2 = n2M2 = (1.35 mol) (60 g mol–1) = 81 g
Mass of solution = Vρ = (103 cm3) (1.012 g cm–3) = 1 012 g
Mass of solvent, ml = Mass of (solution – solute) = (1 012 – 81) g
= 931 g = 0.931 kg
Finally, the molality of solution is

n2 1.35 mol
m= = = 1.45 mol kg -1 (m1 expressed in kg)
m1 0.931 kg

Alternatively, using the conversion formula directly, we get

M (1.35 mol dm -3 )
m= =
r - MM 2 (1.012 g cm ) - (1.35 mol dm -3 ) (60 g mol -1 )
-3

1.35 mol dm -3
= -3 -1
{1.012 (10 kg) (10 dm) } - (1.35 mol dm -3 ) {60 (10 -3 kg) mol -1}
-3

1.35
= mol kg -1 = 1.45 mol kg -1
1.012 - 1.35 ¥ 60 ¥ 10 -3

The expression relating molality (m) and molarity (M) is

M
m= (ρ is density of solution and M2 is molar mass of solute)
r - MM 2

Rearranging this expression, we get

mr
M= (2.2.8)
1 + mM 2

Example 2.2.7 The density of 1.450 molal solution of acetic acid is 1.012 g cm–3. Calculate its molarity.
Solution Let the mass of solvent be 1 kg. We have
Amount of solute, n2 = 1.450 mol
Mass of solvent, m1 = 1 kg
Mass of solute, m2 = n2M2 = (1.450 mol) (60 g mol–1) = 87.0 g
Mass of solution, msoln = mass of (solvent + solute)
= 1 000 g + 87.0 g = 1 087 g
msoln 1 087 g
Volume of solution, V = = = 1 074.1 cm 3
r 1.012 g cm -3
 Colligative Properties 41

Finally, molarity of solution is

n2 1.450 mol
M = = = 1.35 mol dm –3 (V expressed in dm3)
V 1.074 1 dm 3
Alternatively, using the conversion formula directly, we get

mr (1.450 mol kg -1 ) (1.012 g cm -3 )

M = =
1 + mM 2 1 + (1.450 mol kg -1 ) (60 g mol -1 )
(1.450 mol kg -1 ) {1.012(10 -3 kg) (10 -1 dm)-3}
=
1 + (1.450 mol kg -1 ) {60(10 -3 kg) mol -1}
1.450 ¥ 1.012
= mol dm -3
1 + 1.450 ¥ 60 ¥ 10 -3
= 1.35 mol dm -3

2.3 LOWERING OF VAPOUR PRESSURE — EXPERIMENTAL OBSERVATIONS

It is observed that when a nonvolatile solute is dissolved in a volatile solvent,

vapour pressure of the latter is lowered.
If a liquid is placed in an evacuated vessel, there occurs migration of solvent
molecules from the liquid surface to the empty space above and vice versa. The
system attains an equilibrium when the rates of these two migrations become
equal. At this stage, the pressure recorded at the space above the liquid is known
as the vapour pressure of the liquid. In the presence of a nonvolatile solute, the
number of solvent molecules available for migration from surface of solution
relative to those present in the pure solvent is decreased. As a consequence of
this, the vapour pressure of the solution is lesser than that of the pure solvent.
Let p* be the vapour pressure of the pure solvent and p be that of a solution.
Experimentally, it is found that the decrease in vapour pressure p* – p depends
upon the concentration of the solute in the solution. Figure 2.3.1 shows the
vapour pressure of the solvent when plotted against the amount fraction of the
solute in the solution. It can be seen from the figure that the vapour pressure
of the solution approaches the dashed line connecting p*(x2 = 0) to zero
(x2 = 1) in the lower concentration region (x2 near zero). At higher concentration
region, the observed pressure is found to lie below the dashed line—the deviation
becoming more as x2 increases.†
The above experimental observation at x2 0 can be summarized as
follows.
The vapour pressure of the solution approaches that of the dashed line
as the concentration decreases. In the lower concentration range (x2 0), the

†The case discussed here is the negative deviation from the straight-dashed line. Examples
with positive deviation, i.e. the actual vapour pressure line lies above the dashed line are
also known. These lines show the characteristic of approaching dashed line as x2 0.
The dashed-line plot is exhibited by the so-called ideal solutions.
42 A Textbook of Physical Chemistry

Fig. 2.3.1 Variation in

vapour pressure of a
solution with the amount
fraction of solute in the
solution

dashed line is tangent to the vapour pressure curve. In other words, the dashed
line represents the behaviour of a solution when its concentration is very small.
The above behaviour is exactly parallel to that observed in case of real gases.
It is found that the real gases deviate from the experimental gas laws such as
Boyle’s law, Charles law, etc. The deviation from these laws becomes less and
less as the pressure decreases and it is only in the very low pressure region as
p 0, the real gases follow the experimental gas laws. There we have imagined
an ideal gas, which is supposed to follow these gas laws under all conditions
of temperature and pressure. The real gas behaves like an ideal gas only in the
low pressure region and exactly as an ideal gas only when p 0. Thus the
characteristics of an ideal gas can be obtained from the characteristics of a real
gas by extrapolation to p = 0. In a similar way, we can define an ideal solution
which is supposed to follow the dashed line for variation of vapour pressure of
the solution with the concentration of the solute. Since for real solutions, this
dashed line is approached only when the concentration of the solution is small
(i.e. in dilute solution), it, therefore, follows that only the dilute solution for which
x2 0 behaves like an ideal solution. The characteristics of an ideal solution
can be obtained by extrapolating the characteristics of a real solution to x2 = 0.
The dashed line can be represented by an equation of straight line of the type
p = b + mx2 (2.3.1)
with the characteristics of
p = p* at x2 = 0
and p = 0 at x2 = 1.
 Colligative Properties 43

With these characteristics, Eq. (2.3.1) modifies to

p = (1 – x2)p* = x1p* (2.3.2)
that is, the vapour pressure of the solution containing a nonvolatile solute is
equal to the vapour pressure of the pure solvent multiplied by the amount
fraction of the solvent in the solution. This law, which is a limiting law, was
discovered by P. M. Raoult and is known as the Raoult’s law.† It is followed
by an ideal solution over the entire range of concentrations, whereas for a real
solution it is followed only when the concentration of solute approaches zero
(i.e. ideally dilute solution).‡

2.4 RELATIVE LOWERING OF VAPOUR PRESSURE

According to Raoult’s law, the lowering of vapour pressure of a solvent is given
by
p* - p = p* - x1 p* = p* (1 - x1 ) = p* x2
p* - p
Thus = x2 (2.4.1)
p*
The expression ( p* – p)/p* is known as the relative lowering of vapour pressure
and according to Eq. (2.4.1), this is equal to the amount fraction of the solute
in the solution.

Example 2.4.1 Exactly 100 g water contains 1.0 g urea and 2.0 g sucrose at 298 K. The vapour pressure
of water at 298 K is 0.031 67 bar. Predict the vapour pressure of the solution.
Solution Amount fraction of solvent
Amount of solvent
=
Amount of (solvent + solute)
(100 g/18 g mol -1 )
=
(100 g/18 g mol ) + (1 g/60 g mol -1 ) + (2 g/342 g mol -1 )
-1

5.556
=
5.577
According to Raoult’s law
p1 = p1* x1 = (0.031 67 bar) (5.556/5.577) = 0.031 55 bar

The amount fraction x2 of solute is given by

n2 n2 N A
x2 = =
n1 + n2 n1 N A + n2 N A
Number of molecules of solutee
=
Total number of molecules of solute and solvent

†
See Section 4.3 for the kinetic-molecular treatment of Raoult’s law.
‡
Raoult’s law applicable to solvent in a nonideal solution may be written as p = a1 p*,
where a1 is the activity of solvent in the solution. See also, Section 4.14.
44 A Textbook of Physical Chemistry

Since x2 involves only the number of solute molecules relative to all the molecules
present and not on their individual nature, it is obvious that the relative lowering
of vapour pressure is a colligative property.
By definition,
p1* - p1
= x2 (Eq. 2.4.1)
p1*
where x2, the amount fraction of the solute, is given by
m2 /M 2
x2 = (2.4.2)
(m1 /M1 ) + (m2 /M 2 )

where m2 is the mass of solute (molar mass M2) that is dissolved in the solvent
(molar mass M1) of mass m1. Substituting Eq. (2.4.2) in Eq. (2.4.1), we get
p1* - p1 m2 /M 2
= (2.4.3)
p1* (m1 /M1 ) + (m2 /M 2 )

Equation (2.4.3) can be employed to determine the molar mass of a solute if

all other quantities are known. However, a simplified expression can be used if
the solution is dilute. In this case since m2/M2 << m1/M1, we have
p1* - p1 m2 /M 2
p1* m1 /M1

Êm ˆ Ê p1* ˆ
M 2 = Á 2 M1 ˜ Á
¯ Ë p* - p ˜¯
i.e. (2.4.4)
Ë m1
1 1

Example 2.4.2 Ten grams of a solute was dissolved in 80 g of acetone at 303 K. The vapour pressure
of the solution was found to be 271 Torr. Calculate the molar mass of the solute. Given:
Vapour pressure of pure acetone at 303 K is 283 Torr.
Solution The given data are
m1 = 10 g, m2 = 80 g, p1 = 271 Torr, p1* = 283 Torr,
–1
M1 = 58 g mol , M2 = ?
Substituting the data in the expression
p1* - p1 m2 /M 2
=
p1* (m1 / M 1 ) + ( m2 /M 2 )

283 Torr - 271 Torr (10 g/M 2 )

we get =
283 Torr (80 g/58 g mol -1 ) + (10 g/M 2 )
(10 g/M 2 )
0.042 4 =
(1.379 mol) + (10 g/M 2 )

(10 g) (1 - 0.042 4)
This gives M 2 = = 163.8 g mol -1
(0.042 4) (1.379 mol)
 Colligative Properties 45

Example 2.4.3 When 2 g of a nonvolatile hydrocarbon containing 94.4 per cent carbon is dissolved in
100 g benzene, the vapour pressure of benzene at 20 °C is lowered from 0.099 54 bar
to 0.098 67 bar. Calculate the molecular formula of the hydrocarbon.

Solution The given data are

m1 = 100 g, m2 = 2 g, p1* = 0.099 54 bar, p1 = 0.098 67 bar
–1
M1 = 78 mool , M2 = ?
Substituting the given data in the expression
p1* - p1 (m2 /M 2 )
= x2 =
*
p1 ( m1 / M 1 ) + ( m2 /M 2 )

0.099 54 bar - 0.098 67 bar (2 g/M 2 )

we get =
0.099 54 bar (100 g/78 g mol -1 ) + (2 g/M 2 )

(2 g/M 2 )
0.008 740 =
(1.282 mol) + (2 g/M 2 )

(2 g) (1 - 0.008 740)
This gives M 2 = = 176.9 g mol -1
(0.008 740) (1.282 mol)
Given mass ratio is mC : mH :: 94.4 : 5.6
Thus, atomic ratio is
94.4 5.6
N C : N H :: : fi 7.87 : 5.6 fi 1.4 : 1 fi 7 : 5
12 1
Hence, Empirical formula : C7H5
Empirical molar mass : (12 × 7 + 5 × 1) g mol–1 = 89 g mol–1
Number of units of C7H5 present in the given molecule
Molar mass 176.9 g mol -1
n= = 2
Empirical molar mass 89 g mol -1

Thus, Molecular formula: C14H10

The substance is anthracene.

2.5 CHEMICAL POTENTIALS OF SOLUTE AND SOLVENT IN AN IDEAL LIQUID SOLUTION

For the equilibrium

Solvent molecules in solution Solvent molecules in vapour

the thermodynamic condition of equilibrium is
*
m1(sol) = m1(v) (2.5.1)
If the vapour is assumed to be an ideal gas, the chemical potential of
vapour in terms of its pressure is given by
m1*( v ) = m1∞( v ) + RT ln ( p/p∞) (2.5.2)
46 A Textbook of Physical Chemistry

where μ 1(v)
º is the standard chemical potential of the solvent vapour and p is
the vapour pressure of the solution. Substituting Eq. (2.5.2) in Eq. (2.5.1), we
have
∞ + RT ln (p/p∞)
m1(sol) = m1(v) (2.5.3)

Using Raoult’s law ( p = x1p1*), we get

m1(sol ) = m1∞( v ) + RT ln ( x1 p1* /p∞)

= m1∞( v ) + RT ln ( p1* /p∞) + RT ln x1 (2.5.4)

If in the above expression x1 = 1 (i.e. pure liquid solvent), we will have
m1*(1) = m1∞( v ) + RT ln ( p1* /p∞) (2.5.5)

With this, Eq. (2.5.4) becomes

m1(sol) = m1*(1) + RT ln x1 (2.5.6)

The form of Eq. (2.5.6) is exactly the same as that of an ideal gas in a mixture
of gases.
The expression of chemical potential for the solute in a binary ideal solution
can be obtained by making use of the Gibbs-Duhem equation:
n1 dm1(sol) + n2 dm2(sol) = 0 (constant T and p) (2.5.7)

Rearranging Eq. (2.5.7), we get

Ên ˆ
dm2(sol) = - Á 1 ˜ dm1(sol) (2.5.8)
Ë n2 ¯
Since n1/n2 = x1/x2, we have
Êx ˆ
dm2(sol) = - Á 1 ˜ dm1(sol) (2.5.9)
Ë x2 ¯
For the solvent, we have
m1(sol) = m1*(1) + RT ln x1 (Eq. 2.5.6)

Therefore, at constant T and p, we have

RT
dm1(sol) = dx1 (2.5.10)
x1
Substituting this relation in Eq. (2.5.9), we have

Ê x ˆ Ê RT ˆ
dm2(sol) = - Á 1 ˜ Á dx
Ë x2 ¯ Ë x1 ˜¯ 1
dx1
= - RT (2.5.11)
x2
 Colligative Properties 47

Now, since x1 + x2 = 1, therefore

dx1 + dx2 = 0 or dx1 = - dx2
With this, Eq. (2.5.11) becomes
dx2
dm2(sol) = RT (2.5.12)
x2
Equation (2.5.12) is similar in form as Eq. (2.5.10). Integrating Eq. (2.5.12), we
have
m2(sol) = RT ln x2 + I (2.5.13)
where I is the constant of integration. For pure liquid solute x2 = 1. Thus I = μ*2(1)
and Eq. (2.5.13) becomes

m2(sol) = m*2(1) + RT ln x2 (2.5.14)

a form similar to that of the solvent.

Thus, we conclude that the expression
mi (sol) = mi*(1) + RT ln xi (2.5.15)

is applicable to both the constituents of an ideal solution. Since x1 or x2 is less

than one, it is obvious that
mi (sol) < mi*(1) (2.5.16)

2.6 ORIGIN OF COLLIGATIVE PROPERTIES

The depression of freezing point and the elevation of boiling point when a
nonvolatile solute is dissolved in a volatile solvent can be explained qualitatively
by plotting μ versus T curves. For a pure substance in solid, liquid and vapour
phases, the variations of μ* with T are shown by solid lines in Fig. 2.6.1. The
point of intersection of the μs* line with the μ 1* line and that of the μ 1* line
with the μ v* line represent, respectively, the freezing point and the boiling point
of the solvent.
Consider now a solution formed by the dissolution of a nonvolatile solute
in the above solvent. At the freezing point, we have the separation of the solid
solvent from the solution and thus an equilibrium of the type
Solvent in solution Solid solvent
exists at the freezing point of the solution. Similarly at the boiling point of the
solution, the equilibrium of the type
Solvent in solution Vapour solvent
exists. Since the solute is nonvolatile, the vapour will not contain any solute
molecules.
48 A Textbook of Physical Chemistry

Fig. 2.6.1 The elevation

of boiling point and the
depression of freezing
point on the basis of μ
versus T curves

Since the solid which separates at the freezing point of the solution and the
vapour which appears at the boiling point are of pure solvent, the variations of
chemical potentials for these two phases with temperature remain unaltered and
thus are represented by the same solid and vapour lines in Fig. 2.6.1. However,
the chemical potential of the liquid solvent will be decreased by an amount
RT ln xl (Eq. 2.5.6). This decrease is shown by the broken line in Fig.2.6.1. This
line intersects μ *solid and μ *vapour curves at points Tf and Tb and are, therefore,
the respective freezing and boiling points of the solutions. It can be seen from
Fig. 2.6.1 that:
The boiling point of the solution is higher than that of the solvent (Tb >
T b*) and thus there occurs an elevation of the boiling point.
The freezing point of the solution is smaller than that of the solvent
(Tf < Tf*) and thus there occurs a depression of the freezing point.
The depression of freezing point for a solution of a given concentration is
greater in magnitude than the corresponding elevation of the boiling point.
The elevation of boiling point and the depression of freezing point can also be
illustrated on the phase diagram. Let the solvent chosen be water. Its phase
diagram is represented by the solid lines in Fig. 2.6.2.
Now if a nonvolatile solute is added to it, the vapour pressure is lowered
at every temperature. The new liquid-vapour equilibrium curve will lie below
the corresponding liquid-vapour curve of the pure solvent. The new solid-liquid
equilibrium curve can be drawn from the point where the new liquid-vapour
curve meets the solid-vapour curve of the pure solvent. The freezing point and
the boiling point can be obtained from the intersections of a line drawn
horizontally from the given external pressure to the solid-liquid and liquid-
vapour curves, respectively. From Fig. 2.6.2, it is obvious that the boiling point
is elevated, whereas the freezing point is depressed on adding a nonvolatile
solute in a volatile solvent.
 Colligative Properties 49

Fig. 2.6.2 The elevation

of the boiling point and
the depression of freezing
point on the basis of
phase diagram

The third colligative property, the osmotic pressure, arises because of the
equilibrium between the solvent in solution and the pure liquid solvent. Let the
given solution be separated from the pure solvent by a semipermeable membrane
(Fig. 2.6.3) which allows only the flow of solvent molecules from one side to
the other. Since
*
m1(sol) < m1(l)
therefore, the situation shown in Fig. 2.6.3 will not be at equilibrium. The solvent
will flow from the region of high chemical potential (pure solvent) to the region
of low chemical potential (solution). This can, however, be stopped either by
raising the chemical potential of the solvent in the solution by increasing the
external pressure on the solution or by lowering the chemical potential of the pure
solvent by decreasing the external pressure on the pure solvent till the chemical
potential of the solvent becomes the same on both sides of the membrane. This
excessive pressure on the solution side or the lowering of external pressure on the
solvent side which is just sufficient to equate the chemical potential of solvent
on both sides is known as the osmotic pressure of the solution.

Fig. 2.6.3 Osmotic

pressure of the solution
50 A Textbook of Physical Chemistry

2.7 ELEVATION OF BOILING POINT

A liquid starts boiling when its vapour pressure becomes equal to the external
pressure. The temperature at which this occurs is known as the boiling point
of the liquid. If the external pressure is 1 atm, this temperature is known as
the normal boiling point of the liquid. When a nonvolatile solute is added to a
liquid solvent, the boiling point of the resultant solution is increased.
The vapour pressure of the solution is comparatively smaller than that of the pure
solvent (Raoult’s law). Consequently, the temperature at which the vapour pressure
of solution becomes equal to the external pressure, will be greater than that of
pure solvent, thus raising its boiling point. Since the decrease in vapour pressure
is directly proportional to the amount fraction of the solute in the solution, it
is, therefore, expected that the corresponding increase in the boiling point also
depends on the amount fraction of the solute in the solution.
The quantitative relation between the elevation of boiling point and the
concentration of the solution can be derived thermodynamically. Consider a
solution which is in equilibrium with the vapour of the pure solvent. Basically,
we have the following equilibrium at the boiling point of the solution.
Solvent in solution Vapour of pure solvent
The thermodynamic condition of equilibrium is
* (Tb , p)
m1(sol) (Tb , p) = m1(v) (2.7.1)
where Tb is the boiling point of the solution. At constant pressure, this temperature
is a function of x1, the amount fraction of the solvent in solution. For an ideal
solution, we have
* + RTb ln x1
m1(sol) = m1(1) (Eq. 2.5.6)

Substituting the above relation in Eq. (2.7.1) and rearranging, we have

* - m1(1)
m1(v) *
ln x1 = (2.7.2)
RTb

D vap m1*
or ln x1 = (2.7.3)
RTb
where D vap m1* = m1(
* v ) - m1(1)
* and is the molar free energy of evaporation of the
pure solvent at temperature Tb and pressure p. Equation (2.7.3) is the required
relation between the composition of the solution and the boiling point.
As stated above Tb = f (x1). The actual relation between Tb and x1 can be determined
by differentiating Eq. (2.7.3) with respect to x1 at constant p, such that

1 1 ÏÔ ∂( D vap m1* /Tb ) ¸Ô Ê ∂Tb ˆ

= Ì ˝ Á ˜
x1 RÔ
Ó
∂Tb Ô˛ p Ë ∂x1 ¯ p
 Colligative Properties 51

Using the Gibbs-Helmholtz equation

{ ∂( Dm/T )
∂T } p
=-
DH m
T2

1 D vap H1, m Ê ∂Tb ˆ

we get =- Á ˜ (2.7.4)
x1 RTb2 Ë ∂x1 ¯ p

dx1 D vap H1, m

or =- dTb ( p constant) (2.7.5)
x1 RTb2

where vapH1, m is the molar enthalpy of vaporization of the pure solvent at

temperature Tb.
The relation between boiling point (Tb) and amount fraction of solvent
(x1) can be obtained by integrating Eq. (2.7.5). Thus, we have
x1 dx1 Tb D vap H1, m dTb
Ú1 x1
=-Ú *
Tb R Tb2
(2.7.6)

where Tb and T *b are the boiling points of solution and pure solvent, respectively.
If vapH1, m is assumed to be independent of over the temperature range Tb and
T *b, Eq. (2.7.6) on integrating gives

D vap H1,m Ê 1 1 ˆ
ln x1 = – Á– + ˜ (2.7.7)
R Ë Tb T *b ¯

1 1 R ln x1
i.e. = + (2.7.8)
Tb Tb* D vap H1,m

Equation (2.7.8) can be used to compute the boiling point of a solution in which
the amount fraction of solvent is x1, T *b and vapH1, m are the boiling point and
the molar enthalpy of vaporization of the pure solvent, respectively.
By definition, we have

n1 m1 /M1 1 1
x1 = = = =
n1 + n2 (m1 /M1 ) + n2 1 + (n2 /m1 ) M1 1 + mM1
where m is the molality of the solution.

Ê 1 ˆ
Hence, ln x1 = ln Á = - ln (1 + mM1 )
Ë 1 + mM1 ˜¯
Differentiating this expression, we get
dx1 1
=- M dm
x1 1 + mM1 1
52 A Textbook of Physical Chemistry

Substituting this in Eq. (2.7.5), we get

1 D vap H1, m
– M 1 dm = – dTb
1 + mM1 RTb2

Ê RTb2 ˆ Ê M1 ˆ
or dTb = Á ˜Á ˜ dm (2.7.9)
Ë D vap H1, m ¯ Ë 1 + mM1 ¯

For a dilute solution, as m 0, Tb T *b. Thus, the limiting value of the derivative
Tb / m at zero molality is

Ê ∂Tb ˆ RM1T *b 2
ÁË ˜ = (2.7.10)
∂m ¯ m Æ 0 D vap H1,m

From Eq. (2.7.10), it follows that the limiting value of ( Tb / m) depends only
on the characteristics of the solvent. The derivative ( Tb/ m)m 0 is known as
the boiling point elevation constant or the ebullioscopic constant and is
represented by the symbol Kb.
Equation (2.7.9) may be written as
dTb = Kb dm ( p constant, very dilute solution) (2.7.11)
For a finite value of dm, we have
Tb = Kb m (2.7.12)†
Kb The unit of Kb may be worked out as follows.

unit of DTb K
unit of K b = = = K kg mol -1
unit of m mol kg -1

Kb The numerical value of Kb for a given solvent can be determined from its T *b and
vap Hm values. For example, for water we have

M1 RT *b 2 (18 ¥ 10 –3 kg mol –1 ) (8.314 J K –1 mol -1 ) (373 K)2

Kb = =
D vap H m (40 658 J mol –1 )
= 0.51 K kg mol –1

Kb The values of Kb for other commonly used solvents are given in Table 2.7.1.

†
Equation (2.7.12) may be derived directly from Eq. (2.7.8) by invoking the following
approximations.
ln x1 = – ln (1 + mM1) – mM1
Tb T *b T *b 2
 Colligative Properties 53

Table 2.7.1 Boiling-Point Elevation Constants

Solvent Molar mass

g mol–1 b.pt ./ºC Kb /(K kg mol–1)
Water 18.0 100 0.51
Methyl alcohol 32.0 64.7 0.86
Ethyl alcohol 46.1 78.5 1.23
Acetone 58.1 56.1 1.71
Benzene 78.1 80.2 2.53
Cyclohexane 84.2 81.3 2.79
Chloroform 119.5 61.3 3.63
Carbon tetrachloride 154.0 76.8 5.03

Problem 2.7.1 The expression Tb = Kbm for the boiling point elevation can also be obtained by applying
the Clausius-Clapeyron equation to the solution-vapour equilibrium curves. Derive the
relation by drawing the necessary diagram.

Solution The variations in vapour pressure of the solvent and that of the solution with temperature
are given by the respective solvent-vapour and solution-vapour curves of the phase diagram
(Fig. 2.7.1).

Fig. 2.7.1 Clausisus-

Clapeyron equation as
applied to the solution-
vapour curve

For a given value of the external pressure pext, the pure solvent will boil at temperature
T *b and the solution at temperature Tb. Let pext be equal to p*, the vapour pressure of
pure solvent. Let p be the vapour pressure of the solution at temperature T *b.
Applying the Clausius-Clapeyron equation to the solution-vapour equilibrium for two
values of p, T *b and p*, Tb, we have

p* D vap H1,m Ê 1 1ˆ D vap H1,m DTb

ln = Á – ˜ = (2.7.13)
p R *
Ë T b Tb ¯ R T *b Tb

where Tb = Tb – T *b, the elevation of boiling point. For a dilute solution, Eq. (2.7.13)
may be simplified under the following approximations.
54 A Textbook of Physical Chemistry

(1) Tb will be very near to T *b , so that the term TbT * *

b can be replaced by T b , i.e.
2

T*
b Tb T*
b
2
(2.7.14)
(2) The term ln p*/p can be written as
p* p Ê p* - p* + p ˆ Ê p* - p ˆ
ln = - ln = - ln Á ˜¯ = - ln ÁË 1 - ˜
p p* Ë p* p* ¯

The term ( p* – p)/p*, the relative lowering of vapour pressure, is very small in comparison
to 1, thus the term – ln (1 – (p* – p)/p*) can be approximated to
Ê p* - p ˆ Ê p* - p ˆ p* - p
- ln Á 1 - ˜ - Á- ˜ = p
Ë p* ¯ Ë p* ¯ *
p* p* - p
Hence ln =
p p*
(3) According to Raoult’s law, we have

p* - p n2
= x2 =
p* n1 + n2
For a dilute solution n2 << n1, and, therefore, n2 can be neglected in comparison to
n1. Thus, we have
p* p* - p n2 n2
ln = (2.7.15)
p p* n1 m1/M1
Substituting Eqs (2.7.14) and (2.7.15) in Eq. (2.7.13), we get
n2 D vap H1, m DTb
=
T*
2
m1/M1 R b

Rearranging this, we get

Ê M RT *2 ˆ Ê n ˆ
1 b 2
DTb = Á ˜ = Kb m
ÁË D vap H1, m ˜¯ ÁË m1 ˜¯

Problem 2.7.2 According to Raoult’s law p1 = x1p*1 or ln ( p1/pº) = ln xl + ln ( p*/p°).

1
If p1 = pext
= constant, then

d ln ( p1/p∞) d ln x1 d ln ( p1* /p∞)

=0= +
dTb dTb dTb
Now if the Clapeyron equation

d ln ( p1/p∞) D vap H m
=
dT RT 2
is introduced in the previous expression, show that it leads to the expression Tb = Kb m
for a dilute solution.

d ln ( p1* /p∞) D vap H1,m

Solution Substituting the Clapeyron equation = in the expression
dT *b RT *
b
2
 Colligative Properties 55

d ln x1 d ln (p1* /p1∞ )
=- ,
dT *
b dT *
b

d ln x1 D vap H1, m d ln (1 - x2 ) D vap H1, m

we get =- or =-
dT *
b RT *
b
2
dT *
b RT *
b
2

Integrating within the limits, we get

x2 Tb D vap H1, m dT *
Ú0 d ln (1 – x2 ) = – Ú
Tb* R T*
b
2
b

D vap H1, m Ê 1 1 ˆ
i.e. ln (1 - x2 ) = - Á- + ˜
R Ë Tb T*b¯

For a dilute solution, we will have

n2 n2 n
ln (1 - x2 ) - x2 = - - = - 2 M1 = - mM1
n1 + n2 n1 m1

T *b
2
Tb T *b so that TbT *
b

With these, the previous expression becomes

D vap H1, m DTb
- mM1 = –
T*
2
R b

Ê M RT *2 ˆ
or DTb = Á 1 b ˜ m = K b m
ÁË D vap H1, m ˜¯

Example 2.7.1 A solution containing 0.512 6 g of naphthalene (molar mass 128.2 g mol–1) in 50 g
CCl4, yields a boiling point elevation of 0.402 K, while a solution of 0.621 6 g of an
unknown solute in the same mass of the solvent gives a boiling point elevation of 0.647
K. Find Kb of the solvent the molar mass of the unknown solute.
Solution Mass of dissolved naphthalene = 0.512 6 g
Mass of solvent = 50 g
n2 m /M (0.512 6 g/128.2 g mol -1 )
Molality of the solution, m = = 2 2 =
m1 m1 (0.050 kg)
= 0.079 97 mol kg -1
From the relation, Tb = Kbm, we get
DTb 0.402 K
Kb = = = 5.027 K kg mol -1
m 0.079 97 mol kg -1

Let M2 be the molar mass of the unknown substance. The molality of solution containing
unknown compound is

m2 /M 2 (0.621 6 g)/M 2 12.432

m= = = g kg –1
m1 0.050 kg M2
56 A Textbook of Physical Chemistry

Substituting the above molality along with Tb = 0.647 K in the relation Tb = Kbm,
we get
Ê 12.432 ˆ
0.647 K = (5.027 K mol –1 kg) Á g kg –1 ˜
Ë M2 ¯
5.027 ¥ 12.432
or M2 = g mol –1 = 96.59 g mol –1
0.647

Example 2.7.2 A complex compound of unknown molar mass is known to dissolve in benzene without
association or dissociation. A solution of this compound in benzene has a vapour pressure
of 100 Torr at 300.15 K. Pure benzene boils at 353.15 K at 760 Torr pressure; its entropy
of vaporization is 87.03 J K–1 mol–1. What would be the amount fraction of the complex
compound in this solution and the boiling point of the solution?
Solution Vapour Pressure of the Pure Solvent at 300.15 K The given data are

p2 = 760 Torr T2 = 353.15 K

p1 = ? T1 = 300.15 K
The Clausius-Clapeyron equation is
p2 D vap H m Ê 1 1 ˆ Ê D vap H m ˆ Ê DTb ˆ
ln = Á - ˜ =Á
p1 R Ë T1 T2 ¯ Ë R ˜¯ ÁË T1T2 ˜¯
But vapHm = T2 vapSm, therefore

p2 Ê D vap Sm ˆ Ê DTb ˆ
log =Á
p1 Ë 2.303 R ˜¯ ÁË T1 ˜¯

Substituting the given data, we get

Ê 760 Torr ˆ È (87.03 J K –1 mol –1 ) ˘ È (53 K) ˘

log Á ˜ = Í –1 ˙ Í
Ë p1 ¯ Î (2.303) (8.314 J K mol ) ˚ Î (300.15 K) ˙˚
–1

= 0.802 6
760 Torr 760 Torr
or = 6.35 or p1 = = 119.7 Torr
p1 6.35
Amount Fraction of the Solute According to the relative lowering of vapour pressure,
we get
p* - p 119.7 Torr - 100 Torr
x2 = = = 0.164 6
p* 119.7 Torr
Boiling Point of the Solution Substituting the data in the expression
1 1 R ln x1 1 1 R ln (1 - x2 )
= + i.e. = +
Tb T *b D vap H1, m Tb T *b T *b D vap S1, m

1 1 (8.314 J K -1 mol -1 ) ln (1 - 0.164 6)

we get = +
Tb 353 15 K (353.15 K) (87.03 J K -1 mol -1 )
= 0.002 832 K -1 - 0.000 048 6 K -1 = 0.002 783 K -1
Tb = 359.3 K
 Colligative Properties 57

Example 2.7.3 For a solution of 3.795 g sulphur in 100 g CS2 the boiling point was 319.81 K. For
pure CS2, the boiling point is 319.45 K and the enthalpy of vaporization is 351.87 J g–1.
What is the molar mass and formula of sulphur in CS2?
Solution The given data are
m2 = 3.795 g m1 = 100 g M CS2 = 76 g mol –1
Tb = 319.81 K T *b = 319.45 K
D vap H1,m = 351.87 ¥ 76 J mol –1

Determination of Kb(CS2)

M1RT *b
2
(76 ¥ 10 –3 kg mol –1 ) (8.314 J K –1 mol –1 )(319.45 K)2
Kb = =
D vap H1, m (351.87 ¥ 76 J mol –1 )
= 2.41 K kg mol –1
Molality of the given solution

DTb Tb – T * (319.81 K - 319.45 K)

m= = b
= = 0.149 mol kg –1
Kb Kb (2.41 K kg mol –1 )

Molar mass of solute Since m = (m2/M2)/m1, we get

m2 (3.795 g)
M2 = = = 0.255 kg mol -1
mm1 (0.149 mol kg -1 ) (100 g)
= 255 g mol -1
(255 g mol -1 )
Number or sulphur atoms in 1 molecule of sulphur = 8
(32 g mol -1 )
Hence, Molecular formula = S8

2.8 DEPRESSION OF FREEZING POINT

We have seen in Section 2.6 that when a nonvolatile solute is dissolved in a

volatile solvent, the freezing point of the resultant solution is lowered relative to
that of the pure solvent. The quantitative relation between the depression of
freezing point and the concentration of the solution can be derived
thermodynamically following the sequence of steps adopted in the derivation
of expression for the elevation of boiling point.
Basically, at the freezing point of the solution, we have the equilibrium
Solvent in solution Solid solvent
The condition of equilibrium is
* (Tf , p)
m1(sol) (Tf , p) = m1(s) (2.8.1)
where Tf is the freezing point of the solution. At a constant pressure, this
temperature will be a function of x1, the amount fraction of the solvent in
solution. If the solution is ideal, then
58 A Textbook of Physical Chemistry

m1(sol ) = m1*(1) + RTf ln x1

Substituting the above relation in Eq. (2.8.1) and rearranging, we have

* - m1(s)
m1(1) *
ln x1 = – (2.8.2)
RTf
D fus m1*
or ln x1 = - (2.8.3)
RTf

where fus μ1* is the molar free energy of fusion of the pure solvent at temperature
Tf and pressure p.
In order to derive the relation governing the freezing point of a solution with its
composition, we differentiate Eq. (2.8.3) with respect to x1 at constant pressure,
such that

1 1 ÏÔ ∂( D fus m1* /Tf ) ¸Ô Ê ∂Tf ˆ

=- Ì ˝ Á ˜
x1 R ÓÔ ∂Tf ˛Ô p Ë ∂x1 ¯ p

Using the Gibbs-Helmholtz equation

{ ∂( Dm/T )
∂T } p
=-
DH m
T2

1 D fus H1, m Ê ∂Tf ˆ

we get = Á ˜ (2.8.4)
x1 RTf2 Ë ∂x1 ¯ p

dx1 D fus H1, m

or = dTf ( p constant) (2.8.5)
x1 RTf2
where fusH1,m is the molar enthalpy of fusion of the pure solvent at temperature
Tf .
The relation between freezing point (Tf) and amount fraction of solvent (x1)
can be obtained by integrating Eq. (2.8.5). Thus, we have
x1 dx1 Tf D fus H1, m dTf
Ú1 x1
= ÚT f
*
R Tf2
(2.8.6)

where Tf and Tf* are the freezing points of solution and pure solvent, respectively.
If fusH1,m is assumed to be independent over the temperature range Tf and Tf*,
Eq. (2.8.6) on integrating gives
D fus H1, m Ê 1 1 ˆ
ln x1 = Á - + ˜ (2.8.7)
R Ë Tf Tf* ¯

1 1 R ln x1
i.e. = - (2.8.8)
Tf Tf* D fus H1, m
 Colligative Properties 59

Equation (2.8.8) can be used to compute the freezing point of a solution in

which the amount fraction of solvent is x1; Tf* and fusH1,m are the freezing
point and the molar enthalpy of fusion of the pure solvent, respectively.
By definition, we have
n1 m1 /M1 1 1
x1 = = = =
n1 + n2 (m1 /M1 ) + n2 1 + (n2 /m1 ) M1 1 + mM1

where m is the molality of the solution.

Ê 1 ˆ
Hence, ln x1 = ln Á = - ln (1 + mM1 )
Ë 1 + mM1 ˜¯

Differentiating this expression, we get

dx1 1
=- M dm
x1 1 + mM1 1
Substituting this in Eq. (2.8.5), we get
1 D fus H1,m
- M 1 dm = dTf
1 + mM1 RTf2

Ê RTf2 ˆ Ê M1 ˆ
or dTf = - Á Á ˜ dm (2.8.9)
Ë D fus H1, m ˜¯ Ë 1 + mM1 ¯

For a dilute solution, as m 0, Tf Tf*. Thus, the limiting value of the derivative
Tf / m at zero molality is

Ê ∂Tf ˆ RM1Tf*2
ÁË ˜¯ = (2.8.10)
∂m m Æ 0 D fus H1, m

From Eq. (2.8.10), it follows that the limiting value of ( Tf / m) depends only
on the characteristics of the solvent. The derivative ( Tf / m)m 0 is known as
the freezing point depression constant or the cryscopic constant of the solvent
and is represented by the symbol Kf.
Equation (2.8.9) may be written as
– dTf = Kf dm ( p constant, very dilute solution) (2.8.11)
For a finite value of dm, we have
– Tf = Kf m (2.8.12)†

†
Equation (2.8.12) may be derived directly from Eq. (2.8.8) by invoking the following
approximations.
ln x1 = – ln (1 + mM1) = – mM1
TfTf* Tf*2
60 A Textbook of Physical Chemistry

K The unit of Kf may be worked out as follows.

unit of DTf K
unit of Kf = = = K kg mol -1
unit of m mol kg -1
K The numerical value of Kf for a given solvent can be determined from its Tf* and
fusH1, m values. For example, for water, we have

M1 RTf* (18 ¥ 10 -3 kg mol –1 ) (8.314 J K –1 mol –1 ) (273 K)2

2

Kf = =
D fus H1, m (6 009.5 J mol –1 )
= 1.86 K kg mol –1

K The values of Kf for other commonly used solvents are given in Table 2.8.1.

Table 2.8.1 Freezing Point Depression Constants

Molar mass Kf
Solvent m. pt./ º C
g mol -1 K kg mol -1
Water 18.0 0 1.86
Acetic acid 60.0 16.6 3.57
Benzene 78.1 5.45 5.07
Cyclohexane 84.2 6.5 20.0
Dioxane 88.1 11.7 4.71
Naphthalene 128.3 80.1 6.98
Camphor 152.2 178.4 37.7

Problem 2.8.1 The expression – Tf = Kf m for the freezing point depression can also be obtained from
the shift in triple point of a solvent on forming a solution† of the substance and by
applying the Clausius-Clapeyron equation to the solid-vapour and the solution-vapour
equilibria. Derive the relation by drawing the necessary diagram.

Solution The solution-vapour curve will lie below that of the solvent-vapour curve and thus it
intersects the solid-vapour curve at a temperature (triple temperature) smaller than the
corresponding intersection temperature for the solvent-vapour curve. This is shown in
Fig. 2.8.1. There occurs a depression in the triple point of the substance when a nonvolatile
solute is dissolved in it.
Applying the Clausius-Clapeyron equation to the solution-vapour equilibrium for the
two values of p2, T and p1, Tf*, we have

p1 D vap H1, m Ê 1 1 ˆ D vap H1, m ( - DTf )

ln = Á - *˜ = (2.8.13)
p2 R Ë T Tf ¯ R T T f*

where DTf = T - T f*

†
The effect of pressure on the equilibrium temperature of solid to liquid equilibrium is
usually very small and thus the triple point may be taken as the freezing point. Take,
for example, the triple point of water system, it lies at 0.007 5 °C and 4.6 mmHg. The
normal freezing point of water is 0 °C (at 1 atm).
 Colligative Properties 61

Fig. 2.8.1 Clausius-

Clapeyron equation as
applied to the depression
of triple point

Applying now the Clausius-Clapeyron equation to the solid-vapour equilibrium for

the two values of p2, T and p*, Tf*, we have

p * D sub H1, m Ê 1 1 ˆ D sub H1, m Ê - DTf ˆ

ln = Á - *˜ = Á ˜ (2.8.14)
p2 R Ë T Tf ¯ R Ë TT *
f ¯

Subtracting Eq. (2.8.13) from Eq. (2.8.14), we get

p* p D H Ê - DT ˆ D vap H1, m Ê - DT ˆ
ln - ln 1 = sub 1, m Á f
˜- Á
f
˜
p2 p2 R Ë TT* ¯ f
R Ë TT* ¯ f

p* - DTf - DTf
or ln = ( D sub H1,m - D vap H1,m ) = ( D fus H1,m ) (2.8.15)
p1 TT*fR TT*fR

Equation (2.8.15) can be simplified under the following approximations.

(i) T will be very near Tf*, so that the term T Tf* may be replaced by Tf*2, i.e.

TT *
f T*
f
2
(2.8.16)
(ii) The term ln p*/p1 can be written as

p* p Ê p* - p* + p1 ˆ Ê p* - p1 ˆ
ln = - ln 1 = - ln Á ˜¯ = - ln ÁË 1 - ˜
p1 p* Ë p* p* ¯

Since the term ( p* – p1)/p*, the relative lowering of vapour pressure at temperature Tf*, is
very small in comparison to 1, the term – ln (1 – (p* – p1)/p*) can be approximated as

Ê p* - p1 ˆ Ê p* - p1 ˆ p* - p1
- ln Á 1 - ˜ = - ËÁ - ˜ =
Ë p* ¯ p* ¯ p*
62 A Textbook of Physical Chemistry

(iii) According to Raoult’s law

p * - p1 n2
= x2 =
p* n1 + n2

For a dilute solution n2 << n1, and therefore n2 can be neglected in comparison to n1.
Thus, we have

p* p * - p1 n2 m /M
ln = 2 2 (2.8.17)
p1 p* n1 m1/M1

Substituting Eqs (2.8.16) and (2.8.17) in Eq. (2.8.15), we get

m2 /M 2 D H ( - DTf )
= fus 1,m
m1/M1 R Tf*2

Rearranging this, we get

M1RT * 2
Ê m2 /M 2 ˆ
( - DTf ) = f
= Kf m (2.8.18)
D fus H1, m ÁË m1 ˜¯

Example 2.8.1 A sample of camphor used in the Rast method for the determination molar mass had
melting point of 451.55 K. The melting point of a solution containing 0.522 g camphor
and 0.038 6 g of an unknown compound was 433.85 K. If the unknown compound was a
hydrocarbon containing 7.7% H, find its molecular formula. The molar mass of camphor
is 152.2 g mol–1 and its fusH1,m = 6.844 kJ mol–1.

Solution The given data are

m1 = 0.522 g, m2 = 0.038 6 g, Tf = 433.85 K, T*

f = 451.55 K,
-1 -1
M1 = 152.2 g mol , D fus H1,m = 6.844 kJ mol

Calculation of Kf

M1 R T *f
2
(152.2 ¥ 10 –3 kg mol –1 ) (8.314 J K –1 mol –1 )(451.55 K)2
Kf = =
D fus H1, m (6.844 ¥ 103 J mol –1 )
= 37.7 K kg mol –1

Calculation of molality of solution

- DTf - (Tf - T *
f ) - (433.85 K - 451.55 K)
m= = = = 0.47 mol kg -1
Kf Kf (37.7 K kg mol -1 )

Calculation of molar mass of solute Since m = (m2/M2)/m1, we get

m2 (0.038 6 g)
M2 = = = 0.157 kg mol –1
mm1 (0.47 mol kg –1 )(0.522 g)
 Colligative Properties 63

Determination of molecular formula

The given mass ratio is mC : mH :: 92.3 : 7.7
92.3 7.7
The atomic ratio is NC : NH :: : 7.7 : 7.7 1:1
12 1
Hence, Empirical formula : CH
Empirical molar mass = 13 g mol–1
molar mass 157 g
Number of units of CH = = 12
empirical molar mass 13 g

Hence, Molecular formula = C12H12

Example 2.8.2 A solution comprising 0.1 mol of naphthalene and 0.9 mol of benzene is cooled until
some solid benzene freezes out. The solution is then decanted off from the solid, and
warmed to 353 K, where its vapour pressure is found to be 670 Torr. The freezing and
normal boiling points of benzene are 278.5 K and 353 K, respectively, and its enthalpy
of fusion is 10.67 kJ mol–1. Calculate the temperature to which the solution was cooled
originally and the amount of benzene that must have frozen out. Assume conditions of
ideal solution.
Solution The given data are:
n1 = 0.9 mol, n2 = 0.1 mol, T*
f = 278.5 K, T*
b = 353 K,

p* = 760 Torr, p = 670 Torr, D fus H1,m = 10.67 kJ mol -1

From the relative lowering of vapour pressure, we obtain the amount fraction of the
solute (i.e. naphthalene).
p* - p 760 Torr - 670 Torr
x2 = = = 0.118 5
p* 760 Torr
Since x2 = n2/(n1 + n2), we get
n2 0.1 mol
n1 + n2 = = = 0.844 mol
x2 0.118 5

Since n2 = 0.1 mol, we get

n1 = 0.844 mol - n2 = 0.844 mol - 0.1 mol = 0.744 mol

Hence, the amount of benzene frozen out = 0.9 mol – 0.744 mol = 0.156 mol
The freezing point depression constant of benzene is
M1RTf* (0.078 kg mol -1 )(8.314 J K -1 mol -1 )(278.5 K)2
2
Kf = =
D fus H1, m (10 670 J mol -1 )
= 4.714 K kg mol -1
Molality of the solution is
n2 n2 (0.1 mol)
m= = = = 1.723 mol kg -1
m1 n1 M1 (0.744 mol)(0.078 kg mol -1 )
Finally – DTf = Kf m = (4.714 K kg mol –1 ) (1.723 mol kg –1 ) = 8.12 K
Tf = Tf* + DTf = 278.5 K - 8.12 K = 270.38 K
64 A Textbook of Physical Chemistry

2.9 OSMOSIS AND OSMOTIC PRESSURE

We have seen in Section 2.6 that a solution when separated from the pure solvent
with the help of a semipermeable membrane, the flow of solvent molecules
from the pure solvent side to the solution side takes place. This flow of solvent
molecules from a region of higher concentration (i.e. pure solvent) to the region
of lower concentration (i.e. solution) of solvent molecules is known as the
phenomenon of osmosis.
As a result of osmosis, level of the solution in the tube rises, whereas that of
the pure solvent falls (Fig. 2.9.1). After some time an equilibrium is reached
where the level of the solution in the tube does not rise further. At this stage,
the excessive hydrostatic pressure created on the solution side exactly balances
the tendency of the solvent to pass through the membrane as shown in
Fig. 2.9.1. This excessive hydrostatic pressure is known as the osmotic pressure
of the solution and is represented by the symbol Π.

Fig. 2.9.1 The

phenomenon of osmosis
and generation of
osmotic pressure

The phenomenon of osmosis can also be checked by increasing the external

pressure on the solution by an amount equivalent to the hydrostatic pressure Π
as shown in Fig. 2.9.2.†
Alternatively, this can also be checked by reducing the external pressure
on the solvent side by an amount equivalent to this hydrostatic pressure.
The osmotic pressure of a solution depends on its concentration—larger the
concentration larger the osmotic pressure. The expression relating the osmotic
pressure with concentration of the solution can be derived thermodynamically.
Initially, there exists a difference of chemical potential of the solvent on
either sides of the membrane and thus the solvent flows from the pure solvent
side to the solution side. This flow of solvent to the solution side generates an

†
lf the applied excessive pressure becomes larger than the osmotic pressure, the reverse of
osmosis is observed, i.e. solvent molecules will flow from the solution to the solvent side.
This is due to larger increase of chemical potential than the required value.
 Colligative Properties 65

Fig. 2.9.2 An alternative

way of stopping the
phenomenon of osmosis

excessive hydrostatic pressure on the solution side, which in turn increases the
chemical potential of the solvent in solution. Consequently, the difference of
chemical potential of solvent on either sides is decreased. After some time,
enough solvent has flown into the solution side so that the difference of chemical
potential is altogether eliminated and thus osmosis stops. At this stage, the system
is in equilibrium and no more solvent flows from the solvent to the solution.
Basically, in the present case we have equilibrium of the type
Solvent in solution Pure solvent
The thermodynamic condition of equilibrium is
* (T , p)
m1(sol) (T , p + P ) = m1(1) (2.9.1)

where Π is the excessive hydrostatic pressure. At constant temperature, Π is a

function of x1, the amount fraction of the solvent in solution. If the solution is
assumed to be ideal, we have
* (T , p + P ) + RT ln x
m1(sol) (T , p + P ) =m1(1) (2.9.2)
1

Substituting Eq. (2.9.2) in Eq. (2.9.1), we get

* (T , p + P ) + RT ln x = m * (T , p)
m1(1) 1 1(1)

or * (T , p + P ) - m* (T , p) = - RT ln x
m1(1) (2.9.3)
1(1) 1

The left side of Eq. (2.9.3) represents the difference in chemical potentials of
the pure solvent under the two different pressures p + Π and p. This difference
may be evaluated by employing the relation
Ê ∂m1(1)
* ˆ
*
Á ˜ = V1,m (2.9.4)
Ë ∂p ¯ T
where V 1,* m is the molar volume of the pure solvent. Rewriting Eq. (2.9.4), we
have
66 A Textbook of Physical Chemistry

* = V * dp
dm1(1) (T constant)
1,m

Integrating the above relation within the limits p and p + Π, we get

p+P p+P
Úp * =
dm1(1) Úp * dp
V1,m (T constant)

p +P
or * (T , p + P ) - m* (T , p) =
m1(1) 1(1) Úp * dp
V1,m

* is independent of pressure and can be

If the solvent is incompressible, V 1,m
removed from the integral. Thus, we have
* (T , p + P ) - m* (T , p) = V * P
m1(1) (2.9.5)
1(1) 1,m

Substituting Eq. (2.9.5) in Eq. (2.9.3), we get

* P = - RT ln x
V1,m (2.9.6)
1

For a dilute solution, Eq. (2.9.6) can be simplified under the following
approximations.
(i) Since the solution is dilute, x2 << 1, the term ln x1 can be approximated as
ln x1 = ln (1 - x2 ) - x2 (2.9.7)
(ii) The amount fraction of the solute is given as
n2 n2
x2 = (since n2 << n1) (2.9.8)
n1 + n2 n1
(iii) For a solution, the total volume V can be written in terms of the partial
molar volumes following the additivity rule
V = n1V1 + n2V2
where V1 is the partial molar volume of the solvent and V2 is the corresponding
volume of the solute. For a dilute solution, we assume that:
(a) Partial molar volume of the solvent in the solution is the same as that
of the pure solvent, i.e. V 1 = V *1,m.
(b) The factor n2V2 << n1Vl since n2 << n1 and can, therefore, be neglected.
Thus we have
V *
n1V1 = n1V1,m (2.9.9)

Substituting Eqs (2.9.7)-(2.9.9) in Eq. (2.9.6), we have

V
P = - RT ( - x2 ) = RTx2
n1
V n
or P = RT 2
n1 n1
 Colligative Properties 67

or V P = n2 RT

Ên ˆ
or P = Á 2 ˜ RT = cRT (2.9.10)
ËV ¯

where c is the molar concentration of solute in the solution. Equation (2.9.10)

is known as the van’t Hoff equation for osmotic pressure of the solution.
The form of van’t Hoff equation is exactly identical to that of the ideal gas
equation except that Π replaces the gas pressure p. This striking resemblance
suggests that the solute molecules are dispersed in the solvent the way the gas
molecules are dispersed in the empty space. Thus the solute is analogous to the
gas molecules and the solvent is analogous to the empty space between the gas
molecules.

Problem 2.9.1 (a) Show that the difference in chemical potential of the solvent on either side of
semipermeable membrane shown in Fig. 2.9.1 is given by
* (T , p*) - m1(sol) (T , p) = - RT ln x1
m1(1)
(b) The osmotic pressure of a solution may be defined as the excessive pressure which
needs to be applied on the solution side so as to prevent osmosis. Using this fact, derive
the relation
V1P = - RT ln x1
where V1 is the partial molar volume of solvent in solution.
(c) The osmotic pressure of a solution may be defined as the pressure which needs to
be lowered on the solvent side so as to prevent osmosis. Using this fact, show that
* P = - RT ln x1
V1,m

Solution (a) Let p* and p be the vapour pressures of pure solvent and solution, respectively. In
Fig. 2.9.1, we have the following two equilibria.
Solvent in solution Solvent vapour at pressure p
Pure solvent Solvent vapour at pressure p*
The thermodynamic relations for these two equilibria are:
∞ + RT ln ( p/ p∞)
* (T , p) = m1(v)
m1(sol) (T , p) = m1(v)

m1* (T , p*) = m1(v) ∞ + RT ln ( p */ p∞)

* (T , p*) = m1(v)
p*
Hence m1* (T , p*) - m1(sol) (T , p) = RT ln (p*/ p∞) - RT ln ( p/ p∞) = RT ln
p
For an ideal solution p = p*x1. With this, the above expression becomes

m1* (T , p*) - m1(sol) (T , p) = RT ln (1/x1 ) = - RT ln x1

(b) By applying the pressure Π on the solution side, the osmosis is prevented. At this
stage, we will have

m1* (T , p*) = m1(sol) (T , p + P )

68 A Textbook of Physical Chemistry

Substituting this expression in the expression derived in part (a), we get

m1(sol) (T , p + P ) - m1(sol) (T , p) = - RT ln x1 (1)

Ê ∂m1(sol) ˆ
Now = V1
ËÁ ∂p ¯˜ T

where V1 is the partial molar volume of solvent in the solution. Rewriting and integrating
within the limits p and p + Π, we get

p+P p+P
Úp dm1(sol) = Úp V1 dp

Assuming V1 to be independent of pressure, we get

m1(sol) (T , p + P ) - m1(sol) (T , p) = V1 (p + P - p)
= V1P
Hence Eq. (1) becomes

V1P = - RT ln x1
(c) By lowering the pressure on the solvent side by an amount Π, the phenomenon of
osmosis is prevented. At this stage, we will have
m1* (T , p * - P ) = m1(sol) (T , p)
Substituting this in the expression derived in part (a), we get

m1* (T , p*) - m1* (T , p * - P ) = - RT ln x1 (2)

Ê ∂m1* ˆ
Now Á *
˜ = V1,m
Ë ∂p ¯ T

or dm1* = V1,m
* dp; (T constant)

p* p*
Thus Ú p* - P dm1* = Ú p* - P V1,m
* dp; (T constant)

* to be independent of pressure, we have

Assuming V1,m

m1* (T , p*) - m1* (T , p * - P ) = V1,m

* { p * - ( p * - P )} = V1,m
*P

Hence Eq. (2) becomes

* P = - RT ln x1
V1,m

The principal application of osmotic pressure measurement is in the determination

of the molar mass of a substance which is either slightly soluble or has a very
high molar mass such as proteins, polymers of various types and colloids. This
is due to the fact that even a very small concentration of the solution produces
fairly large magnitude of the osmotic pressure. In the laboratory, the concentrations
 Colligative Properties 69

usually employed are of the order of 0.001 mol dm–3. At concentration of

0.001 mol dm–3, the magnitude of osmotic pressure at 298 K is
P = cRT = (0.001 mol dm -3 ) (8.314 J K -1 mol -1 ) (298 K)
= 2.477 6 J dm -3 = 2 477.6 J m -3 = 2 477.6 Pa
= 0.0245 atm = 18.58 Torr
At this concentration, the values of other colligative properties such as
the boiling point elevation and the freezing point depression are too small to
be determined experimentally.
The van’t Hoff equation is expected to be valid only at infinite dilution
or to a very dilute solution where the solute-solute interaction is negligible.
This, however, might not be applicable to a substance of high molar mass at
concentrations which are usually employed for experimental measurements. The
method of extrapolation can be employed for such type of substances. The van’t
Hoff equation can be written as
n2 (m2 /M 2 ) Ê m ˆ Ê RT ˆ Ê RT ˆ
P = RT = RT = Á 2 ˜ Á = rÁ
V V Ë V ¯ Ë M 2 ˜¯ Ë M 2 ˜¯
P RT
i.e. =
r M2
where ρ is the density of the solution. The limiting value of Π /ρ at infinite
dilution can be determined by plotting Π /ρ versus ρ and determining the intercept
when ρ 0. This limiting value of (Π /ρ)ρ 0 will be equal to RT/M2.
RT
Thus M2 =
(P /r )rÆ0
The molar mass determined from any of the colligative properties is the number
average molar mass, designated as M n and is given by
Masses
N M + N2 M2 + ◊ ◊ ◊
 Ni Mi
Mn = 1 1 = i
N1 + N 2 + ◊ ◊ ◊ Â Ni
i

where Ni is the number of molecules having molar mass Mi. The above average
gives equal weightage to large and small molecules and simply counts the
number of molecules. It is thus independent of the individual characteristics of
the molecules. For example, all the polymer molecules in any sample do not
contain the same number of units in every chain, and, therefore, there will be a
range of molecular masses in the polymer sample. The molar mass determined
with the help of colligative property will be the number average molar mass.
A second average molar mass is the mass average molar mass, M m , and
is defined as

N M 2 + N 2 M 22 + ◊ ◊ ◊
 Ni M i2
Mm = 1 1 = i
N1 M 1 + N 2 M 2 + ◊ ◊ ◊ Â Ni Mi
i
70 A Textbook of Physical Chemistry

This average gives more weightage to the heavier molecules as compared to

the number average molar mass. This mass can be determined from the property
which depends upon the individual characteristics of the molecules, such as the
light-scattering measurements.

Example 2.9.1 The osmotic pressure values of various concentrations of polyisobutylene in two different
solvents at 298 K are given below. Calculate the molar mass of polyisobutylene by the
method of extrapolation to the infinite dilution.
ρ /g cm–3 0.020 0 0.015 0 0.010 0 0.007 5 0.005 0 0.002 5
Π / atm in benzene 0.002 08 0.001 52 0.000 99 0.000 49
in cyclohexane 0.011 7 0.006 6 0.00 30 0.001 73 0.000 9 0.000 35
–1 3
Solution The values of (Π /ρ)/(atm g cm ) are as follows.
ρ /g cm–3 0.020 0 0.015 0 0.010 0 0.007 5 0.005 0 0.002 5
Π /ρ in benzene 0.104 0.101 0.099 0.098
in cyclohexane 0.585 0.440 0.300 0.230 0.18 0.140

The plots of Π /ρ versus ρ are shown in Fig. 2.9.3.

Fig. 2.9.3 Plot of Π /ρ

versus ρ for
polyisobutylene in
benzene and cyclohexane

RT (82.0 cm3 atm K -1 mol -1 ) (298 K)

Thus Molar mass of polyisobutylene = =
(P /r )rÆ 0 (0.097 atm g -1 cm 3 )
250 000 g mol -1
 Colligative Properties 71

Example 2.9.2 One gram of serum albumin dissolved in 1 dm3 of water gives a solution height of 3.9 mm
when separated from pure water by a semipermeable membrane at 25 °C. What is the
molar mass of serum albumin? Density of the solution may be taken as 1.0 g cm–3.

Solution Osmotic pressure of the solution is

P = hr g = (3.9 ¥ 10 -3m) (103 kg m -3 ) (9.81 m s -2 )

= 38.26 N m -2

m2 RT (10 -3 kg) (8.314 J K -1 mol -1 ) (298 K)

Now M2 = =
PV (38.26 N m -2 ) (10 -3 m 3 )
= 64.78 kg mol -1

Example 2.9.3 The osmotic pressure is measured between water and a solution containing 1 g of
glucose C6H12O6 and 1 g of sucrose C12H22O11 in 1 000 g of water, the temperature being
maintained at 25 °C, and ρ (soln) = 1 g cm–3.
(a) Calculate osmotic pressure of the solution.
(b) If this pressure were measured and if the nature of solutes were not known, what
molar mass would have been calculated?
(c) The measurement of the osmotic pressure (and other colligative properties) gives an
average molar mass of the solute. What kind of average (i.e. number or mass) is this?
Verify the answer.

Ê 1g 1g ˆ
Solution (a) Total amount of solutes = Á + -1 ˜
= 0.008 479 mol
Ë 180 g mol -1 342 g mol ¯
Since ΠV = n2RT, we have

n2 RT (0.008 479 mol) (8.314 J K –1 mol –1 ) (298 K)

P = =
V (10 –3 m 3 )
= 2.101 × 10 4 J m –3 ∫ 2.101 × 10 4 N m –2

(b) Solution will contain a total of 2 g of the solute. Let the molar mass of solute be M.

m
Thus PV = nRT = RT
M

mRT (2 ¥ 10 -3 kg)(8.314 J K -1 mol -1 )(298 K)

or M = =
PV (2.101 ¥ 10 4 N m -2 )(10 -3 m 3 )
= 0.236 kg mol -1

(c) It is the number average molar mass as may be seen from the following calculations.

N1 M 1 + N 2 M 2 n M + n2 M 2 m + m2
Mn = = 1 1 = 1
N1 + N 2 n1 + n2 n1 + n2
10 -3 kg + 10 -3 kg
= = 0.236 kg mol -1
0.008 479 mol
72 A Textbook of Physical Chemistry

2.10 RELATIONS BETWEEN DIFFERENT COLLIGATIVE PROPERTIES

The different colligative properties can be correlated with each other through
the following expressions.
p* - p
= x2 (Eq. 2.4.1)
p*

D vap H1,m Ê 1 1ˆ
ln x1 = - Á *- ˜ (Eq. 2.7.7)
R Ë T b Tb ¯

D fus H1,m Ê 1 1ˆ
ln x1 = Á - ˜ (Eq. 2.8.7)
R Ë Tf* Tf ¯

and V P = - RT ln x1 (Eq. 2.9.6)

* . For dilute solutions, Eqs (2.7.7), (2.8.7) and (2.9.6) may be

where V = V1,m
approximated as shown in the following.

(i) Replacing x1 by 1 – x2 in Eq. (2.7.7), we get

D vap H1, m Ê Tb - Tb* ˆ

ln (1 - x2 ) = - Á ˜
R Ë TbTb* ¯

Since x2 << 1 and Tb T b*, we may write

D vap H1, m Ê DTb ˆ

x2 Á *2 ˜ (2.10.1)
R Ë Tb ¯

(ii) Replacing x1 by 1 – x2 in Eq. (2.8.7), we get

D fus H1, m Ê Tf - Tf* ˆ

ln (1 - x2 ) = Á ˜
R Ë Tf Tf* ¯

Since x2 << 1 and Tf T f*, we may write

D fus H1, m Ê – DTf ˆ

x2 = Á *2 ˜ (2.10.2)
R Ë Tf ¯

(iii) Replacing x1 by 1 – x2 in Eq. (2.9.6), we get

V P = - RT ln (1 - x2 )

Since x2 << 1, we may write

VP RT x2 (2.10.3)
 Colligative Properties 73

Comparing Eq. (2.4.1) with Eq. (2.10.1), we get

p* - p D vap H1, m Ê DTb ˆ

= x2 = ÁË *2 ˜¯ (2.10.4)
p* R Tb
Comparing Eq. (2.4.1) with Eq. (2.10.2), we get

p* - p D fus H1, m Ê - DTf ˆ

= x2 = ÁË T *2 ˜¯ (2.10.5)
p* R f
Comparing Eq. (2.4.1) with Eq. (2.10.3), we get

p* - p VP (2.10.6)
= x2 =
p* RT

Comparing Eq. (2.10.1) with Eq. (2.10.2), we get

D vap H1, m Ê DTb ˆ D fus H1, m Ê - DTf ˆ

Á 2 ˜ = x2 = Á *2 ˜ (2.10.7)
R Ë T *b ¯ R Ë Tf ¯

DTb D fus H1, m Tb*2

or = (2.10.8)
( - DTf ) Tf*2 D vap H1, m

Comparing Eq. (2.10.1) with Eq. (2.10.3), we get

D vap H1, m Ê DTb ˆ PV

Á *2 ˜ = x2 = RT
R Ë Tb ¯

Ê T D vap H1, m ˆ
or P =Á ˜ DTb (2.10.9)
Ë VTb*2 ¯

Ê VTb*2 ˆ
or DΤb = Á ˜P (2.10.10)
Ë T D vap H1, m ¯

Comparing Eq. (2.10.2) with Eq. (2.10.3), we get

D fus H1, m Ê - DTf ˆ PV

Á ˜ = x2 = (2.10.11)
R Ë Tf ¯
*2 RT
74 A Textbook of Physical Chemistry

Ê T D fus H1, m ˆ
or P =Á ˜ ( - DTf ) (2.10.12)
Ë V Tf*2 ¯

Ê V Tf*2 ˆ
or – DTf = Á ˜P (2.10.13)
Ë T D fus H1, m ¯

Example 2.10.1 The osmotic pressure of an aqueous solution of sucrose at 303 K is 2.47 atm; the molar
volume of water at this temperature is 18.10 cm3. Calculate the elevation of boiling point
of this solution. Given: vapH1 = 539 cal g–1.

Solution The given data are

P = 2.47 atm = 2.47 ¥ 101 325 N m -2 = 250 273 N m -2

Ê 8.314 J ˆ
D vap H1, m = (539 ¥ 18 cal mol -1 ) Á = 40 595 J mol -1
Ë 1.987 cal ˜¯
T = 303 K Tb* = 373 K * = 18.1 ¥ 10-6 m 3 mol -1
V1,m

Substituting the data in the expression

* Tb*2
P V1,m
DTb =
T D vap H1, m

(250 273 N m -2 ) (18.1 ¥ 10 -6 m 3 mol -1 ) (373 K)2

we get DTb =
(303 K) (40 595 J mol -1 )
= 0.051 K

Example 2.10.2 The addition of 3 g of a substance to 100 g of CCl4 raises the boiling point of CCl4
by 0.60 K, Kb = 5.03 K mol–1 kg. Calculate the freezing point depression (Kf = 31.8 K
kg mol–1); the relative vapour pressure lowering; the osmotic pressure of the solution at
298 K, and the molar mass of the substance. The density of CCl4 is 1.59 g cm–3.

Solution The given data are

m1 = 100 g, m2 = 3 g, DTb = 0.60 K, r1 (CCl 4 ) = 1.59 g cm -3 ,

K b = 5.03 K kg mol -1, Kf = 31.8 K kg mol -1, M1 (CCl 4 ) = 154 g mol -1

Since Tb = Kbm, we get

DTb 0.60 K
m= = = 0.12 mol kg -1
Kb (5.03 K kg mol -1 )

Since m = n2/m1 = (m2/M2)/m1, we get

m2 (3 g)
M2 = = = 0.25 kg mol -1
m m1 (0.12 mol kg –1 ) (100 g)
 Colligative Properties 75

Now – DTf = Kf m = (31.8 K kg mol –1 ) (0.12 mol kg –1 ) = 3.82 K

Dp n2 (m2 /M 2 )
= x2 = =
p* n1 + n2 (m1/M1 ) + (m2 /M 2 )
(0.003 kg/0.25 kg mol -1 )
= = 0.018
(0.1 kg/0.154 kg mol -1 ) + (0.003 kg/0.25 kg mol -1 )

m1 0.1 kg
* =
V1,m = = 0.062 9 dm 3
r1 1.59 kg dm -3

n2 RT (3 g/250 g mol -1 ) (8.314 J K -1 mol -1 )(298 K)

P = =
*
V1,m (0.062 9 dm 3 )
= 472.67 kPa ∫ 4.66 atm

2.11 COLLIGATIVE PROPERTIES OF STRONG AND WEAK ELECTROLYTES

The colligative properties of an electrolytic solution of a given concentration are
found to be larger than those of a nonelectrolytic solution of the same
concentration. This is due to the fact that an electrolyte in solution dissociates
to give positive and negative charged ions in such a manner that the sum of
the charges on positive ions is equal to the sum of the charges on negative ions
(condition of electroneutrality). The net result is that the total number of species
irrespective of their nature is increased. Since colligative properties depend only
on the number of species and not on their nature, it is obvious that the colligative
effects produced by an electrolytic solution will be larger than those produced by
a nonelectrolytic solution of the same concentration. The colligative properties of
a dilute solution of a strong electrolyte which undergoes complete dissociation
are found to be approximately an integral multiple of the corresponding values
of a nonelectrolytic solution of the same concentration. The value of the integral
number is equal to the total number of ions that are produced on dissociation
of a molecule of the strong electrolyte.
The colligative properties produced by a solution of a weak electrolyte of known
concentration are found to lie between the corresponding properties produced by
the same concentration of a nonelectrolytic solution and of a strong electrolytic
solution; the stoichiometry of the strong electrolyte is the same as that of the
weak electrolyte. This indicates that the weak electrolyte is partially dissociated
in the solution.
The colligative properties of an electrolytic solution can be expressed in terms of
those of a nonelectrolytic solution by use of the van’t Hoff factor i. It is defined as the
ratio of colligative effect produced by a given concentration of an electrolytic solution
and of a nonelectrolytic solution of the same concentration, i.e.
Colligative effect produced by a given concentration
of an electrolytic solution
i= (2.11.1)
Colligative effect produced by thhe same concentration
of a nonelectrolytic solution
76 A Textbook of Physical Chemistry

Thus we may write

- DTf DTb P Dp
i= = = = (2.11.2)
( - DTf )0 (DTb )0 (P )0 (Dp)0
where the quantities without subscript refer to electrolytic solution and those
with subscript refer to nonelectrolytic solution of the same concentration. Writing
Eq. (2.11.2) more explicitly, we have
– DTf = i(– DTf )0 = i Kf m
DTb = i (DTb )0 = i K b m
P = i(P )0 = i c2 RT (2.11.3)
The value of i must be calculated from the experimental data for each
electrolyte at various concentrations.

It is found that for a solution of strong electrolyte, the value of i increases on

dilution and approaches the limit of an integral number equal to the ions produced
by a molecule of the electrolyte. A few examples are given below.

Substance Limiting value of i

(1) HCl, HNO3, NH4Cl, CuSO4
NaCl 2
(2) H2SO4, CoCl2, K2SO4 3
(3) K3[Fe(CN)6] 4
(4) K4[Fe(CN)6] 5

The variation of i for a solution of a weak electrolyte is more wide in nature, i.e.
it increases more rapidly with dilution and attains the limiting value only at
infinite dilution.
The variation of van’t Hoff factor i for a weak electrolyte can be explained on
the basis of Arrhenius theory of electrolytic dissociation. According to this theory,
a weak electrolyte is in equilibrium with its ions. Thus, for AxBy we have
AxBy xAy+ + yBx– (2.11.4)
Let α be the degree of dissociation, then the molalities of various species
at equilibrium will be
m(A x B y ) = m(1 - a ); m(A y + ) = m(xa ); m(Bx - ) = m(ya )

where m is the original molality of the electrolyte.

The total molality mt of substances of all types present in the solution is
mt = m(1 - a ) + m(xa ) + m(ya ) = m[1 + a (x + y - 1)] (2.11.5)
= m[1 + a (n - 1)]
where ν is the total number of ions that are produced when an electrolytic
molecule completely dissociates in the solution and is equal to (x + y).
 Colligative Properties 77

The value of α increases on dilution (Ostwald dilution law) and thus

the molality of the solution increases on dilution. Consequently, the colligative
effects also increase on dilution. Taking, for example, the depression of freezing
point, we have
– DTf = Kf mt = Kf m[1 + a (n - 1)]
Solving for α, we obtain

(- DTf /Kf m) - 1 (- DTf ) - Kf m

a= = (2.11.6)
n -1 (n - 1)Kf m
The degree of dissociation α can also be written in terms of van’t Hoff
factor i. Since for an electrolytic solution
– DTf = iK f m = K f mt
Hence i m = mt = m[1 + a (n - 1)]
or i = 1 + a (n - 1)
i –1
Thus a= (2.11.7)
n –1
In fact, Eq. (2.11.7) is applicable to any of the colligative properties and can
equally be derived from other colligative properties. This equation provides a
method to calculate the degree of dissociation from the van’t Hoff factor i for
a given weak electrolyte.
The variation of colligative effects of a solution of a strong electrolyte on dilution
is not due to the increase in number of species on dilution since it is known
that strong electrolyte is already present in the completely ionized form. The
variation, however, can be explained on the basis of Debye-Hückel theory of
interionic-attraction according to which each ion in the solution is surrounded
on an average with more of the oppositely charged ions than like charges. In
other words, there exists an ionic atmosphere around each and every ion whose
net charge is opposite to that of the central ion. The properties of the electrolyte
are determined by the interaction of the central ion with its atmosphere. For
a given solvent and at a fixed temperature, the interaction between the ions
depend only on the charges of the ions and their concentrations and not at all
on their nature.
The interaction of the ions can be represented by a quantity, called the
ionic strength of the solution. It is defined as
1
m = Â ci zi2 (2.11.8)
2 i
where ci is the concentration of the ith ions in mol per dm3 and zi is its charge
number. The summation is to be carried over all types of ions present in the
solution.
Debye-Hückel showed that the variation of van’t Hoff factor on dilution is
due to the variation in ionic strength of the solution on dilution. The expression
relating these two is
78 A Textbook of Physical Chemistry

i = n (1 - 0.375 z+ | z- | m /m ∞ ) (2.11.9)
where ν is the number of ions yielded by a given molecule of electrolyte.
The agreement between the calculated values of i and the experimental
values is good for very dilute solutions up to molarity equal to 0.01 mol dm–3.
The deviations increase rapidly when molarity is greater than 0.01 mol dm–3
and are larger for electrolytes with higher values of z+ | z_ |.

Example 2.11.1 A solution containing 0.122 kg of benzoic acid in 1 kg of benzene (b. pt. 353 K) boils
at 354.5 K. Determine the apparent molar mass of benzoic acid (which dimerizes) in
the solution and the degree of dimerization. Given: vapH(benzene) = 394.57 J g–1.
Solution The given data are
m1 = 1 kg, m2 = 0.122 kg, Tb* = 353 K, Tb = 354.5 K,
-1
M1 = 78 g mol , D vap H1,m = 394.57 ¥ 78 J mol -1
The value of Kb(benzene) is
M1RTb*2 (0.078 kg mol -1 )(8.314 J K -1 mol -1 )((353 K)2
Kb = =
D vap H1,m (394.57 ¥ 78 J mol -1 )
= 2.626 K kg mol -1
The molality of the solution is

DTb T - Tb* (354.5 K - 353 K)

m= = b = = 0.57 mol kg -1
Kb Kb (2.626 K kg mol -1 )
Since m = n2/m1 = (m2/M2)/m1, we get
m2 0.122 kg
M2 = = = 0.214 kg mol -1
mm1 (0.57 mol kg -1 ) (1 kg)
Let α be the degree of dimerization of benzoic acid. Since the solution contains 1 mol
of benzoic acid, we will have
2C6H 5COOH �
��
��� (C6H 5COOH)2
(1 - a ) mol (a /2) mol
Total amount of solutes = {(1 – α) + α/2)} mol = (1 – α/2) mol
The number average molar mass of solutes in solution is given by
N1 M 1 + N 2 M 2 n M + n2 M 2 m 0.122 kg
Mn = = 1 1 = =
N1 + N 2 n1 + n2 n1 + n2 (1 - a /2) mol
Equating this to 0.214 kg mol–1, we get
0.122
= 0.214 or a = 2(1 - 0.122/0.214) = 0.86
1 - a /2

Example 2.11.2 A solution containing 0.011 kg of barium nitrate in 0.1 kg of water boils at 100.46 °C.
Calculate the degree of ionization of the salt. Kb(water) = 0.52 K kg mol–1.
Solution The given data are
m1 = 0.1 kg, m2 = 0.011 kg, Tb = 100.46 ∞C, Tb* = 100 ∞C,
M 2 = M Ba(NO3 )2 = 261.3 g mol -1
 Colligative Properties 79

The molality of the solution is

n2 m /M (0.011 kg/0.261 3 kg mol -1 )
m= = 2 2 = = 0.421 mol kg -1
m1 m1 (0.1 kg)
The value of Tb assuming the solute to be nonelectrolyte is

(DTb )0 = K b m = (0.52 K kg mol -1 ) (0.421 mol kg -1 ) = 0.22 K

The value of van’t Hoff factor is

DTb 0.46 K
i= = = 2.09
(DTb )0 0.22 K

Finally, the degree of dissociation of the electrolyte is

i -1 2.09 - 1 1.09
a= = = = 0.55
n -1 3 -1 2

Example 2.11.3 When 3.24 g of mercuric nitrate Hg(NO3)2 is dissolved in 1 kg of water, the freezing
point of the solution is found to be – 0.055 8 °C. When 10.84 g of mercuric chloride
HgCl2 is dissolved in 1 kg of water, the freezing point of the solution is – 0.074 4 °C.
Kf = 1.86 mol–1 K kg. Will either of these dissociate into ions in an aqueous solution?

Solution Molar mass of Hg(NO3)2 = 324.6 g mol–1

n2 m /M (3.24 g/324.6 g mol -1 )
Molality of Hg(NO3)2 solution, m = = 2 2 =
m1 m1 (1 kg)
= 0.01 mol kg -1
We will have

(-DTf )0 = Kf m = (1.86 K kg mol -1 )(0.01 mol kg -1 ) = 0.018 6 K

(- DTf ) 0.055 8 K
i= = =3
(- DTf )0 0.018 6 K

i -1 3 -1
a= = =1
n -1 3 -1
that is, the degree of dissociation of Hg(NO3)2 is one and thus the salt is completely
ionized in the solution.
For mercuric chloride, we have
Molar mass of HgCl2 = 271.5 g mol–1

m2 /M 2 (10.84 g/271.5 g mol -1 )

Molality of HgCl2 solution, m = =
m1 (1 kg)
= 0.04 mol kg -1

(-DTf )0 = Kf m = (1.86 K kg mol -1 )(0.04 mol kg -1 ) = 0.074 4 K

Since ( Tf)0 = Tf, the salt HgCl2 does not ionize in the solution.
80 A Textbook of Physical Chemistry

Example 2.11.4 The freezing point of a solution of acetic acid (amount fraction = 0.02) in benzene is
277.4 K. Acetic acid exists partly as a dimer

Calculate the equilibrium constant for the dimerization. The melting point of pure benzene
is 278.4 K, its molar enthalpy of fusion is 10.042 kJ mol–1.

Solution The value of Kf (benzene) is

M1R Tf*2 (78 ¥ 10 -3 kg) (8.134 J K –1 mol –1 ) (278.4 K)2

Kf = =
D fus H1, m (10 042 ¥ 103 J mol –1 )
= 5.0 K kg mol –1

Molality of the solution is

(- DTf ) (1.0 K)
m= = = 0.2 mol kg -1
Kf (5.0 K kg mol -1 )

Given amount fraction of acetic acid = 0.02

For such a dilute solution, we may write
n2 n2 n2
x2 = = = (n2 /m1 )M1 = mM1
n1 + n2 n1 (m1/M1 )

x2 0.02
Hence m= = = 0.257 mol kg -1
M1 78 ¥ 10 -3 kg mol -1
Thus, we have

Given: mm + 2md = 0.257 mol kg -1

Found: mm + md = 0.2 mol kg -1

where the subscripts m and d stand for monomer and dimer, respectively. Solving for
mm and md, we get

mm = 0.143 mol kg -1 and md = 0.057 mol kg -1

The equilibrium constant for the dimerization of acetic acid is

(md /m∞) 0.057
∞ =
Keq = = 2.79
(mm /m∞)2 (0.143)2

Example 2.11.5 The freezing point of an aqueous solution of KCN containing 0.189 mol kg–1 was
– 0.704 °C. On adding 0.095 mol of Hg(CN)2, the freezing point of the solution became
– 0.530 °C. Assuming that the complex is formed according to the equation
Hg(CN)2 + xCN - Æ Hg(CN) xx +2
-

find the formula of the complex.

 Colligative Properties 81

Solution Molality of the solution containing only KCN is

(- DTf ) (0.704 K)
m= = = 0.379 mol kg -1
Kf (1.86 K kg mol -1 )
This is just double of the given molality (= 0.189 mol kg–1) of KCN, indicating complete
dissociation of KCN. Molality of the solution after the formation of the complex
(- DTf ) (0.530 K)
m= = = 0.285 mol kg -1
Kf (1.86 K kg mol -1 )
If it be assumed that the whole of Hg(CN)2 is converted into complex, then the amounts
of various species in 1 kg of solvent after the formation of the complex will be
n(K + ) = 0.189 mol, n(CN - ) = (0.189 - x ) mol
-
n(Hg(CN) xx +2 ) = 0.095 mol

Total amount of species in 1 kg solvent becomes

ntotal = [0.189 + (0.189 - x ) + 0.095] mol = (0.473 - x ) mol
Equating this to 0.285 mol, we get
(0.473 - x ) mol = 0.285 mol
i.e. x = (0.473 - 0.285) = 0.188
0.188 mol
Number of CN– units combined = =2
0.095 mol
Thus, the formula of the complex is Hg(CN)42–.

Example 2.11.6 The vapour pressure of a solution containing 6.69 g of Mg(NO3)2 dissolved in 100 g
of water is 747 Torr at 373 K. Calculate the degree of dissociation of the salt in the
solution.
Solution Molar mass of Mg(NO3)2 = 148.31 g mol–1
Amount fraction of the solute in the solution is
n2 (m2 /M 2 ) (6.69/148.31)
x2 = = =
n1 + n2 (m1/M1 ) + (m2 /M 2 ) (1100/18) + (6.69/148.3)
0.045
= = 8.03 ¥ 10 –3
5.556 + 0.045

The depression in the vapour pressure is

(Dp)0 = x2 p* = (8.03 ¥ 10 -3 )(760 Torr) = 6.10 Torr

The value of van’t Hoff factor is

Dp (760 - 747) Torr
i= = = 2.13
(Dp)0 (6.10 Torr)
The degree of dissociation of the salt is
i -1 2.13 - 1 1.13
a= = = = 0.565
n -1 3 -1 2
82 A Textbook of Physical Chemistry

Example 2.11.7 A solution is 0.5 molar in MgSO4, 0.1 molar in AlCl3 and 0.2 molar in (NH4)2SO4. What
is the total ionic strength?

Solution The ionic strength of the solution is given by

1
m= Â ci zi2
2 i

where ci is the molar concentration of the ith ion and zi is its charge number. Thus

1
m= [(c 2+ )(zMg2+ )2 + (cSO2- )(zSO2- )2 + (cAl3+ )(zAl3+ )2
2 Mg 4 4

+ (cCl - )(zCl - )2 + (cNH+ )(zNH+ )2 ]

4 4

Substituting the given data, we get

1
m/mol dm -3 = [(0.5)(2)2 + (0.7)( - 2)2 + (0.1)(3)2 + (0.3)( - 1)2 + (0.4)(1)2 ]
2
1 1
= [2.0 + 2.8 + 0.9 + 0.3 + 0.4] = (6.4)
2 2
= 3.2

Example 2.11.8 A 0.2 molar aqueous solution of KCl freezes at – 0.680 °C. (a) Calculate the van’t Hoff
factor i and the apparent degree of dissociation of KCl. (b) Using the Debye-Hückel
equation, calculate the value of the van’t Hoff factor and compare it with the value
obtained in part (a), (c) Calculate the expected values of Tb and Π at 0 °C using the
value of i obtained in part (a). Assume molality and molarity have the same value.

Solution (a) We have

( – DTf )0 = Kf m = (1.86 K kg mol –1 )(0.2 mol kg –1 ) = 3.72 K

( – DTf ) 0.680 K
i= = 1.83
( – DTf )0 0.372 K

The apparent degree of dissociation of KCl is

i - 1 1.83 - 1
a= = = 0.83
n -1 2 -1

(b) The ionic strength of the solution is given by

1
m= Â ci zi2
2 i

Substituting the given data, we get

1
m/mol dm -3 = [(0.2)(1)2 + (0.2)(- 1)2 ] = 0.2
2
 Colligative Properties 83

According to Debye-Hückel theory, we get

i = n (1 - 0.375 z+ | z- | m /m ∞ )
= 2[1 - (0.375)(1)(1) 0.2 ] = 2 (1 - 0.1688)
= 1.644
(c) DTb = i (DTb )0 = i K b m
= (1.83)(0.52 K kg mol -1 )(0.2 mol kg -1 )
= 0.19 K
P = i(P )0 = icRT
= (1.83)(0.2 ¥ 103 mol m -3 )(8.314 J K -1 mol -1 ) (273 K)
Ê 1 atm ˆ
= 8.307 ¥ 105 Pa ∫ (8.307 ¥ 105 Pa) Á = 8.2 atm
Ë 1.01325 Pa ¯˜

2.12 SOLUBILITY OF A SOLUTE IN AN IDEAL SOLUTION

At saturation point, where no more solute dissolves in a solution, there exists an

equilibrium between the solute in solution and the pure solid solute, i.e.
Solute in solution Pure solid solute
The thermodynamic condition of equilibrium is
* (T , p)
m2(sol) (T , p, x2 ) = m2(s) (2.12.1)

where x2 is the amount fraction of solute in the saturated solution. If the solution
is ideal, then
* (T , p) + RT ln x
m2(sol) (T , p, x2 ) = m2(1) (2.12.2)
2

Substituting Eq. (2.12.2) in Eq. (2.12.1) and rearranging, we have

* + RT ln x = m *
m2(1) 2 2(s)

* - m*
m2(s) D fus m2*
2(1)
or ln x2 = =- (2.12.3)
RT RT
According to Eq. (2.12.3), the amount fraction of solute in the saturated
solution is a function of the temperature of the solution. In order to determine
the functionality, we differentiate Eq. (2.12.3) with respect to x2, keeping p
constant. Thus, we have
1 1 ÔÏ ∂( D fus m2* /T ) Ô¸ Ï ∂T ¸
=- Ì ˝ Ì ˝
x2 R ÓÔ ∂T ˛Ô p Ó ∂x2 ˛ p
Using Gibbs-Helmholtz equation, we get
1 D fus H 2,m Ê ∂T ˆ
= Á ˜
x2 RT 2 Ë ∂x2 ¯ p
84 A Textbook of Physical Chemistry

dx2 D fus H 2,m dT

or = ( p constant) (2.12.4)
x2 R T2
To determine the variation of x2 with T, we integrate the above expression
to give

x2 dx T D fus H 2, m dT
Ú1 x2
= ÚT
f
*
R T2
(2.12.5)

where T f* is the freezing point of the pure solute (x2 = 1) and x2 is the solubility
of the solute at temperature T of the solution.
Assuming fusH2,m to be independent of temperature, Eq. (2.12.5) yields

D fus H 2, m Ê 1 1 ˆ
ln x2 = - Á - ˜ (2.12.6)
R Ë T Tf* ¯
Equation (2.12.6) is an expression of the ideal law of solubility. According
to this law, the solubility of a substance depends only on the characteristics of
the solute through fusH2, m and T f* and is independent of the nature of the
solvent.
The following dependence on the solubility of the solute may be concluded.

A comparatively lesser value of T f* (i.e. low freezing point of the solute)

makes the right side of Eq. (2.12.6) more positive indicating larger value
of x2 (i.e. more is the solubility).
A comparatively lesser value of fusH2,m makes the right side of Eq. (2.12.6)
less negative indicating larger value of x2 (i.e. more is the solubility).
Increasing the value of T also makes the right side of Eq. (2.12.6) lesser
negative indicating larger value of x2 (i.e. more is the solubility).
Equation (2.12.6) can be written as

D fus S2, m Ê T*ˆ

ln x2 = Á 1- f ˜ (2.12.7)
R Ë T ¯

where fusS2,m is the molar entropy of fusion of solute. Figure 2.12.1 shows the
variation of solubility, x, as a function of temperature for two substances with
the same entropy of fusion but different freezing points. Larger the value T f*,
lesser the solubility of the substance.
In deriving Eq. (2.12.6), we have assumed that fusH2,m remains constant within
the temperature range T f* and T. This is true only if the temperature of the
solution is not far away from the melting point of the solute. If the temperature
of the solution is very far away from T f*, then the solubility as calculated from
Eq. (2.12.6) is no longer accurate.
 Colligative Properties 85

Fig. 2.12.1 Variation of

solubility with
temperature

If x1 and x2 are the solubilities of solute at temperatures T1 and T2, respectively,

we can write

D fus H 2, m Ê 1 1 ˆ
ln x1 = - Á - ˜ (2.12.8)
R Ë T1 Tf* ¯
D fus H 2, m Ê 1 1 ˆ
ln x2 = - Á - ˜ (2.12.9)
R Ë T2 Tf* ¯
Subtracting Eq. (2.12.8) from Eq. (2.12.9), we get
x2 D fus H 2, m Ê 1 1ˆ
ln =- ÁË T - T ˜¯ (2.12.10)
x1 R 2 1
Equation (2.12.10) relates the solubility of the solute in a solvent with temperature
of the solution.

Example 2.12.1 The molar enthalpy of fusion of naphthalene is 10.0 kJ mol–1 at 298.15 K and its normal
melting point is 353.35 K. Calculate the solubility of naphthalene at 298.15 K in a liquid
with which it forms an ideal solution.
Solution The given data are
D fus H 2, m = 10.0 kJ mol –1, T = 298.15 K, Tf* = 353.35 K
Substituting the given data in the expression
D fus H 2, m Ê 1 1 ˆ
ln x2 = - Á - ˜
R Ë T Tf* ¯

(10 4 J mol -1 ) Ê 1 1 ˆ
we get ln x2 = - -1 -1 Á
- ˜¯ = - 0.273 6
(8.314 J K mol ) Ë 298.15 K 353.35 K
x2 = 0.532 6
86 A Textbook of Physical Chemistry

Example 2.12.2 Given the following data, compute the molar enthalpy of fusion of sucrose assuming
ideal solution.
Saturation solubility at 298 K = 6.2 mol per kg of solvent
Freezing point of solute = 473 K.

Solution The given data are

T = 298 K, Tf* = 473 K

n2 (6.2 mol)
x2 = = = 0.1000 4
n1 + n2 (1 000/18) mol + (6.2 mol)
Substituting the data in the expression

D fus H 2, m Ê 1 1 ˆ
ln x2 = - Á - ˜
R Ë T Tf* ¯

D fus H 2, m Ê 1 1 ˆ
we get ln 0.100 4 = – Á – ˜
(8.314 J K –1 mol –1 ) Ë 298 K 473 K ¯
This gives

(ln 0.100 4) (8.314 J K -1 mol -1 ) (298 K) (473 K)

D fus H 2, m = -
(473 K - 298 K)
= 15 422 J mol -1

REVISIONARY PROBLEMS

2.1 What do you understand by the terms (a) solution, (b) solute molecules in a solution,
and (c) colligative properties?
2.2 (a) Explain the following concentration units.
(1) Mass %. (2) Volume %. (3) Molarity. (4) Molality. (5) Normality.
(6) Amount fraction.
(b) How will you convert:
(1) Amount fraction into molarity and vice versa?
(2) Amount fraction into molality and vice versa?
(3) Molarity into molality and vice versa?
(c) Explain which of the concentration units given in part (a) vary with temperature.
2.3 Derive the following conversion expressions of concentration units.
Amount fraction into molarity M = x2 r / ( x1 M1 + x2 M 2 )
Molarity into amount fraction x2 = MM1/{r + M ( M1 - M 2 )}
Amount fraction into molality m = x2 /(x1 M1 )
Molality into amount fraction x2 = mM1/(1 + mM1 )
Molarity into molality m = M/(r - MM 2 )
Molality into molarity M = mr /(1 + mM 2 )
Show that for a very dilute solution, molality of the solution is virtually identical
with its molarity.
 Colligative Properties 87

2.4 (a) Describe the experimental behaviour regarding the variation of vapour pressure
when a nonvolatile solute is added to a volatile solvent.
(b) What is the characteristic of the curve of vapour pressure versus amount fraction
of solute x2 as x2 0?
(c) What do you understand by an ideal solution? Explain, why a real solution
deviates from the ideal behaviour as x2 is increased.
(d) State Raoult’s law as applicable to ideal solutions. Under what conditions does
a real solution follow Raoult’s law?
2.5 Show that the relative lowering of vapour pressure of a solvent is equal to the
amount fraction of the nonvolatile solute and hence show that this relative lowering
is a colligative property. Discuss how the relative lowering of vapour pressure of a
dilute solution can be utilized in determining the molar mass of the solute.
2.6 Show that the chemical potential for the solute and solvent in an ideal solution is
given by
mi(sol) = mi* + RT ln xi
2.7 Show that the origin of colligative properties such as elevation of boiling point,
depression of freezing point and osmotic pressure lies in the relation
* + RT ln x1
m1(sol) = m1(1)
where μ1(sol) is the chemical potential of the solvent in the solution, μ *1(1) is that of
pure liquid solvent and x1 is the amount fraction of the solvent in the solution.
2.8 Draw chemical potential versus temperature diagrams for a solvent in solid, liquid
and vapour phases. What changes in the above diagrams occur when a nonvolatile
solute is added to the solvent?
Explain with the help of these diagrams that there occurs (a) an elevation in boiling
point and (b) a depression in freezing point of the solvent when a nonvolatile solute
is added to the solvent. Show also that the depression in freezing point is larger than
the elevation in boiling point.
2.9 (a) Derive thermodynamically the relation
1 1 RT ln x1
= +
Tb Tb* D vap H1,m

where Tb is the boiling point of the solution in which the amount fraction of the
solvent is x1 and Tb* is the boiling point of the pure solvent.
(b) Starting from the relation
dx1 D vap H1, m
=- dTb
x1 RTb2
derive the relation
dTb = K b dm i.e. DTb = K b m

as applicable to dilute solutions. Explain the meaning of the term Kb and the factors
on which its value depends. What is the unit of Kb?
2.10 (a) Derive thermodynamically the relation

dx1 D fus H1, m dTf

=
x1 R Tf2
and its integrated form,
1 1 R ln x1
= -
Tf Tf* D fus H1, m
88 A Textbook of Physical Chemistry

where Tf is the freezing point of the solution, Tf* is that of the pure solvent and x1
is the amount fraction of the solvent in the solution.
(b) Starting from the relation

dx1 D H dT
= fus 1,m 2f
x1 R Tf

derive the relation

– dTf = K f dm i.e. – DTf = K f m

On what factors does the value of Kf depend? What is its unit?

2.11 (a) What do you understand by the osmotic pressure of the solution? Derive
thermodynamically the relation

PV = - RT ln x1

where Π is the osmotic pressure, V is the molar volume of the pure solvent and x1
is the amount fraction of the solvent in solution.
(b) Show that the above relation can be simplified to

P = cRT
where c is the molar concentration of the solute in the solution. Discuss the types
of approximations made in deriving the above relation.
(c) Explain why the osmotic pressure measurement is preferred for the determination
of molar mass of polymers, proteins and colloids over the other colligative properties.
Discuss whether the molar mass obtained is the number average molar mass or the
mass average molar mass.
2.12 Derive the following relations connecting the different colligative properties.

p* - p D vap H1, m Ê DTb ˆ D fus H1, m Ê - DTf ˆ PV

= Á 2˜ = Á ˜ =
p* R Ë Tb* ¯ R Ë Tf* ¯
2 RT

DTb D fus H1, m Tb*2

=
- DTf Tf* 2 D vap H1, m

P VTb*2 P VTf*2
DTb = and - DTf =
T D vap H1, m T D fus H1, m

where V = V1,m
* .

2.13 (a) Discuss why the colligative properties of a solution containing either a strong
electrolyte or a weak electrolyte are larger than those of a solution containing
nonelectrolyte of the same concentration. What effect does the dilution have on the
colligative properties of an electrolytic solution?
(b) What is the van’t Hoff factor i? Show that this is given as

- DTf DTb P Dp
i= = = =
( - DTf )0 (DTb )0 (P )0 (Dp)0

where the quantities without subscript refer to the electrolytic solution and those
with subscript refer to the nonelectrolytic solution of the same concentration.
 Colligative Properties 89

(c) Discuss how the Arrhenius theory of electrolytic dissociation for a weak electrolyte
and the Debye-Hückel theory of interionic attraction for a strong electrolyte explain
the variation of colligative properties on dilution? Derive the relation

i -1
a=
n -1
where α is the degree of dissociation, i is the van’t Hoff factor and ν is the total
number of ions that are produced on complete dissociation of the electrolytic molecule.
2.14 (a) Show that the ideal solubility expression at temperature T is given by

D fus H 2,m È 1 1˘
ln x2 = - Í - *˙
R Î T Tf ˚
where x2 is the amount fraction of the solute in the saturated solution, fusH2, m is
the molar enthalpy of fusion of the pure solute and Tf* is the freezing point of the
pure solute. Discuss the approximations made in deriving the above relation.
(b) On what factors does the ideal solubility of the solute depend?

TRY YOURSELF PROBLEMS

2.1 In the Rast method of determining molar mass, camphor is used as the solvent.
Outline the merits of choosing camphor as the solvent. How will you determine the
value of Kf for camphor theoretically?
2.2 Osmotic pressure measurements are preferred over the other colligative properties to
determine the molar mass of high polymers. Give reasons.
2.3 The accurate determination of molar mass is done by the method of extrapolation
where the plot of (Π/c) versus c is extrapolated to zero concentration. Justify this
procedure.
2.4 Justify the statements:
(a) The classification of solute and solvent in a solution is a matter of convenience
only.
(b) Molality of a solution is independent of temperature of the solution.
(c) The expressions – Tf = Kf m, Tb = Kb m and Π = cRT are applicable only for
dilute solutions.
(d) For solvents obeying Trouton’s rule, the values of Kb and Kf are directly proportional
to the factor (MT *).
(e) The solubility as calculated from the ideal solubility law shows large deviation
from the observed value if the temperature of interest is far below the melting point
of the solid.
(f) Colligative properties of a given electrolytic solution are larger than the corresponding
properties produced by the same concentration of a nonelectrolytic solution.
2.5 Discuss what types of graphs do you expect for the following. What will be their
slopes and intercepts?
(a) ln x1 versus l/Tb. (b) ln x1 versus 1/Tf. (c) ln x2 versus l/T, where x2 is the amount
fraction of solute in the saturated ideal solution.
2.6 (a) If a system contains particles of the same mass, it is called the monodisperse
system, whereas if it contains particles of different masses, it is called the polydisperse
system. Show that for a monodisperse system, the number average and mass average
molar masses have the same value whereas for a polydisperse system, the mass
average is greater than the number average.
90 A Textbook of Physical Chemistry

(b) Name at least one property which depends on each of the number average molar
mass and mass average molar mass.
(c) Determine the number average and the mass average of a system containing the
following particles.
5 particles of m = 1 g
3 particles of m = 2 g
3 particles of m = 3 g
1 particle of m = 4 g
(Ans. (b) any colligative property and light scattering, (c) 2.0 g and 2.5 g)
2.7 (a) In deriving Eq. (2.12.6), it has been assumed that fusH2,m is independent of the
temperature. Suppose fusH2,m depends upon the temperature and is given by

Ê Db ˆ Ê Dc ˆ
DH = DH 0 + (Da )T + Á ˜ T 2 + Á ˜ T 3 + ◊ ◊ ◊
Ë 2 ¯ Ë 3¯

where H0, a, b, c, . . ., etc., are constants. Taking the above temperature

dependence, show that the solubility expression is given by
DH 0 Da Db Dc T 2
ln x2 = - + ln (T / K) + T + + ◊◊◊ + K
RT R 2R 3R 2
where K is the constant of integration.
(b) Predict for which substance (1 or 2) having following characteristics, the ideal
solubility is larger, and give reasons:
(i) Same fusHm but T *1 > T 2*.
(ii) Same T * but fusH1, m > fusH2, m
2.8 Given below is a cell.

The membrane allows the diffusion of small ions and not of large ions such as
P–. Such a system will not be in equilibrium as the Cl– ions can diffuse from right
side to left side. This diffusion will also be accompanied by the diffusion of Na+
ions in order to maintain the electroneutrality. Equilibrium will be achieved when
the chemical potential of NaCl is same on each side of the membrane, i.e.
(m NaCl )L = (m NaCl )R
For dilute solutions, we can write
m*NaCl + RT ln (m± , NaCl )2L = m*NaCl + RT ln (m± , NaCl )2R
or (m± , NaCl )L = (m± , NaCl )R
or (mNa + )L (mCl - )L = (mNa + )R (mCl - )R
If x is the concentration of NaCl that has diffused from right side to left side, show
that it is equal to
b2
x=
a + 2b
The above equilibrium is known as Donnan membrane equilibrium.
 Colligative Properties 91

2.9 Given below is a cell

The membrane allows the passage of small ions Na+ and Cl– and not large ion
such as R–. If x is the concentration of NaCl that has diffused from left to right
side, show that

a( a + b)
x=
2a + b
2.10 Given below is a cell.

The membrane allows the passage of small ions Na+ and Cl– and not large ion
such as P 4–. If b > a and if x is the concentration of NaCl that has diffused from
right to left side, show that

b2
x=
4 a + 2b

2.11 Given below is a cell.

The membrane allows the passage of small ion Mg2+ and Cl– and not large ion such
as P–. If a > b and if x is the concentration of MgCl2 that has diffused from left to
right, show that the value x is obtainable from the expression.
2x3 + x2(b – 3a) + 3a2x – a3 = 0
(Hint: [Mg2+]L [Cl–]L2 = [Mg2+]R [Cl–]L2)
2.12 Why does increase in pressure reduce cooking time?
2.13 Will an egg cook faster if boiled in pure water or in water to which salt has been
added? Give reason.
2.14 The phenomenon of osmosis can be stopped by either increasing the external pressure
on the solution side or by lowering the external pressure on the solvent side. Explain.
2.15 Show that the relative lowering in the freezing – Tf /Tf*, when a nonvolatile solute
is dissolved in a volatile solvent, is given by RTf*x2/ fusH1,m, where x2 is the amount
fraction of solute in the solution. Does the freezing point remain constant as more
and more of the solvent crystallizes out?
92 A Textbook of Physical Chemistry

NUMERICAL PROBLEMS

2.1 An aqueous solution of HCl has 2.0% by mass of HCl and a density of l.016 g cm–3.
Calculate the amount fraction of solute, molarity and molality of the solution.
(Ans. 0.01, 0.557 mol dm–3, 0.559 mol kg–1)
2.2 In 804 g of water, 30 g sucrose (C12H22O11) and 30 g glucose (C6H12O6) were dissolved.
What is the vapour pressure of this solution at 303 K if the vapour pressure of water
is 31.82 mmHg? (Ans 31.64 mmHg)
2.3 The relative lowering of vapour pressure can be determined conveniently by the
Ostwald and Walker’s dynamic method. In this method, a fixed volume of dry air is
first passed through bulbs containing the solution and then through the bulbs containing
the pure solvent, the losses in masses of these two sets of bulbs are related to psol and
p as follows.

m1 psol

m2 p* – psol

Dp p * - psol Dm2
Hence = =
p* p* Dm1 + Dm2

Using the above relation, determine the molar mass of solute from the following
data:
m1 = 1.949 g, m2 = 0.087 g, the solution contains 26.66 g of solute in 200 g of
water.
(Ans. 56.15 g mol–1)
2.4 The boiling point of ethyl alcohol is 78.4 °C and its vapHm = 39.42 kJ mol–1.
Calculate the boiling point elevation constant for ethyl alcohol.
(Ans. 1.19 K kg mol–1)
2.5 Benzene and cyclohexane follow Trouton’s rule. If their boiling points are 80.2 °C
and 81.4 °C, respectively, calculate the values of the boiling point elevation constants.
(Ans. 2.625 K kg mol–1, 2.833 K kg mol–1)
2.6 A 10% solution of cane sugar has undergone partial inversion according to the reaction
sucrose + water glucose + fructose
The boiling point of the solution is 100.27 °C: (a) What is the average molar mass
of the dissolved material? (b) What fraction of the sugar has inverted?
(Ans. (a) 209.9 g mol–1, (b) 0.63)
2.7 (a) The molar mass and the melting point of camphor are 152.2 g mol –1 and
178.4 °C, respectively. The cryscopic constant of camphor is 37.7 K kg mol–1.
Calculate fusH1, m for camphor. (Ans. 6.844 kJ mol–1)
(b) A mixture which contains 0.52 g of camphor and 0.045 g of an organic solute
freezes at 157.2 °C. The solute contains 93.46% of C and 6.54% of H by mass.
Determine the molecular formula of the compound. (Ans. C12H10)
2.8 Pure benzene freezes at 5.4 °C and a solution of 0.223 g of phenylacetic acid
(C6H5CH2COOH) in 4.4 g of benzene freezes at 4.47 °C. The molar enthalpy of
fusion of benzene is 9.89 kJ mol–1. Calculate the relative molar mass of phenylacetic
acid and comment on the form of the acid in the solution.
(Ans. M = 273 g mol–1, dimerizes in solution)
 Colligative Properties 93

2.9 (a) Assuming fusH1, m to be independent of temperature. Show that the integrated
expression of Eq. (2.8.9) is given by
1 R ln (1 + mM1 ) 1
= +
Tf D fus H1, m Tf*

Calculate Tf for aqueous solutions having

m/mol kg–1 0.1, 0.2, , 0.8, 0.9.
–1
Given: fusH1, m = 6009.5 J mol .
(b) Calculate Tf by using the expression, – Tf = Kf m (an expression derived for dilute
solutions in which m 0) for the aqueous solutions mentioned in part (a). Given:
Kf = M1RTf*2/ fusH1, m.
(c) Determine graphically or otherwise the maximum molality of aqueous solution for
which Tf s calculated in parts (a) and (b) do not differ more than 0.01 K
(Ans. 0.59 mol kg–1)
2.10 The average osmotic pressure of human blood is 7.7 atm at 40 °C. (a) What should be
the total concentration of various solutes in the blood? (b) Assuming this concentration
to be essentially the same as the molality, find the freezing point of blood.
(Ans. – 0.56 ºC)
2.11 Consider the following arrangement, in which a solution containing 20 g of hemoglobin
in 1 dm3 of the solution is placed in the right compartment and pure water is placed
in the left compartment. At equilibrium, the height of water in the right-side column
is 77.8 mm in excess of that in the left-side column. What is the molar mass of
hemoglobin? The temperature of the system is maintained at 298 K.
(Ans. 65 040 g mol–1)
2.12 The chemical potential of pure water is – 285.84 kg mol–1. What is the chemical
potential of water in a solution containing 0.1 mol of solute per 120 g of water at
298.15 K and 1 atm total pressure? Assume ideal behaviour.
(Ans. – 285.88 kJ mol–1)

2.13 The freezing point of a solution of 0.138 g of a nonvolatile solute in 15.2 g benzene
is 0.53 K less than the freezing point of pure benzene. What are the molar mass of
the substance and the normal boiling point of solution?
(Ans. 88 g mol–1, 80.4 °C)
2.14 An aqueous solution of cane sugar (M = 342 g mol–1) has an osmotic pressure of
1.5 × 101.3 kPa at 18 °C. What will be the vapour pressure of this solution at 40 °C?
If 100 g of this solution is cooled to – 3.0 °C, what mass of ice will separate out?
Vapour pressure of water at 40 °C = 55.324 mmHg.
(Ans. 55.26 mmHg, 94 g).
2.15 Blood freezes at – 0.56 °C and a solution of 3.0 g of urea (M = 60 g mol–1) in
250 g of water freezes at – 0.37 °C. What is the concentration of blood solution and
its osmotic pressure at 37 °C?
(Ans. 0.3 mol dm–3, 750 kPa)
2.16 The vapour pressure of a solution of urea is 736.2 mmHg at 100 °C. What is the
osmotic pressure of this solution at 15 °C? At what temperature would the solution
begin to freeze? Kf for water = 1.86 K kg mol–1.
(Ans. 4.17 kPa, –3.2 °C.)
94 A Textbook of Physical Chemistry

2.17 Two grams of a complex of high molar mass compound (M = 12 400 g mol–1) is
dissolved in 100 g of water at 25 °C. Calculate Tf, Tb, p and Π of the solution
at 25 °C. On the basis of values obtained suggest the most appropriate method for
determining the molar mass.
(Ans. – Tf = 3 × 10–3 °C, Π = 29 mmHg, Tb = 8 × 10–4 °C,
p = 6.9 × 10–4 mmHg)

2.18 A 0.4 molal solution of K2SO4 freezes at – 1.52 °C. Assuming that van’t Hoff factor
i is constant with temperature, calculate the vapour pressure at 25 °C and the
normal boiling point of the solution. Given: p1*(298 K) = 0.031 67 bar.
(Ans. 0.0312 bar, 100.42 ºC)
2.19 An aqueous solution contains 5% by mass of urea, 1.0% by mass of KCl and 10% by
mass of glucose. Calculate its freezing point. Assume complete ionization for KCl.
(Ans. – 4.29 ºC)
2.20 When phenol (C6H5OH) is dissolved in a particular solvent, it is partially dimerized.
If 2.58 g of phenol is dissolved in 100 g of the solvent, the freezing point of solvent
(Kf = 14.1 K mol–l kg) is depressed by 2.37 K. Find how much of the phenol is
dimerized in solution. (Ans. 77.55%)
2.21 (a) An involatile solute A dimerizes in a solvent:

2A A2
K b (K b m - DTb )
show that Keq =
(2 DTb - K b m)2
where m is the molality of the solute in the solvent and Kb is the boiling point
elevation constant of the solvent.
(b) A 0.103 3 molal solution of A in the above solvent produces Tb = (0.070 4 mol
kg–1) Kb. Calculate the value of Keq. (Ans. 23.4 mol–1 kg)
2.22 125 g benzoic acid (molar mass = 121 g mol–1) when dissolved in 100 cm3 of benzene
produces osmotic pressure of 1.73 atm at 300 K. Benzoic acid is known to form
dimer in benzene. Calculate (i) the percentage of benzoic acid in the associated state
and (ii) the equilibrium constant of the dimerization reaction.
(Ans. 63.93%, 23.78 mol–1 dm3)
2.23 (a) The freezing point of 0.01 molal CaCl2 is – 0.051 12 °C. What freezing point is
predicted by the Debye-Hückel theory? What is the osmotic pressure of 0.01 molal
CaCl2 at 0 °C?
(b) Using the Debye-Hückel equation, calculate the values of i at 0 °C for 0.000 5
molar aqueous solutions of HCl, BaCl2, H2SO4, and La(NO3)3.

2.24 The solubility values of picric acid in benzene are:

θc / °C 5 10 15 20 25 35
g /100 g benzene 3.70 5.37 7.29 9.56 12.66 21.38.
Calculate the freezing point and molar enthalpy of fusion of picric acid.

2.25 If in Q 2.11 of Try Yourself Problem, a = 0.003 M and b = 0.001 M, Show that
x = 1.3628 × 10–3 M.
(Hint: By the method of successive approximation, determine the value of x using
the expression x = [{x2(3a – b) – 3a2x + a3}/2]1/3
 3 Phase Rule

3.1 INTRODUCTION AND DEFINITIONS

The various conditions of equilibrium between phases, such as the number of
phases, the number of components and the degrees of freedom (or the variance),
can be correlated with one another with the help of a general rule, known as the
phase rule. This rule was deduced theoretically by J.W. Gibbs. Before proceeding
with the deduction of the rule, it is necessary to define and explain the terms
involved, viz., phase, component and degree of freedom.
Phase A phase is defined as any homogeneous and physically distinct part of a system
which is separated from other parts of the system by definite bounding surfaces.
The term homogeneous means that the system has identical physical properties
and chemical composition throughout the whole of the system.
In general, we have:
For gaseous system Only one phase is possible since gases are completely
miscible with one another in all proportions.
For liquid system The number of phases is equal to the number of layers
present in the system. For completely miscible liquids, the number of phases is
equal to one.
For solid system In general, every solid constitutes a single phase except when
a solid solution is formed. Thus the number of phases in the solid system is equal
to the number of solids present. In solid solution, the number of phases is equal
to one. Each polymorphic form and allotropic modification constitutes a separate
phase.
Number of It is the smallest number of independent chemical constituents by means of
Components which the composition of each and every phase can be expressed. The
independent chemical constituent is the one whose concentration can be varied
independent of other constituents of the system. Some typical examples are given
below.
One-component system The water system is a typical example of one-component
system. We can have the following equilibria between the different phases of water:
solid water (ice) liquid water
solid water water vapour
96 A Textbook of Physical Chemistry

liquid water water vapour

solid water liquid water water vapour
The composition of any one phase (solid, liquid or vapour) can be expressed
in terms of the single constituent water and hence the number of components
is one. The variable could be either H2 or O2 since specification of one fixes
the other through the formula H2O. However, this choice is never considered
since H2 or O2 does not exist as the individual constituent in the above
equilibrium.
Two-component system The typical example of a two-component system is the
salt-water system such as sodium sulphate-water, copper sulphate-water, etc. In
Na 2 SO 4 -H 2 O system, the various phases that may occur are Na 2 SO 4 ,
Na2SO4 7H2O, Na2SO4 10H2O, an aqueous solution of Na2SO4, water present
as ice, liquid and vapour. The composition of any of the above phases can be
stated in terms of the two constituents, namely, sodium sulphate and water:
Na2SO4 : Na2SO4 + 0H2O
Na2SO4 7H2O : Na2SO4 + 7H2O
Na2SO4 10H2O : Na2SO4 + 10H2O
Na2SO4(aq) : Na2SO4 + x H2O
H2O(s), H2O(l), H2O(g) : 0Na2SO4 + H2O
It can be seen that the composition of some of the phases can be represented
by only one constituent while the others necessarily require two constituents.
Since two constituents are the smallest number by which the compositions of
all the phases can be defined, the number of components in sodium sulphate-
water system is two.
Another example is the equilibrium between CaCO3(s), CaO(s) and CO2(g)
as represented by the equation
CaCO3(s) CaO(s) + CO2(g)
Here the number of phases are three, viz., solid CaCO3, solid CaO and gaseous
CO2. The number of components in the above system is two since two species
out of the three are sufficient to express the compositions of all the three phases.
It is immaterial which of the two are selected for this purpose. For example:
(a) If CaO and CO2 are chosen, then
CaCO3(s) : CaO + CO2
CaO(s) : CaO + 0CO2
CO2(g) : 0CaO + CO2
(b) If CaCO3 and CaO are chosen, then
CaCO3(s) : CaCO3 + 0CaO
CaO(s) : 0CaCO3 + CaO
CO2(g) : CaCO3 – CaO
and so on.
 Phase Rule 97

Thus it is the number and not the nature that is important for determining
the components of the system.
Another example, which makes a clear distinction between the one
component system and the two-component system, is the dissociation of
ammonium chloride:
NH4Cl(s) NH3(g) + HCl(g)
This system has two phases, viz., solid NH4Cl and gaseous phase containing
ammonia and hydrogen chloride. If the dissociation is carried out in vacuum, then
the number of components of the system is one. This is due to the fact that in
the gaseous phase both HCl and NH3 are always present in equal amounts and
thus its composition can be represented by NH4C1 (= x NH3 + x HC1). But if
the dissociation is carried out in the presence of arbitrary amounts of NH3 or/
and HCl, then the number of components of the system becomes two:
Solid NH4Cl : NH3 + HCl
Gaseous phase : x NH3 + y HCl
Degree of Freedom The degree of freedom or variance of the system is the minimum number of
independent variables such as temperature, pressure and concentration, that
must be ascertained so that a given system in equilibrium is completely defined.
For an illustration, we cite an example of water system. If only one phase
is present (solid, liquid or gas), then we have to describe values of at least two
parameters, namely, temperature and pressure, in order to define the system. For
example, we can have liquid water under different conditions of temperature and
pressure. Thus the water system has two degrees of freedom or it is bivariant.
Now consider two phases in equilibrium, for example, solid and liquid water, i.e.
solid water liquid water
It is well known that the temperature at which a solid melts depends upon the
external pressure. Thus if the value of one of the variables is fixed, the other
will automatically have a definite value. The usual melting point of 0 °C is
referred to one atm external pressure. In order to describe the above equilibrium
completely, we need to specify only one variable—either temperature or pressure;
hence the system has one degree of freedom, i.e. it is an univariant system.
Alternatively, The degree of freedom of the system may be defined as the
number of factors, such as temperature, pressure and concentration, which can
be varied independently without altering the number of phases. For a single
phase system, both temperature and pressure can be varied independently of
each other and thus the system is bivariant. For two phases in equilibrium, only
one variable can be varied as the other one will automatically have a fixed value
and thus the system is univariant.
Consider now the situation at the triple point of water where all the three
phases are in equilibrium with each other. This equilibrium is achieved at a
temperature of 0.009 8 °C and a pressure of 4.58 mmHg. Any change in the
values of these variables, converts the three-phase system into either two-phase
or one-phase system. Thus, none of the variables can be changed so long as we
98 A Textbook of Physical Chemistry

want to have all the three phases in equilibrium. Thus the system has zero degree
of freedom, or it is nonvariant (or invariant).

3.2 DERIVATION OF PHASE RULE

Phase rule is a general rule which is applicable to all types of reactive and
nonreactive systems. In a nonreactive system, we simply have the distribution
of various components in different phases without any complications such as
the chemical reaction between the components. We derive the rule, first, for a
nonreactive system and then show how the same rule can be used for a reactive
system.
Nonreactive System Consider a heterogeneous system of P phases at equilibrium containing in all
C components. Let us start with the assumption that all the C components are
present in all P phases. The system at equilibrium can be completely described
if we know the values of the variables listed in Table 3.2.1.
Table 3.2.1 Number of Variables to be Known to Define a
Given System Completely

Variables Number
(i) Temperature of the system 1
(ii) Pressure of the system 1
(iii) Concentration of each and every component in all the
P phases. For each phase, we will have to specify the
values of C concentration terms and thus for P phases,
we will have to specify in all PC values PC
Total number of variables that need to be specified PC + 2
Values of these variables can be obtained by solving the equations which
are applicable when the system is at equilibrium. There are two types of equations
which are available (Table 3.2.2).
Mathematically, we know that the number of variables that can be obtained
from a set of equations is equal to the number of equations. Thus if there are
as many equations as there are variables, then the temperature, pressure and
composition of the whole system in equilibrium can be determined. Such a
system, as stated earlier, is the nonvariant system. If the number of variables
exceeds the number of equations by one, then the equilibrium of the system
cannot be determined until one of the variables is arbitrarily chosen. Such a
system is called monovariant (or univariant) and has one degree of freedom.
Thus we see that the excess of variables over equations, which is called the
variance F of the system, is given as

Variance = Ê
Total number of variablesˆ ÊTotal number of equationsˆ
-
Ëthat need to be specifeed ¯ Ëthat are available ¯

Thus, from Tables 3.2.1 and 3.2.2, we have

F = (PC + 2) - {P + C (P - 1)}
 Phase Rule 99

Table 3.2.2 Types and Number of Equations which are Available

Equations Number
(i) Condition of sum of the amount fractions in any phase being
equal to one,
x1(1) + x2(1) + ◊ ◊ ◊ + xc (1) = 1

x1( 2 ) + x2( 2 ) + ◊ ◊ ◊ + xc ( 2 ) = 1
..........................................
x1( P ) + x2( p ) + ◊ ◊ ◊ + xc ( P ) = 1

There will be as many equations as the number of phases.

Thus their total number will be P. P
(ii) Thermodynamic condition of phase equilibria:
According to this, the species will be distributed in such a
manner that value of free energy of the system at equilibrium is
minimum. The condition for this is that the chemical
potential of any component will have the same value in all
the P phases, i.e.
m1(1) = m1(2) = ◊ ◊ ◊ = m1(P )
m2(1) = m2(2) = ◊ ◊ ◊ = m2(P )
... ... ... ... ...
mc(1) = mc(2) = ◊ ◊ ◊ = mc (P )

For each component, we will have (P – 1) equations and thus

for C components, the number of equations will be C(P – 1) C(P – 1)
Total number of equations that are available P + C(P – 1)
or F=C–P+2
or F+P=C+2 (3.2.1)
Equation (3.2.1) is the phase rule which connects the number of phases and
components with the variance of the system.
Let us verify the rule by calculating the variance of a one-component system:
Phase Rule One phase only P = l, F = C – P + 2 = l – l + 2 = 2
Two phases in equilibrium P = 2, F = C – P + 2 = l – 2 + 2 = l
Three phases in equilibrium P = 3, F = C – P + 2 = l – 3 + 2 = 0
Thus, we see that the calculated degrees of freedom agree with
experimentally observed values of the one-component water system.
Comment on the The condition that all the components must be present in every phase, which
Phase Rule has been used above in deriving the phase rule, is not altogether essential. The
rule is applicable even if any component is missing in any of the phases. Say,
for example, the component number 1 is missing from the phase number 1.
We can once again derive the phase rule by following the procedure described
earlier. Tables 3.2.3 and 3.2.4 describe the number of variables and equations
for the present case.
100 A Textbook of Physical Chemistry

Table 3.2.3 Number of Variables to be Known to Define a given System Completely

Variables Number

(i) Temperature 1
(ii) Pressure 1
(iii) Concentration of components in different phases:
For the first phase, (C – 1) concentration terms and
for the remaining (P – 1) phases, C terms for each phase (C–1)+C(P–1)
Total number of variables that need to be specified (C–1)+C(P–1)+2
= CP + 1

Table 3.2.4 Types and Number of Equations Available

Equations Number
(i) Condition of amount fraction:
x2(1) + x3(1) + ◊ ◊ ◊ + xc (1) = 1
x1(2) + x2(2) + ◊ ◊ ◊ + xc (2) = 1

x1(P ) + x2(P ) + ◊ ◊ ◊ + xc(P ) = 1

There will again be in all P equations P

(ii) Condition of thermodynamic equilibrium:
For the component 1
m1(2) = m1(3) = ◊ ◊ ◊ = m1(P )
(P – 2)
For other components
m2(1) = m2(2) = ◊ ◊ ◊ = m2(P )

mc(1) = mc(2) = ◊ ◊ ◊ = mc (P )
(C – 1) (P – 1)
There will be (P – 2) equations for the component
number 1, one less as compared to others as it is
absent in the phase number 1
Total number of equations that are available P + (P – 2) + (C – 1) (P – 1)
= {P + C(P – 1)} – 1

From Tables 3.2.3 and 3.2.4, we have

Ê Total number ˆ Ê Total number of ˆ

Variance of the system = Á -
Ë of variables ˜¯ ÁË equations ˜¯
F = CP + 1 - [P + C (P - 1) - 1]
F =C-P +2
The above equation is the same as Eq. (3.2.1). Thus we see that the effect of
one of the components missing is that both the number of variables and the
number of equations have been reduced by one. Thus the difference is the same
and the phase rule remains unchanged
 Phase Rule 101

Reactive System Let us consider a heterogeneous system composed of arbitrary amounts of C

constituents. For the sake of simplicity we assume that four of the constituents
are chemically active, capable of undergoing the reaction
ν1A1 + ν2A2 ν3A3 + ν4A4 ; (All ν s are positive)
As usual, we can write down the number of variables that are needed to
describe the system completely and the number of equations that are available
at equilibrium (Tables 3.2.5 and 3.2.6).
Table 3.2.5 Number of Variables to be Stated to Define a Given System Completely

Variables Number
(i) Temperature 1
(ii) Pressure 1
(iii) Concentration of constituents in different phases CP
Total number of variables CP + 2

Table 3.2.6 Types and Number of Equations which are Available

Equations Number

(i) Condition of amount fraction:

x1(1) + x2(1) + ◊ ◊ ◊ + xc (1) = 1
x1(2) + x2(2) + ◊ ◊ ◊ + xc (2) = 1

x1(P ) + x2(P ) + ◊ ◊ ◊ + xc(P ) = 1

P
(ii) Condition of thermodynamic equilibrium between phases:
m1(1) = m1(2) = ◊ ◊ ◊ = m1(P )
m2(1) = m2(2) = ◊ ◊ ◊ = m2(P )

mc(1) = mc(2) = ◊ ◊ ◊ = mc (P ) C(P – 1)

(iii) Besides above two conditions, there is another condition
which has to be satisfied for the reactive system, that is,
the thermodynamic condition of reaction equilibrium.
~
At
equilibrium, the value of reaction potential, rG is zero. Thus

Èpositive for products

0 = D rG = Â n jm j where n j -Í
Înegative for reactants
j

For the given reaction, we have

0 = n 3 m3 + n 4 m 4 - n1m1 - n 2 m2

or n1m1 + n 2 m2 = n 3 m3 + n 4 m 4
Thus, we get one more equation 1
Total number of equations that are available P + C(P – 1) + 1
102 A Textbook of Physical Chemistry

From Tables 3.2.5 and 3.2.6, we have

Variance = Number of variables - Number of equations
F = CP + 2 - [P + C (P - 1) + 1}
F = (C - l) - P + 2

Similarly, if two independent reactions are possible, then we get

F = (C - 2) - P + 2
Generalizing, we have
F = (C - r ) - P + 2
where r is the number of independent reactions that are taking place in the
system.
Example Involving Up to now, we have considered three kinds of equations amongst the variables
Chemical Equilibrium T, P, and the xs. These are: (a) equations of phase equilibria; (b) equations of
with Additional reaction equilibria; and (c) equations of the type  xi = 1. Sometimes a chemical
i
Restricting reaction takes place in such a manner that additional equations expressing further
Conditions restriction upon the xs are to be satisfied. One such example, as cited earlier, is
the decomposition of NH4Cl(s) in vacuum:
NH4Cl(s) NH3(g) + HCl(g)
In the gaseous phase, the additional restriction which always exists is that
xNH3 = xHCl

This constitutes a fourth types of equation, which should also be included

wherever it is applicable.
Another example of additional restricting equation among the xs is provided
by the phenomenon of dissociation in solution. Suppose that we have a system in
which a salt is dissolved in a solvent. Suppose that the salt dissociates according
to the scheme given below:
AB A+ + B–
All the ions remain in the solution and no precipitate is formed.
Consequently, we have the additional restricting equation
x A + = x B-

If multi-dissociation takes place as shown below.

A B+ + C –
C– D+ + E2–
E2– F+ + G3–
 Phase Rule 103

then three independent restricting equations among the xs are available. These are
xB+ = xG3- + xE2- + xC-

xD+ = xG3- + xE2-

and xF+ = xG3-

Adding these equations, we get the dependent equation

xB+ + xD+ + xF+ = 3xG3- + 2xE2- + xC-

which expresses the condition of electrical neutrality.

Final Form of the If, in general, a reactive system has r independent reactions and Z independent
Phase Rule restrictive conditions, then the number of equations that are available at
equilibrium is:

of equations (
Total number = Equations due to the
condition of amount fractions ) (
+ Equations due to the
phase equilibria )
+ ( Equations due to the ) + ( Equations due to
chemical reactions restricting conditions)
= P + C (P - 1) + r + Z

Thus the variance is

F = (CP + 2) - {P + C (P - 1) + r + Z}
or F = (C - r - Z} - P + 2
or F = C¢ - P + 2

where C = C – r – Z and is known as the number of components of the system.

It is thus equal to the total number of constituents present in the system less
the number of independent chemical reactions and the number of independent
restricting equations. With this definition, we have put the phase rule in the form
that is applicable for a nonreactive system.

Problem 3.2.1 Show explicitly without using the phase rule that the one-component system has
(1) F = 2 when P = 1, (2) F = 1 when P = 2, and (3) F = 0 when P = 3.
Solution For a one-component system, we usually state the values of two variables, namely,
temperature and pressure, in order to define it completely. The concentration term is
not stated as it has a constant value for a given component. For example, water has a
concentration of 55.56 mol dm–3 (= 1000 g dm–3/18 g mol–1 at t = 4 °C and p = 1 atm)
when present in the liquid state and in the gaseous form (assumed to be ideal) it is
(n/V ) = p/RT
Now if we have only one phase, then two variables T and p will have to be stated and
thus its variance is two. If the number of phases at equilibrium are two, then we have one
relation
m(1) (T , p) = m(2) (T , p)
104 A Textbook of Physical Chemistry

where μ(1) and μ(2) are the chemical potentials in phases 1 and 2, respectively. Thus,
we have one relation connecting T and p and we have seen earlier that it is Clapeyron
equation. Hence if one variable is stated, then the other one can be calculated from the
above relation and thus the variance is only one.
For three phases in equilibrium, two equations are available:
m(1) = m(2) and m(2) = m(3)
Thus the values of the two variables, namely, temperature and pressure, can be obtained
from the above relations and therefore the system is nonvariant.

3.3 SOME TYPICAL EXAMPLES TO COMPUTE THE NUMBER OF COMPONENTS

We have earlier defined the number of components as the minimum number of
independent chemical constituents required to express the composition of each
and every phase of a system. This definition is completely in agreement with
the definitions given below for the reactive and the nonreactive systems.
For nonreactive system: Number of components = Number of
constituents
For reactive system: Number of components = (Number of
constituents)
– (Number of chemical
reactions)
– (Number of restricting
conditions)
Let us illustrate the above consistency with the help of a few typical
examples.
Sodium Sulphate- As stated earlier, it is a two-component system. It can be shown that so long as
Water System no precipitate is formed by virtue of a reaction between salt and water, the
number of components is always two no matter what else is assumed to take
place in the solution. We consider below four typical assumptions regarding the
nature of the system.
Neglecting all dissociations There are two constituents, no chemical reaction,
and no restricting equation. Hence
C¢ = C - r - Z = 2 - 0 - 0 = 2
Complete dissociation of the salt The total number of constituents present
in the solution are three: Na+, SO 42– and H2O. Since there is one restricting
condition:,
xNa + = 2xSO2-
4

we have
C¢ = C - r - Z = 3 - 0 - 1 = 2
Partial dissociation of the salt The dissociation may be represented as
+
Na2SO4 Na + SO42–
 Phase Rule 105

Now the system possesses four constituents, namely, Na2SO4, Na+, SO42– and
H2O. There is one reaction and one restricting condition:

xNa + = 2xSO2-
4

Thus, we have

C¢ = C - r - Z = 4 - 1 - 1 = 2

Dissociation of water also We have the following two equilibrium reactions:

Na2SO4 Na+ + SO42–

H2O H+ + OH–

The different constituents are Na2SO4, Na+, SO42–, H2O, H+ and OH–, a total of
six. There are two reactions and two restricting conditions:

xNa + = 2xSO2- and xH+ = xOH -

4

Thus C¢ = C - r - Z = 6 - 2 - 2 = 2

Sodium Dihydrogen It can be shown that this system is a two-component system irrespective of
Phosphate-Water whatever chemical changes may be considered in the solution except that no
System precipitate is formed.
Neglecting all dissociations There are two constituents, no chemical reaction
and no restricting equation. Hence

C¢ = C - r - Z = 2 - 0 - 0 = 2
Single dissociation of the salt We may represent the dissociation as
NaH2PO4 Na+ + H2PO4–

There are four constituents (NaH2PO4, H2O, Na+ and H2PO4–), one chemical
reaction and one restricting equation:
xNa + = xH -
2 PO 4

Hence C¢ = C - r - Z = 4 - 1 - 1 = 2

Multiple dissociation of the salt The multistep dissociation may be represented

as

NaH2PO4 Na+ + H2PO4–

H2PO4– H+ + HPO42–

HPO42– H+ + PO43–
106 A Textbook of Physical Chemistry

There are seven constituents, NaH2PO4, Na+, H2PO4–, H+, HPO42–, PO43– and H2O.
Number of chemical reactions = 3
Number of independent restricting equations = 2:
xNa + = xPO3- + xHPO2- + xH - (3.3.1)
4 4 2 PO 4

xH+ = 2xPO3- + xHPO2- (3.3.2)

4 4

(Note: One may consider the charge balance expression

xNa + + xH+ = xH - + 2 xHPO2- + 3 xPO3-

2 PO 4 4 4

Equation (3.3.2) may be obtained by subtracting Eq. (3.3.1) from the above
expression).

Thus C¢ = C - r - Z = 7 - 3 - 2 = 2

Dissociation of water also Besides the dissociation given in part (iii), we also
have
H2O H+ + OH–

There are total eight constituents, NaH2PO4, Na+, H2PO4–, H+, HPO42–,
PO43–, OH– and H2O.
Number of chemical reactions = 4
Number of restricting equations = 2:
xNa + = xPO3- + xHPO2- + xH -
4 4 2 PO 4

xH+ = 2xPO3- + xHPO2- + xOH -

4 4

Thus C¢ = C - r - Z = 8 - 4 - 2 = 2

Aluminium Chloride- In this case, AlCl3 combines with water according to the equation:
Water System
AlCl3 + 3H2O = Al(OH)3 + 3HCl
Some of the Al(OH)3 is precipitated out. The dissociation of the various species
will be as follows:

AlCl3 Al3+ + 3Cl–; Al(OH)3 Al3+ + 3OH–

H2O H+ + OH–; HCl H+ + Cl–

Total number of constituents = 8:

AlCl3, H2O, Al(OH)3, HCl, Al3+, Cl–, H+ and OH–

Number of chemical reactions = 4

 Phase Rule 107

Since some of the Al(OH)3 has precipitated out, there is only one restricting
equation, namely, that expressing the electrical neutrality of the solution

3xAl3+ + xH+ = xOH - + xCl -

Thus the number of components = 8 – 1 – 4 = 3.

If we assume complete dissociation of AlCl3 and that of HCl, we will have
C = 6, r = 2 and Z = 1
Thus C =C–Z–r=6–1–2=3

Example 3.3.1 Show that an aqueous system containing K+, Na+ and Cl– is a three-component system
whereas K+, Na+, Cl– and Br– is a four-component system. What are the number of
components if the salts are present in equal amounts?

Solution (a) K+, Na+, Cl– and H2O system: In this case, we have

Number of reactions, r = 3:

H2O H+ + OH–

KCl K+ + Cl–

NaCl Na+ + Cl–

Number of constituents, C = 8:
H2O, KCl, NaCl, H+, OH–, K+, Cl– and Na+
Number of restricting equations, Z = 2:
Electrical neutrality xNa + + xK + + xH+ = xCl - + xOH -
Water dissociation xH+ = xOH -
Hence, Number of components, C = C – r – Z = 8 – 3 – 2 = 3
If the salts are present in equal amounts, then one more restricting equation exists, i.e.
xNa + = xK +

Hence, here

Number of components, C = C – r – Z = 8 – 3 – 3 = 2

Alternatively, leaving KCl and NaCl on the basis that they are strong electrolytes, we
have

Number of constituents, C = 6:

H2O, H+, OH–, Na+, K+, Cl–

Number of reactions, r = 1:
H2O H+ + OH–
108 A Textbook of Physical Chemistry

Number of restricting equations, Z = 2:

xH + = xOH - and xNa + + xK + = xCl -

Hence, Number of components, C = C – r – Z = 6 – l – 2 = 3

If the salts are present in equal amounts, then one more restricting equation exists,
i.e.
xNa + = xK +

Hence, here
Number of components, C = C – r – Z = 6 – l – 3 = 2
(b) K , Na+, Cl–, Br– and H2O system: In this case, we have
+

Number of reactions, r = 5;
H2O H+ + OH– NaCl Na+ + Cl–
KC1 K+ + Cl– KBr K+ + Br–
NaBr Na+ + Br–
Number of constituents, C = 11
H2O, H+, OH–, KCl, K+, Cl–, NaBr, Na+, Br–, NaCl and KBr
Number of restricting equations, Z = 2:

Electrical neutrality xNa + + xK + + xH + = xCl - + xBr - + xOH -

Water dissociation xH + = xOH -

Hence, Number of components, C = C – r – Z = 11 – 5 – 2 = 4

If the salts are present in equal amounts, then we have three independent restricting
equations:
xNa + = xK + ; xH+ = xOH - ; and xCl - = xBr -

Hence, Number of components, C = C – r – Z = 11 – 5 – 3 = 3

Alternatively, leaving KCl, NaBr, NaCl and KBr as they are strong electrolytes, we
have:
Number of constituents, C = 7:
H2O, H+, OH–, Na+, K+, Cl– and Br–
Number of reactions, r = 1:
H2O H+ + OH–
Number of restricting conditions, Z = 2:
xH + = xOH - and xNa + + xK + = xCl - + xBr -
Hence, Number of components, C = C – r – Z = 7 – 1 – 2 = 4
 Phase Rule 109

If the salts are present in equal amounts, then we have three independent restricting
equations:

xNa + = xK + ; xCl - = xBr - and xH+ = xOH -

Hence, Number of components, C = C – r – Z = 7 – 1 – 3 = 3

Example 3.3.2 Show that NH4Cl(s) – NH3(g) – HCl(g) system in which pNH3 = pHCl is a one-component
system whereas when pNH3 pHCl is a two-component system.

Solution (a) NH4Cl(s) – NH3(g) – HCl(g) when pNH3 = pHCl. The condition of pNH3 = pHCl would
arise only when the gases are obtained by the sublimation of NH4Cl(s). Thus, we have
Number of reactions, r = 1 :
NH4Cl(s) NH3(g) + HCl(g)
Number of constituents, C = 3:
NH4Cl(s), NH3(g) and HCl(g)
Number of restricting equations, Z = 1:
pNH3 = pHCl
Hence, Number of components, C = C – Z – r = 3 – l – l = l
(b) NH4Cl(s) – NH3(g) – HCl(g) when pNH3 pHCl: Here, we have
Number of reactions, r = 1
Number of constituents, C = 3
Number of restricting equations, Z = 0
Hence, Number of components, C = C – Z – r = 3 – 0 – l = 2

Example 3.3.3 Determine the number of components in a system containing NH4Cl(s), NH4+(aq),
Cl–(aq), H2O(1), H3O+(aq), H2O(g), NH3(g), OH–(aq), and NH4OH(aq).

Solution We have
Number of constituents, C = 9
Number of equilibrium reactions, r = 5:
NH4Cl(s) + aq NH +4(aq) + Cl–(aq)
NH4+(aq) + 2H2O NH4OH(aq) + H3O+(aq)
NH3(g) + H2O(l) NH4OH(aq)
2H2O(1) H3O+(aq) + OH–(aq)
H2O(l) H2O(g)
Number of restricting conditions, Z = 1:
xNH+ + xH + = xCl - + xOH - (condition of electroneutrality)
4 3O

Hence, Number of components, C = C – r – Z = 9 – 5 – 1 = 3

110 A Textbook of Physical Chemistry

Example 3.3.4 Consider a homogeneous mixture of four ideal gases capable of undergoing the reaction
ν1A1 + ν2A2 ν3A3 + ν4A4

Solution Determine the components if we start with (a) arbitrary amounts of A1 and A2 only, (b)
arbitrary amounts of all the four gases, and (c) ν1 moles of A1 and ν2 moles of A2 only.
(a) Number of constituents, C = 4:
A1, A2, A3 and A4
Number of reactions, r = 1
Number of restrictions, Z = 1:
[A3] : [A4] : : ν3 : ν4
Hence, Number of components, C = C – r – Z = 4 – 1 – 1 = 2
(b) Number of constituents, C = 4
Number of reactions, r = 1
Number of restrictions, Z = 0
Number of components, C = C – r – Z = 4 – 1 – 0 = 3
(c) Number of constituents, C = 4
Number of reactions, r = 1
Number of restrictions, Z = 2
[A1] : [A2] : : ν1 : ν2 and [A3] : [A4] : : ν3 : ν4
Hence, Number of components, C = C – r – Z = 4 – l – 2 = l

REVISIONARY PROBLEMS

3.1 (a) Explain with suitable examples the terms involved in the phase rule
F+P=C+2
(b) What do you understand by the reactive and nonreactive systems?
3.2 (a) Derive the expression of phase rule as applicable to a nonreactive system.
(b) Prove that the expression of phase rule remains unchanged even if one of the
components is missing in some of the phases present at equilibrium.
3.3 (a) What is the difference between the number of constituents and the number of
components of a given system?
(b) Show that for the reactive systems, the form of the phase rule remains unaltered
provided we define the number of components as
C =C–r–Z
where C is the number of constituents present, r is the number of independent
reactions, and Z is the number of independent restricting equations.

TRY YOURSELF PROBLEMS

3.1 Show explicitly without using the phase rule that the two-component system has
(1) F = 3 if P = 1; (2) F = 2 if P = 2; (3) F = 1 if P = 3; and (4) F = 0 if P = 4.
3.2 Show that it is not possible to have more than three phases at equilibrium for a
one-component system.
 Phase Rule 111

3.3 Blue copper sulphate crystals decompose and release their water of hydration when
heated. How many phases and components are present in an otherwise empty heated
vessel?
3.4 The absence of a few components in some phases does not alter the phase rule
relation, F + P – C + 2. Derive the above conclusion by taking the following system
of three components distributed over five phases:

A+B �
��
��� B+C �
��
��� A+B+C �
��
��� A ��
���� A+C
Phase 1 Phase 2 Phase 3 Phase 4 Phase 5

3.5 How many degrees of freedom, number of phases and number of components are
present in each of the following systems:
(a) Solid carbon in equilibrium with gaseous CO, CO2 and O2 at 100 °C.
(b) Solid CaCO3 is heated in a sealed tube.
(c) I2 dispersed between liquid water and CCl4 at 1 atm pressure with no solid I2
present.
(d) CuSO4 5H2O(s) CuSO4 3H2O(s) + 2H2O(g)
(e) Fe(s) + H2O(g) FeO(s) + H2(g)
(f) Liquid and its vapour in equilibrium with each other.
(g) An aqueous solution of NaCl and Na2SO4.
(h) An aqueous solution of KCl and Na2SO4.
(i) CH3COONH4(s), CH3COO–(aq), NH+4(aq), H3O+(aq), OH–(aq), CH3COOH(aq),
H2O(1), H2O(g), taking hydrolysis into account.
(j) An azeotrope in a binary system.
(k) Water vapour heated to 2 000 K so that H2O, H2, O2, OH, O and H are present
at equilibrium.
(l) An arbitrary mixture of H2 and O2 has been heated to 2 000 K, so that H2O,
H2, O2, OH, H and O are present at equilibrium.
(m) A pure substance at its critical point.
(n) An aqueous solution containing LiCl, NaCl, KC1 and CsCl.
3.6 Suppose that a one-component system exhibits a gas phase, a liquid phase and three
solid modifications. How many one-, two-, three-, and four-phase, equilibria are
theoretically possible?
3.7 Compute the number of components in the following systems:
(i) A solution containing Na+, Cl–, Ag+, NO–3, AgCl(s) and H2O.
(ii) A solution containing H+, OH–, Na+, Cl–, Ag+, NO–3, AgCl(s) and H2O.
(iii) A solution containing H2O, Na+, Cl–, K+, NO3–, NH +4 , NH3, H+ and OH–.
(iv) An aqueous solution containing H3PO4, H2PO4, HPO4–, PO43–, Na+, and H+
at 1 atm pressure.
(v) NH4Cl(s), NH4+(aq), Cl–(aq), H2O(1), H3O+(aq), H2O(g), NH3(g), OH–(aq),
and NH4OH(aq).
(Ans. (i) 4, (ii) 4, (iii) 6, (iv) 3, (v) 3)
 4 Solutions

4.1 IDEAL SOLUBILITY OF GASES IN LIQUIDS

Application of the Solubility of a gas in a liquid depends on temperature and pressure. Therefore,
Phase Rule both these variables should be stated while expressing the solubility of a gas in
a liquid. This conclusion can also be arrived at with the help of the phase rule.
In the present case, we have
Number of components, C = 2 (Gas and liquid)
Number of phases, P=2 (Liquid phase and gaseous phase)
Thus Degrees of freedom of the system, F = C + P – 2 = 2 + 2 – 2 = 2
that is, the system is bivariant and values of two parameters, namely, temperature
and pressure, must be stated in order to define the system completely.
Thermodynamic At the saturation point, where no more gas dissolves in a solution, there exists
Derivation of Ideal an equilibrium between the dissolved gas and the undissolved gas, i.e.
Law of Solubility of Dissolved gas in solution Undissolved gas
Gases
The thermodynamic condition of equilibrium is
* (T , p)
m2(sol) (T , p, x2 ) = m2(g) (4.1.1)

where x2 is the amount fraction of the gas in the saturated solution. If the
solution is assumed to be ideal, then
* + RT ln x
m2(soln) = m2(1) 2 (4.1.2)†

Substituting Eq. (4.1.2) in Eq. (4.1.1), we get

* + RT ln x = m *
m2(1) 2 2(g)

* - m*
m2(g) D vap m2*
2(1)
or ln x2 = = (4.1.3)
RT RT

†
If the solution is not ideal but an ideally dilute solution, then μ*2(1) is replaced by μ2(1, hs)
where μ2(1, hs) represents the chemical potential of liquid solute in a hypothetical state.
See, section 4.6 for detail. In applying Eq. (4.1.2), the temperature of the gas is below
its critical temperature so that the gas exists in the liquid form in the solution.
 Solutions 113

According to Eq. (4.1.3), the amount fraction of solute in a saturated solution

is a function of temperature of the solution. To determine this functionality, we
differentiate Eq. (4.1.3) with respect to x2, keeping p constant. Thus, we have

1 1 Ï ∂( D vap m2* /T ) ¸ Ï ∂T ¸
= Ì ˝ Ì ˝
x2 RÓ ∂T ˛ p Ó ∂x2 ˛ p

Using Gibbs-Helmhlotz equation, we get

1 D vap H 2, m Ê ∂T ˆ
=- Á ˜
x2 RT 2 Ë ∂x2 ¯ p

dx2 D vap H 2, m dT
or =- ( p constant) (4.1.4)
x2 R T2

To determine the variation of x2 with T, we integrate the above expression to

give
x2 dx2 T D vap H 2, m dT
Ú1 x2
=-Ú *
Tb R T2
(4.1.5)

where T *b is the boiling point of the pure liquid solute (x2 = 1) and x2 is the
solubility of the solute at temperature T of the solution.
Assuming vapH2, m to be independent of temperature, Eq. (4.1.5) yields

D vap H 2, m Ê 1 1 ˆ
ln x2 = Á - *˜ (4.1.6)
R Ë T Tb ¯

Equation (4.1.6) is an expression of the ideal law of solubility. According to

this law, the solubility of a substance depends only on the characteristics of the
gas through vapH2,m and T *b and is independent of the nature of the solvent.
Factors Determining The following dependence on the solubility of the gases may be concluded.
Ideal Solubility
A comparatively lesser value of T *b makes the right side of Eq. (4.1.6) more
negative indicating the lesser value of x2 (i.e. lesser is the solubility). For
example, hydrogen and helium are much less soluble as compared to carbon
dioxide ammonia and sulphur dioxide.
A comparatively larger value of T *b makes the right side of Eq. (4.1.6) lesser
negative indicating the larger value of x2 (i.e. larger is the solubility).
A comparatively lesser value of vapH2, m makes the right side of Eq. (4.1.6)
lesser positive indicating the lesser value of x2 (i.e. lesser is the solubility).
Increasing the value of T makes the right side lesser positive indicating the
lesser value of x2 (i.e. lesser is the solubility).
Correlating If x2 and x 2 are the solubilities of gases at temperatures T1 and T2, respectively,
Solubilities at Two we may write
Temperatures
114 A Textbook of Physical Chemistry

D vap H 2, m Ê 1 1ˆ
ln x2 =
R ÁË T - * ˜¯ (4.1.7)
1 Tb

D vap H 2, m Ê 1 1ˆ
ln x2¢ = Á - *˜ (4.1.8)
R Ë T2 Tb ¯

Subtracting Eq. (4.1.7) from Eq. (4.1.8), we get

x2¢ D vap H 2, m Ê 1 1ˆ
ln = Á - ˜ (4.1.9)
x2 R Ë T2 T1 ¯
Equation (4.1.9) relates the solubility of a gas in a solvent at two
temperatures of the solution.
Exception to Ideal It may be point out here that Eq. (4.1.6) represents ideal gas solubility and is
Solubility independent of the nature of the solvent. Solubility of a gas which can interact
with the solvent is very much enhanced. That is why gases like ammonia, carbon
dioxide, sulphur dioxide and hydrochloric acid are very easily soluble in water.
The interaction reactions are:
NH3 + H2O NH4OH NH4+ + OH–
CO2 + H2O H2CO3 HCO3– + H+
SO2 + H2O H2SO3 HSO3– + H+
HCl + H2O H3O+ + Cl–

Coefficients for Expressing Solubility of a Gas in a Liquid

Solubilities of gases can be expressed either in terms of absorption coefficient
or the coefficient of solubility.
Absorption The absorption coefficient was suggested by R. Bunsen and is known as Bunsen
absorption coefficient. At a given temperature, this coefficient is defined as the
volume of gas, reduced to STP (0 °C and 1 atm pressure), that has been dissolved
by unit volume of solvent under a partial pressure of 1 atm of the gas. If v0 is
the volume of gas dissolved, reduced to STP, by the volume V of the solvent
under the partial pressure p of the gas, the absorption coefficient is given by
v0 /p
a= (4.1.10)
V
The amount of gas dissolved by unit volume of solvent under the partial
pressure p is
(v0 /vm ) a
c= = (4.1.11)
Vp vm
where vm is the molar volume of the gas at STP.
The second unit of coefficient of solubility was suggested by W. Ostwald and
Solubility is defined as the volume of gas measured under given conditions of temperature
 Solutions 115

and pressure, that has been dissolved in a unit volume of the solvent. If v is the
volume of gas dissolved by the volume V of the solvent, then the coefficient of
solubility is
v
b= (4.1.12)
V
Relation between Assuming ideal behaviour for gas, we can write

pv (1 atm)v0
=
nRT nR(273 K)
v0T
Thus v= (4.1.13)
(273 K)( p/atm)
Substituting Eq. (4.1.13) in Eq. (4.1.12), we get

v v0T 1 Ê v ˆ T (1 atm)
b= = ◊ = Á 0˜
V (273 K)( p/atm) V Ë Vp ¯ (273 K)

T (1 atm)
or b =a (4.1.14)
(273 K)

4.2 EFFECT OF PRESSURE AND TEMPERATURE ON THE SOLUBILITY OF GASES

Effect of Pressure – The solubility of a gas in a liquid increases with the increase in the pressure of
Henry’s Law the gas. The quantitative relation connecting the solubility with pressure was
stated by W. Henry and is known as Henry’s law. The law states that at a
given temperature the mass of dissolved gas in a given volume of solvent is
proportional to the pressure of the gas with which it is in equilibrium.† If m is
the mass of the gas dissolved by unit volume of solvent at equilibrium pressure
p, then according to Henry’s law, we have
m μ p
or m = kp (4.2.1)
where k is the constant of proportionality. Thus, if a graph of the solubility and
the external equilibrium pressure is plotted, a straight line would be observed
(Fig. 4.2.1).

Example 4.2.1 At 273.15 K, 500 cm3 of water dissolves 15.03 cm3 of CH4(STP) under a partial pressure
of methane of 1 atm. If Henry’s law holds, what pressure is required to dissolve 0.001 mol
methane in 300 cm3 water?

Solution Amount of methane dissolved in 500 cm3 of water under a partial pressure of 1 atm of
methane is

†
For the solubility of a gas from a mixture of gases, the equilibrium pressure is the
partial pressure of the gas.
116 A Textbook of Physical Chemistry

Fig. 4.2.1 Variation of

solubility with pressure

v0 15.03 cm 3
n= = = 6.706 ¥ 10 -4 mol
Vm 22 414 cm 3 mol -1
Amount of methane dissolved per unit volume of water is
6.706 ¥ 10 -4 mol
n¢ = = 1.341 ¥ 10 -6 mol cm -3
500 cm 3
Amount of methane to be dissolved per unit volume of water is
0.001 mol
n≤ = = 3.333 ¥ 10 -6 mol cm -3
300 cm 3
Since mass of gas amount of gas, we can write Henry’s law as

n ≤ = k ¢p ≤ and n¢ = k ¢p¢

Ê n¢¢ ˆ Ê 3.33 ¥ 10 -6 mol cm -3 ˆ

Hence, p¢¢ = Á ˜ p¢ = Á (1 atm)
Ë n¢ ¯ Ë 1.341 ¥ 10 -6 mol cm -3 ˜¯
= 2.485 atm

A Consequence of A direct consequence of Henry’s law is that the volume of an ideal gas, measured
Henry’s Law at the experimental pressure, that is dissolved in a given volume of the solvent
has a constant value. This can be proved as follows.
If v is the dissolved volume of the gas, measured at the experimental
pressure p, in a given volume of the solvent at temperature T, then according
to ideal gas law, we have
m
pv = nRT = RT
M
Ê m ˆ RT
or v= Á ˜
Ë p¯ M
 Solutions 117

Substituting the value of (m/p) from Eq. (4.2.1), we have

RT
v=k
M
Since the right side of the above equation is constant for a given gas
(M constant) at a given temperature (T constant), it follows that the volume of
the gas dissolved in a given volume of the solvent has a constant value.
Thermodynamic The thermodynamic condition of equilibrium between dissolved and undissolved
Derivation of gases is
Henry’s Law * (T , p)
m2(sol) (T , p, x2 ) = m2(g) (4.2.2)
If the solution is considered to be ideally dilute, we have
*
m2(sol) = m2(1, hs) + RT ln x2

where the subscript 2(1, hs) represents hypothetical state of pure solute in the
liquid phase.† If the gas is assumed to be ideal, then
* = m ∞ + RT ln (p/p∞)
m2(g) 2(g)

With these, Eq. (4.2.2) becomes

*
m2(1, ∞
hs) + RT ln x2 = m 2(g) + RT ln (p/p∞)

x2 ∞ - m2(1,
m2(g) *
hs)
or ln = (4.2.3)
(p/p∞) RT

At a constant temperature, the right side of Eq. (4.2.3) is a constant. Hence

x2
ln = constant
(p/p∞)

or x2 = (constant) p (4.2.4)

For a dilute solution, we can write

n2 n2 m /M Ê 1 ˆ
x2 = = 2 2 = Á m
n1 + n2 n1 n1 Ë M 2 n1 ˜¯ 2
i.e. x2 μ m2

With this, Eq. (4.2.4) becomes

m2 = k p (Eq. 4.2.1)

which is Henry’s law.

†
See Section 4.6 for the hypothetical state of liquid solute.
118 A Textbook of Physical Chemistry

Applicability of It will be shown that Henry’s law is a special case of more generalized laws such
Henry’s Law as the distribution law and Raoult’s law. Since these laws are applicable only
for ideal systems, it is, therefore, expected that Henry’s law is also applicable
only to ideal systems.
A solution of gas in liquid will show ideal behaviour, provided the solubility
of the gas in the liquid is low (i.e. dilute solution) and that the gas itself shows
ideal behaviour. The real gases are known to behave ideally under the conditions
of high temperature and low pressure, but show deviations at low temperature
and high pressure. The deviations are pronounced for easily liquefiable gases.
Thus, it is expected that Henry’s law will be applicable for low soluble gases
at high temperatures and low pressures. The deviations from Henry’s law are
expected to be large at low temperatures and high pressures. These facts are in
agreement with the experimental results.
Henry’s Law and the It can be shown that Henry’s law is a special case of the distribution law.†
Distribution Law According to Henry’s law, we have

m
=k (4.2.5)
p

where m is the mass of the gas dissolved by a unit volume of the solvent, p
is the equilibrium pressure of the gas, and k is constant whose value depends
upon the temperature of the system.
The term m in Eq. (4.2.5) is the concentration term of the dissolved gas
expressed in mass of the gas dissolved per unit volume of solvent. It is proportional
to the concentration expressed as amount of gas dissolved per unit volume of
solvent or per unit volume of solution, if it is assumed that no change of volume
occurs when the gas dissolves in the solvent. Similarly, the pressure p of the
gas will be proportional to the concentration of the gas expressed as amount of
gas per unit volume of the gaseous phase. Thus Eq. (4.2.5) can be written as

Concentration of gas in liquid phase

= Constant (4.2.6)
Concentration of gas inn gaseous phase

The value of constant depends only on temperature and not on pressure of the
gas.
Equation (4.2.6) is, in fact, the statement of the distribution law. It may be
stated that the distribution law is applicable only for common species in both the
phases. Thus a gas which undergoes a change in a solvent, such as change in
molecular complexity, compound formation between solute and solvent, ionization,
etc., will not follow the conventional definition of Henry’s law as given by
Eq. (4.2.6). However, if concentration of the gas in the liquid phase which exists
in the same form as that of the gaseous phase, is determined and substituted in
Eq. (4.2.6), the ratio is found to be independent of the pressure of the gas. Thus

†
See Section 4.19
 Solutions 119

Henry’s law is still applicable provided concentration of the gas in the liquid
phase, which exists in the same form as that of gaseous phase, is taken into
consideration. One example is the dissolution of ammonia in water, where the
following reaction takes place:
NH3 + H2O NH4+ + OH–

If cl and cg represent the total concentrations of ammonia in the liquid and

gaseous phases, respectively, then c1/cg is not constant. If α is the fraction of
the dissolved ammonia which has undergone reaction with water, then the ratio
c1(1 – α)/cg is found to have a constant value irrespective of the total amount
of NH3 that has been dissolved.
Effect of Temperature The solubility of gases in water is generally exothermic in nature. In accordance
on Solubility to Le-Chatelier principle, their solubility decreases with increase in temperature.
of Gases in Water If Henry’s law is interpreted as

Concentration of gas in liquid phase

K= (Eq. 4.2.6)
Concentration of gaas in gaseous phase

then the effect of temperture on K may be expressed by the van’t Hoff equation:

d ln K D H∞
= r 2m (4.2.7)
dT RT

where r Hºm is the differential enthalpy of solution for 1 mol of the gas in the
saturated solution at temperature T. If r H mº is assumbed to be independent of
temperature, the integrated form of the above expression is

K2 D H Ê 1 1ˆ
ln =- r m Á - ˜ (4.2.8)
K1 R Ë T2 T1 ¯

For the constant external pressure of the gas, we find from Eq. (4.2.6) that
K μ (cgas )liquid

Hence, Eq. (4.2.8) may be written as

c2 D H Ê 1 1ˆ
ln =- r m Á - ˜ (4.2.9)†
c1 R Ë T2 T1 ¯

where c1 and c2 are the solubilites of the gas at tempeturares T1 and T2,
respectively.
Since Bunsen absorption coefficient (α), is directly proportional to the
concentration is gas in the solution, Eq. (4.2.9) may also be expressed as

†
Comparing Eqs (4.1.9) and (4.2.9) we find that r Hm =– vap H2, m for an ideal solution.
120 A Textbook of Physical Chemistry

a2 D H Ê 1 1ˆ
ln =- r m Á - ˜ (4.2.10)
a1 R Ë T2 T1 ¯

Accoridng to Eqs (4.2.9) and (4.2.10), it follows that the graph between
ln c2 (or ln α) and 1/T is linear with the slope equal to (– r Hm/R).

4.3 HENRY’S LAW AND RAOULT’S LAW

Henry’s Law in Equation (4.2.4) is, in fact, Henry’s law expressed in amount fraction form. This,
Amount Fraction however, may be obtained from the conventional Henry’s law expressed in the
Form mass of the gas dissolved in the given volume of solution. If m2 is the mass of
the gas that is dissolved at the gaseous pressure p2, then according to Henry’s
law, we have

m2 = kp2 (Eq. 4.2.1)

Dividing throughout by m1, the mass of the solvent, we have

m2 Ê k ˆ
= Á ˜ p2 = k ¢p2
m1 Ë m1 ¯

Dividing the two masses by the respective molar masses, we have

m2 /M2 Ê M ˆ
= Á k ¢ 1 ˜ p2 = k ¢¢p2
m1 /M1 Ë M2 ¯

n2
or = k ¢¢p2 (4.3.1)
n1

The amount fraction of the gas in the above solution is given by

n2
x2 =
n1 + n2

For a dilute solution as is the case for gases in liquids, n2 << n1, and thus
the amount fraction can be approximated as

n2
x2
n1

Substituting this in Eq. (4.3.1), we get

x2 = k ¢¢p2 (4.3.2)
 Solutions 121

Thus for a dilute solution Henry’s law can also be stated in terms of amount
fraction of gaseous solute in the saturated solution. According to this, the
solubility of a gas expressed in amount fraction is directly proportional to the
pressure of the gas.
Henry’s Law The solubility of a gas may be considered from the following two points of view:
Constant
(i) x2 may be regarded as the solubility of the gas under pressure p2.
(ii) p2 may be taken as the vapour pressure of a volatile solute when its
amount fraction in the dilute solution is x2, the vapour pressure of a solute in a
solution is proportional to its amount fraction. Mathematically, we have

1 (4.3.3)
p2 = x = kH x2
k ¢¢ 2
where kH is equal to 1/k and is known as Henry’s law constant. It has the unit
of pressure.
The values of Henry’s law constant for some gases in water and benzene
at 25 ºC are shown in Table 4.3.1.

Table 4.3.1 Henry’s Law constant for some Gases at 25 ºC

kH /kbar kH/kbar

Gas Water Benzene Gas Water Benzene

H2 71.7 3.93 CO 58.8 1.52

N2 86.4 2.27 CH4 40.4 0.49
O2 44.1 1.24 C2H6 30.3 0.068

From Eq. (4.3.3), it follows that the gases will have the same value of kH x2
provided the gaseous pressure p2 has the same value. From this it follows that
the larger the value of kH, the smaller the solubility (in terms of x2) of the
gas.
Correspondence In a special case where Henry’s law is applicable over the entire range of
between Henry’s concentrations starting from x2 = 0 (infinitely dilute solution, i.e. pure solvent)
and Raoult’s Laws to x2 = 1 (pure liquid solute), the constant k is given as
x2 1 1
k ¢¢ = = and thus kH = = p2*
p2 p2* k ¢¢
where p2* is the vapour pressure of pure liquid solute (x2 = 1). With this
Eq. (4.3.3) can be written as

p2
x2 = or p2 = x2 p2* (4.3.4)
p2*
122 A Textbook of Physical Chemistry

Equation (4.3.4) is the statement of Raoult’s law when applied to a volatile

solute. Hence it may be concluded that Raoult’s law is a special case of Henry’s
law; all systems which obey Raoult’s law must satisfy Henry’s law, but the
reverse is not true unless Henry’s law is applicable over the entire range
of concentrations.
Comment on Equation (4.3.4) is useful in computing the solubility (in terms of amount
Eq. (4.3.4) fraction x2) of a gas in a solvent at a temperature lower than its critical temperature,
provided the solution behaves in an ideal manner. Since x2 and p2* have inverse
dependence, a lower value of p2* results into higher value of x2 (i.e. solubility)
and vice versa. A gas which is difficult to liquefy has a low boiling point.
Consequently, it has a larger vapour pressure and thus has a lower solubility
in a solvent. Easily liquefiable gases have higher boiling points, lower vapour
pressures and thus exhibit larger solubility.
Equation (4.3.4) is also useful in estimating the solubility of a gas at a
temperature higher than its critical temperature provided the hypothetical vapour
pressure of the gas in the liquid form at the said temperature is available. This
vapour pressure may be estimated by the extrapolation method or by the use
of Clapeyron-Clausisus equation

p2 D vap H m Ê 1 1ˆ
ln =- Á - ˜
p1 R Ë T2 T1 ¯

provided vapHm may be assumed to be independent of temperatures. For example,

the hypothetical vapour pressure of liquid methane (critical temperature – 95.5 ºC)
at 20 ºC is estimated to be 310 atm. Its solubility at 1 atm gaseous pressure in
any solvent would be
p2 1 atm
x2 = = = 0.003 2
p2* 310 atm

which is very near to its solubility in n-hexane.

The solubility of gas in amount fraction is theoretically independent of
the nature of the solvent. Any deviation may be attributed to departure from
the ideal behaviour.

Example 4.3.1 (a) For a solution of acetone in chloroform, it is found that the value of Henry’s law
constant is 150 Torr when the solution is at a temperature of 308 K. Calculate the value
of vapour pressure of acetone when the amount fraction is 0.12.
(b) Assuming that Henry’s law is applicable over sufficient range of composition to
make the calculation valid, compute the composition at which Henry’s law pressure of
chloroform is equal to Henry’s law pressure of acetone at 308 K. (Given: Henry’s law
constant for chloroform 175 Torr.)
Solution (a) Henry’s law is given as p = kH x
Substituting the given values of kH and x, we get
p = (150 Torr) (0.12) = 18.0 Torr
 Solutions 123

(b) Here p = 18.0 Torr and kH = 175.0 Torr.

p 18.0 Torr
Hence x= = = 0.103
kH 175 Torr

Example 4.3.2 Henry’s law constants as defined by the relation kH = pA/xA for oxygen and nitrogen
dissolved in water at 273 K are 2.53 × 109 Pa and 5.47 × 109 Pa, respectively. A sample
of water at a temperature just above 273 K was equilibrated with air (20% oxygen and
80% nitrogen) at 1 atm. The dissolved gas was separated from a sample of this water
and then dried. (a) Determine the composition of this gas. (b) Calculate the freezing
point of the saturated water. Given: Kf = 1.86 K kg mol–1.

Solution (a) Partial pressure of oxygen, pO2 = 0.2 atm = 20 265 Pa

Partial pressure of nitrogen, pN2 = 0.8 atm = 81 060 Pa
Amount fraction of dissolved oxygen in water

pO2 20 265 Pa
= = = 8.01 ¥ 10 -6
kH (O2 ) 2.53 ¥ 109 Pa

Amount fraction of dissolved nitrogen in water

pN2 81 060 Pa
= = = 1.48 ¥ 10 -5
kH (N 2 ) 5.47 ¥ 109 Pa

Amount of dissolved oxygen 8..01 ¥ 10 -6

= = 0.541
Amount of dissolved nitrogen 1.48 ¥ 10 -5

0.541
Hence Amount per cent of O2 = ¥ 100 = 35.11
1.541

Amount per cent of N2 = 100 – 35.11 = 64.89

(b) Total amount fraction of dissolved gas = 8.01 × 10–6 + 1.48 × 10–5 = 2.281 × 10–5
For such a small value of amount fraction, we may write

nsolute = 2.281 ¥ 10 -5 mol and nwater = 1 mol

Hence, molality of the solution is

nsolute (2.28 ¥ 10 -5 mol)

m= = = 1.267 ¥ 10 -3 mol kg -1
msolvent (18 ¥ 10 -3 kg)

The depression in freezing point of water is

– DTf = Kf m = (1.86 K kg mol –1 ) (1.267 × 10 –3 mol kg –1 )

= 0.002 36 K

The freezing point of the saturated water is – 0.002 36 °C.

124 A Textbook of Physical Chemistry

4.4 RAOULT’S LAW FOR SOLVENT AND HENRY’S LAW FOR SOLUTE
Application of It can be shown that if Henry’s law is applicable to the volatile solute, then
Duhem-Margules Raoult’s law is applicable to the volatile solvent. We start with the Duhem-
Equation Margules equation (Section 4.15), such that
d log (p1 /p∞) d log (p2 /p∞)
= (4.4.1)
d log x1 d log x2
Henry’s law in the amount fraction form as applicable to the solute is
p2 = kH x2 (Eq. 4.3.3)

Taking logarithm, we have

log (p2 /p∞) = log (kH /p∞) + log x2 or d log (p2 /p∞)) = d log x2

d log (p2 /p∞)

i.e. =1 (4.4.2)
d log x2
Hence, from Eq. (4.4.1), we have
d log (p1 /p∞)
=1 (4.4.3)
d log x1
which on integration gives
log (p1 /p∞) = log x1 + constant
p1 /p∞ = K ¢x1
or p1 = Kx1 (4.4.4)
For the pure solvent x1 = 1 and p1 = p1* where p1* is the vapour pressure of the
pure solvent. Thus
K = p1*
With the above identity, Eq. (4.4.4) becomes
p1 = x1 p1* (4.4.5)
Equation (4.4.5) is obtained provided Eq. (4.4.3) is applicable to the solvent.
In deriving Eq. (4.4.3), we have used Henry’s law in the amount fraction form
as applicable to the solute (Eq. 4.3.3). Thus, it is obvious that Eq. (4.4.5) holds
good for the solvent as long as Eq. (4.3.3) is obeyed by the solute. If Eq. (4.3.3)
is applicable to solute only in the limited range of low concentration (in dilute
solutions where x2 is small), then Eq. (4.4.5) will be applicable to solvent over
the same range of concentration. When Henry’s law is not obeyed by the solute,
Raoult’s law is also not obeyed by the solvent.
Illustration To make the above discussion more clear, let us take a specific example of a
solution of liquid A in liquid B. If the partial pressure of B is plotted against
its amount fraction in the solution, we get a curve as shown in Fig. 4.4.1a. The
curve as expected from Raoult’s law can be obtained by connecting the zero
 Solutions 125

point at the left (xB = 0) with the point representing p*B at the right (xB = 1).
It can be seen from Fig. 4.4.1a that Raoult’s law curve meets the partial
vapour pressure curve tangentially in the region where xB 1. Thus, we see
that Raoult’s law is applicable only in the limited range of concentrations
where B is present in excess amounts and is thus acting as a solvent. Now
if a line tangent to the curve of the observed partial vapour pressure at very
low concentration of B is drawn, we get the graph of Henry’s law. The
extrapolation of this line to the right axis where xB = 1 gives the hypothetical
vapour pressure which would be observed if Henry’s law be applicable over
the entire range of concentration, that is, up to xB = 1.

Fig. 4.4.1 Schematic graphs indicating applicability of Henry’s law to the solute and
Raoult’s law to the solvent. (a) For liquid B and (b) for liquid A.

From Eq. (4.3.3), it follows that at xB = 1, we have

pB = kH
Thus, Henry’s law constant has a value of the vapour pressure which pure
B would have if the vapour pressure obeyed Henry’s law instead of Raoult’s law.
Note that according to Raoult’s law, the constant KH would have been equal to
p*B. In other words, Henry’s law constant for nonideal system is different from
Raoult’s law constant.
Now, if a graph between the partial vapour pressure of liquid A and its
amount fraction in the solution is drawn, we would get a plot as shown in
Fig. 4.4.1b. The associated Raoult’s law curve and Henry’s law curve are also
shown in Fig. 4.4.1b. It may be seen that Raoult’s law curve meets the partial
vapour pressure curve tangentially in the region xA 1 indicating that Raoult’s
126 A Textbook of Physical Chemistry

law is applicable to the solvent. On the other hand, Henry’s law curve meets
the partial vapour pressure curve in the region xA 0 indicat ing that Henry’s
law is applicable to solute.
Figure 4.4.1 also illustrates the fact that Raoult’s law is applicable to the
solvent over the same range where Henry’s law is applicable to the solute. For
example, if the applicable range of Henry’s law for liquid A (solute) were from
0 to 8% of A (shown by the line aa in Fig. 4.4.1b), then the applicable range
for B (solvent) will be from 92 to 100% of B as shown by the line aa in
Fig. 4.4.1a. On the other side, if Henry’s law applicable range for B were from
0 to 5% of B (shown by the line bb in Fig. 4.4.la), then Raoult’s law applicable
range for liquid A will be from 95 to 100% of A as shown by the lines bb in
Fig. 4.4.1b.

Example 4.4.1 The total vapour pressure of a 4 mol % solution of a gas B in water at 293 K is 50.0
Torr; the vapour pressure of pure water is 17.0 Torr at this temperature. Applying Henry’s
and Raoult’s laws, calculate the two partial pressures and the total vapour pressure for a
solution of 5 mol % B.

Solution The given data are

p*water = 17.0 Torr

ptotal (4 mol % solution) = pB + pwater = 50.0 Torr

xB = 0.04 and xwater = 0.96

Now accor ding to Raoult’s law, we have

pwater = xwater p*water = 0.96 ¥ 17.0 Torr = 16.3 Torr

Thus pB = ptotal - pwater = 50.0 Torr - 16.3 Torr = 33.7 Torr
Now Henry’s law constant for the gas B is
pB 33.7 Torr
kH (B) = = = 842 Torr
xNH3 0.04

Hence for 5 mol % solution, we have

pNH3 = kH (B) xNH3 = (842 Torr) (0.05) = 42.1 Torr

pwater = p*water xwater = (17 Torr) (0.95) = 16.1 Torr

Thus ptotal (5 mol % solution) = pB + pwater = 42.1 Torr + 16.1 Torr

= 58.2 Torr

4.5 DERIVATIONS OF RAOULT’S AND HENRY’S LAWS FROM KINETIC-MOLECULAR

THEORY
Raoult’s and Henry’s laws may be derived from the view-point of kinetic-
molecular theory as follows.
 Solutions 127

Raoult’s Law For a pure liquid solvent in equilibrium with its vapour, we may write
r1, cond = r1, evap (4.5.1)
where r1, cond and r1, evap are the rates of condensation of solvent molecules from
vapour phase and of evaporation of solvent molecules from pure liquid solvent,
respectively. The rate of condensation may be taken as proportional to the number
of collisions per second of vapour molecules with the liquid’s surface and this
number is proportional to pressure p*1. Thus, we have
r1, cond = r1, evap = bp1* (4.5.2)
where b is the constant of proportionality.
In an ideal binary liquid solution, the vapour pressure of solvent is p1. Hence
r1, cond = bp1 (4.5.3)
Since the sizes of solute and solvent molecules in an ideal solution are identical,
the number of molecules of solvent in unit surface area of the solution will be
x1 times the number of solvent molecules in unit surface area of pure solvent,
where x1 is the amount fraction of solvent in solution. Consequently, the rate
of evaporation of molecules from the surface of solution will also be x1 times
the rate of evaporation from the pure solvent’s surface. Hence

r1, evap = x1 (bp1* ) (4.5.4)

Equating Eqs (4.5.3) and (4.5.4), we get

p1 = x1 p1*

which is Raoult’s law.

Henry’s Law For a pure liquid solute in equilibrium with its vapour, we may write
r2, cond = r2, evap (4.5.5)

where r2, cond and r2, evap are the rates of condensation of solute molecules from
vapour phase and of evaporation of solute molecules from pure liquid solute,
respectively. As in the case of pure solvent, we write

r2, cond = r2, evap = bp2* (4.5.6)

In an ideally dilute solution, the rate of condensation of solute molecules

is proportional to the partial vapour pressure p2. But because of the fact that in
the liquid phase solute interacts only with solvent molecules, the proportionality
constant in the present case will be different from that appearing in Eq. (4.5.6).
Thus we write
r2, cond = b ¢p2 (4.5.7)
For the rate of evaporation of solute molecules from an ideally dilute
solution, we consider the following two facts:
128 A Textbook of Physical Chemistry

(i) Size of solute and solvent molecules are different If x2 is the amount fraction
of solute in solution, then the number of solute molecules present in unit surface
area of solution will be reduced by a factor ax2 compared with those present
in unit surface area of pure solute, where the constant a takes into account the
different sizes of solute and solvent molecules.
(ii) Solute molecule interacts with solvent molecules only Because of this
interaction, the rate of evaporation of solute molecules will not be simply equal
to ax2 times but c(ax2) times the rate of evaporation from pure liquid solute,
where the constant c takes into account the different interactions in pure solute
and in ideally dilute solution. Thus, we write
r2, evap = {c(ax2 )}{bp2*} (4.5.8)
Equating Eqs (4.5.7) and (4.5.8), we have
Ê c a b p2* ˆ
b ¢p2 = {c(ax )}{bp2*} or p2 = Á ˜ x2
Ë b¢ ¯
i.e. p2 = kH x2

which is Henry’s law.

4.6 IDEAL AND IDEALLY DILUTE SOLUTIONS

Ideal Solution An ideal solution is the one whose components follow Raoult’s law in the entire
range of composition. Each component also follows Henry’s law where the
Henry’s law constant is equal to the vapour pressure of the pure component
(see Section 4.15).
Ideally Dilute A real solution in the limit x1 1 and x2 0 is known as ideally dilute solution.
Solution In this solution, each solute molecule is surrounded by solvent molecules. The
separation between solute molecules is so large that they do not interact with
one another. Raoult’s law for solvent and Henry’s law for solute are the defining
equations for an ideally dilute solution. Thus, the vapour pressures of solvent
and solute of an ideally dilute solution are given by the expressions:
Raoult’s law for solvent p1 = x1 p1* (4.6.1a)
Henry’s law for solute p2 = x2 kH (4.6.1b)

Expressions of Equations (4.6.1) can be used to derive the expressions of chemical potential for
Chemical Potentials solvent and solute in an ideally dilute solution. From the thermodynamic criterion
of equilibrium, we write

m1(sol) = m1(v) (4.6.2a)

m2(sol) = m2(v) (4.6.2b)

For the vapour phase, we have

m = m* + RT ln ( p/p∞ )
 Solutions 129

With the above expression, Eqs (4.6.2a) and (4.6.2b) become

* + RT ln ( p /p∞ )
m1(sol) = m1(v) 1

* + RT ln ( p /p∞)
m2(sol) = m2(v) 2

which on making use of Eqs (4.6.1a) and (4.6.1b) become

* + RT ln (p* /p∞ )} + RT ln x
m1(sol) = {m1(v) (4.6.3a)
1 1

* + RT ln (k /p∞ )} + RT ln x
m2(sol) = {m2(v) (4.6.3b)
H 2

or * + RT ln x
m1(sol) = m1(1) (4.6.4a)
1

*
m2(sol) = m2(1, hs) + RT ln x2 (4.6.4b)

where the subscript ‘hs’ stands for the hypothetical state. From Eq. (4.6.4a),
we conclude that the standard state of solvent in ideally dilute solution is the
pure liquid solvent. For solute, the standard state is the hypothetical state of
solute where its vapour pressure is kH. Its value is determined by extrapolating
the experimental vapour pressure of solute in the region x2 0 to a value of
x2 1. This hypothetical state has the properties which the pure solute would
have if its limiting low-concentration properties in solution were to be retained
in a pure substance. The actual ‘properties of the pure solute will be different
from those of the hypothetical state, since in the pure form, the solute molecule
is surrounded by another solute molecules whereas in the hypothetical state solute
molecule is surrounded by solvent molecules only. From Eq. (4.6.4b), we may
define the chemical potential for the hypothetical state as

hs) = lim (m 2(sol) - RT ln x2 )

*
m2(1, (4.6.5)
x2 Æ 1

4.7 VARIATION OF HENRY’S LAW CONSTANT WITH TEMPERATURE

From Eqs (4.6.3b) and (4.6.4b), we may write

*
m2(1, *
hs) = m 2(v) + RT ln (kH /p∞)

hs) - m 2(v) D vap m2(1,

*
m2(1, * *
hs)
or ln (kH /p∞) = =- (4.7.1)
RT RT

According to Eq. (4.7.1), the Henry’s law constant is a function of temperature

of the solution. To determine functionality, we differentiate Eq. (4.7.1) with
respect to temperature, i.e.

Ê ∂ ln (kH /p∞) ˆ 1 Ê ∂(D vap m2(1,

*
hs) /T
ˆ
ÁË ˜¯ = - Á ˜ (4.7.2)
∂T p RË ∂T ¯p
130 A Textbook of Physical Chemistry

Using Gibbs-Helmhlotz equation, we get

Ê ∂ ln (kH /p∞) ˆ D vap H m,

* 2(1, hs) (4.7.3)
ÁË ˜¯ =
∂T p RT 2
To determine the variation of kH with T, we integrate the above expression to
give
T2 T2 D vap H m,
* 2(1, hs) dT
ÚT1 d(ln kH /p∞) = ÚT1 R T2
(4.7.4)

kH¢ D vap H m,
* 2(1, hs) Ê 1 1ˆ
ln = Á - ˜ (4.7.5)
kH R Ë T1 T2 ¯
where kH and kH are Henry’s law constants at temperatures T2 and T1, respectively.
Since p2 = kH x2, the variation of x2 with temperature at constant p2 will
given by
x2 D vap H m
* , 2(1, hs) Ê 1 1ˆ
ln = Á - ˜ (4.7.6)
x2¢ R Ë T1 T2 ¯

which is the same as given by Eq. (4.1.9).

From Eq. (4.7.5), it follows that kH increases with increase in temperature.
Since p2 = kH x2, it may be concluded that
(i) p2 increases with increases in T for a constant x2
(ii) x2 decreases with increase in T for a constant p2.

4.8 THERMODYNAMICS OF IDEAL SOLUTIONS OF LIQUID IN LIQUID

When a liquid is completely miscible with another liquid, a homogeneous
Ideal Solution solution consisting of a single phase is formed. If such a solution is placed in
a closed evacuated vessel, the total pressure exerted by the vapour, after the
system has attained equilibrium, will be equal to the sum of partial pressures
of its constituents. A solution is said to be an ideal solution if its constituents
follow Raoult’s law under all conditions of compositions, i.e. the partial pressure
of each and every constituent is given by
pi = xi p1* (4.8.1)
where pi is the partial pressure of the constituent i whose amount fraction in the
solution is xi and p*i is the corresponding vapour pressure of the pure constituent.
Thermodynamics of The various constituents of an ideal solution follow the relation
an Ideal Solution
mi (soln) = mi*(1) + RT ln xi (Eq. 2.5.15)
where μi(sol) is the chemical potential of ith constituent of the solution, μ*i(1)
is that of the pure liquid constituent i and xi is the amount fraction of the
constituent in the solution. The changes in the thermodynamic functions when
an ideal solution is formed by mixing pure components can be readily calculated
as described below.
 Solutions 131

Change of Gibbs free-energy We have

D mixG = Gfinal - Ginitial = Â ni mi(sol) - Â ni mi*(1)

i i

= Â ni (mi(sol) - mi*(1) )
i

Making use of Eq. (2.5.15), we get

D mixG = Â ni RT ln xi = ntotal RT Â xi ln xi (4.8.2)

i i
where ntotal is the total amount of all the constituents present in the solution.
Change of entropy on mixing The entropy of mixing can be obtained from
the relation
Ï ∂( D mixG ) ¸
Ì ˝ = - D mix S
Ó ∂T ˛ p, n j s
Substituting mixG from Eq. (4.8.2) and carrying out the desired differentiation,
we get

Ï ∂(ntotal RT Â xi ln xi ) ¸
Ô Ô
D mix S = - Ì i
˝ = - ntotal R Â xi ln xi (4.8.3)
ÔÓ ∂ T Ô˛ p,n s i
j

Change of enthalpy on mixing This can be determined from the relation

D mixG = D mix H - T D mix S i.e. D mix H = D mixG + T D mix S

Substituting mixG and mixS from Eq. (4.8.2) and (4.8.3), we get
D mix H = ntotal RT Â xi ln xi - T ntotal R Â xi ln xi = 0 (4.8.4)
i i
Thus in the formation of an ideal solution neither heating nor cooling
is observed.
Change of volume on mixing This can be determined from the relation
Ê ∂( D mixG ) ˆ
D mixV = Á ˜
Ë ∂p ¯ T , n s j

Substituting mixG from Eq. (4.8.2), we get

Ê ∂(Â ntotal RT xi ln xi ) ˆ
D mixV = Á i ˜ = 0 (4.8.5)
ÁË ∂p ˜¯
T ,n s j

as mixG is independent of pressure. Equation (4.8.5) implies that the total

volume of an ideal solution will be equal to the sum of individual volumes of
its constituents.
132 A Textbook of Physical Chemistry

Molecular Interpreta- The fact that mix H is zero for the formation of an ideal solution implies that at
tion of mix H = 0 and the molecular level, the cohesive forces between the molecules of its constituents
mixV = 0 must be completely identical in nature, since only then it is expected that on
mixing, the environmental forces of each remain almost unchanged. In other
words, the two liquids A and B are expected to form a binary ideal solution
provided the forces of attraction between A A molecules are identical with those
of B B molecules and thus are also identical with those between A B molecules
which exist in the solution. Thus the molecule A in solution will not be knowing
whether it is attracting a like molecule A or an unlike molecule B and vice versa.
Besides the identical forces between all pairs of molecules in an ideal solution,
the different molecules must also have equal volumes, since only then we would
expect no volume change on mixing its components.
The partial molar volume of a constituent in an ideal solution is equal to
the molar volume of the constituent when present in the pure form.
Examples of Ideal The above conditions are, however, met only in few cases and thus limited
Binary Liquid examples of ideal binary liquid solutions are known. Some of the known examples
Solutions which form nearly ideal solutions are:
(i) Ethylene dibromide and propylene dibromide at 358 K
(ii) Ethyl bromide and ethyl iodide at 303 K
(iii) n-Butyl chloride and n-butyl bromide at 323 K
(iv) n-Hexane and n-heptane at 303 K.
The temperatures mentioned along with the above liquid pairs are those
at which measurements have been reported.

Example 4.8.1 Assuming ideal behaviour, determine mixGm, mixG, mixSm and mixS when 270.0 g of
sugar with a molar mass of 358 g mol–1 is dissolved in 1.0 kg of water at 298 K.
270.0 g
Solution Amount of sugar = = 0.754 mol
358 g mol -1
1 000 g
Amount of water = = 55.556 mol
18 g mol -1

Total amount, ntotal = 0.754 mol + 55.556 mol = 56.310 mol

0.754 mol
Amount fraction of sugar, xs = = 0.013 4
56.310 mol
55.556 mol
Amount fraction of water, xw = = 0.986 6
56.310 mol
Substituting the data in
D mixGm = xs RT ln xs + xw RT ln xw
we get D mixGm = (0.013 4) (8.314 J K –1 mol –1 ) (298 K) (ln 0.013 4)
+ (0.986 6) (8.314 J K –1 mol –1 ) (298 K) (ln 0.986 6)
= – 143.173 J mol –1 – 32.976 mol –1
= - 176.149 J mol –1
 Solutions 133

Now D mixG = ntotal D mixGin = (56.310 mol) ( - 176.149 J mol -1 )

= - 9 919.0 J
D mixGm (- 176.149 J mol -1 )
D mix Sm = - =- = 0.591 J mol -1 K -1
T 298 K
D mixG (- 9 919.0 J)
D mix S = - =- = 33.285 J K -1
T 298 K

Example 4.8.2 Assuming ideal behaviour, determine mixG and mixS when a solution of 1 mol of liquid
A in 9 mol of liquid B is mixed with 10 mol of liquid B at 300 K.

Solution We consider the following three processes.

(i) 9 mol of liquid B + 1 mol of liquid A (solution)1; mixG1

(ii) 10 mol of liquid B + (solution)1 (solution)2; mixG2
(iii) 19 mol of liquid B + 1 mol of liquid A (solution)2; mixG3

Obviously, we have

D mixG3 = D mixG1 + D mixG2 or D mixG2 = D mixG3 - D mixG1

Similarly D mix S2 = D mix S3 - D mix S1

Now D mixG1 = ntotal RT Â xi ln xi

i

Ê 1 1 9 9ˆ
= (10 mol) (8.314 J K -1 mol -11 ) (300 K) Á ln + ln ˜
Ë 10 10 10 10 ¯
= - 8 108.2 J
D G ( - 8112 J)
D mix S = - mix 1 = - = 27.03 J K -1
T (300 K)
D mixG3 = ntotal RT Â xi ln xi
i

Ê 1 1 19 19 ˆ
= (20 mol) (8.314 J K -1 mol -1 ) (300 K) Á ln + ln ˜
Ë 20 20 20 20 ¯
= - 9 902.7 J
D G ( - 9 902.7 J)
D mix S3 = - mix 3 = - = 33.01 J K -1
T (300 K)

Hence D mixG2 = D mixG3 - D mixG1 = (- 9 902.7 J mol -1 ) - (- 8 108.2 J mol -1 )

= - 1 794.5 J mol -1
D mix S2 = D mix S3 - D mix S1 = (33.01 J K -1 ) - (27.03 J K -1 )
= 5.98 J K -1
134 A Textbook of Physical Chemistry

4.9 VAPOUR PRESSURE OF AN IDEAL BINARY LIQUID SOLUTION

Expression of Since both the constituents of an ideal binary liquid system follow Raoult’s law
Vapour Pressure over the entire range of composition, the partial pressures exerted by vapours
of these constituents over the solution will be given by

pA = xA p*A (4.9.1)

pB = xB p*B (4.9.2)

where xA and xB ar e t he amount fractions of the two constituents in the

liquid phase and pA* and pB* are the respective vapour pressures of the pure
constituents.
The total pressure over the solution will be sum of these partial pressures.
Thus, we have

p = pA + pB = xA p*A + xB p*B

Since in a binary solution, xA + xB = 1 or xB = 1 – xA, therefore, we have

p = xA p*A + (1 - xA ) p*B
= p*B + (p*A - p*B ) xA (4.9.3)

Thus, the total vapour pressure over the solution is a linear function of xA
with intercept equal to pB* and slope equal to pA* – pB*. The slope can be positive
or negative depending upon the relative magnitudes of pA* and pB*. If the
constituent A is more volatile, then pA* > pB* and the term pA* – pB* is positive.
For such a case, the total pressure p increases with increase in amount
fraction xA of the more volatile constituent. If the constituent A is less volatile,
then pA* < pB*. In this case, the term pA* – pB* is negative and there occurs a decrease
in vapour pressure with increase in amount fraction xA of the less volatile
constituent.
Equations (4.9.1), (4.9.2) and (4.9.3) have been shown schematically in
Fig. 4.9.1 with pA* > pB*.
Composition of the Composition of the vapour phase can be determined with the help of Dalton’s
Vapour Phase law of partial pressures. Thus, we have

pA xA p*A
yA = = (4.9.4)
p p*B + (p*A - p*B ) xA

pB xB p*B
and yB = = 1 - yA = (4.9.5)
p p*A + ( p*B - p*A ) xB
 Solutions 135

Fig. 4.9.1 Plots of pA, pB

and p against the amount
fraction xA or xB in the
liquid state

Vapour Pressure To express the total vapour pressure in terms of the composition of vapour phase,
Related to Vapour we rearrange Eq. (4.9.4) as
Composition
yA p*B
xA = (4.9.6)
p*A + ( p*B - p*A )yA
and then substitute xA in Eq. (4.9.3). Thus, we have

p = p*B + ( p*A - p*B )xA

yA p*B
= p*B + ( p*A - p*B )
p*A + ( p*B - p*A )yA
p*B p*A
i.e. p= (4.9.7)
p*A + ( p*B - p*A )yA

The plot of p versus yA for a solution in which pA* > pB* is shown in Fig. 4.9.2.
Equation (4.9.7) can be written in a linear form by taking its reciprocal.
Thus, we have

1 p* + ( p*B - p*A )yA 1 Ê 1 1 ˆ

= A = +Á - yA (4.9.8)
p p*B p*A pB Ë p*A p*B ˜¯
*

According to Eq. (4.9.8), the reciprocal of the total pressure varies linearly with
yA, the amount fraction of the constituent A in the vapour phase. This variation
is shown in Fig. 4.9.3.
136 A Textbook of Physical Chemistry

Fig. 4.9.2 Plot of p against yA, the composition Fig. 4.9.3 Plot of 1/p versus yA, the composition
of A in vapour phase of A in vapour phase

Example 4.9.1 Suppose that the vapour over an ideal solution contains the amounts n1 of 1 and n2 of
2 and occupies a volume V under the pressure p = p1 + p2. If we define V *1, m = RT/p*1
and V *2, m = RT/p*2 , then show that Raoult’s law implies that V = n1V *1, m + n2V *2, m.

Solution The pressure p over a solution as calculated by using Raoult’s law is given by

1 1 Ê 1 1 ˆ
= +Á - ˜ y1 (Eq. 4.9.8)
p p*2 Ë p1* p*2 ¯

Replacing ps in terms of Vs we get

V V* ÊV* V * ˆ Ê n1 ˆ
= 2, m + Á 1, m - 2, m ˜ Á
(n1 + n2 ) RT RT Ë RT RT ¯ Ë n1 + n2 ˜¯

or V = (n1 + n2 )V2,* m + n1 (V1,*m - V2,* m )

or V = n1V1,*m + n2V2,* m

Example 4.9.2 The composition of vapour over a binary ideal solution is determined by the composition
of the liquid. If xA and yA are the amount fractions of A in the liquid and vapour,
respectively, find the value of xA for which yA – xA has a maximum. What is the value
of the pressure at this composition?

xA p*A
Solution We have yA =
p*B + ( p*A - p*B )xA
 Solutions 137

Subtracting xA from both sides, we get

xA p*A
yA - xA = - xA
p*B + ( p*A - p*B )xA

Differentiating with respect to xA, we get

d(yA - xA ) p*A xA p*A (p*A - p*B )

= - -1
dxA p*B + ( p*A - p*B )xA {p*B + ( p*A - p*B )xA}2

The value of xA at which yA – xA has a maximum value can be obtained by setting the
above differential equal to zero. Thus, we have

p*A xA p*A ( p*A - p*B )

- -1= 0
p*B + ( p*A - p*B )xA {p*B + ( p*A - p*B )xA}2

Solving for xA, we get

p*A p*B - p*B

xA =
p*A - p*B
The value of p at this composition is

p = xA p*A + xB p*B = p*B + ( p*A - p*B )xA

Ê p*A p*B - p*B ˆ
= p*B + ( p*A - p*B ) Á ˜ = p*A p*B
ÁË p*A - p*B ˜¯

Example 4.9.3 Two liquids A and B form an ideal solution at temperature T. When the total vapour
pressure above the solution is 600 Torr, the amount fraction of A in the vapour phase is
0.35 and in the liquid phase is 0.70. What are the vapour pressures of pure A and pure
B at temperature T ?

Solution The given data are

xA = 0.70 yA = 0.35 p = 600 Torr p*A = ? p*B = ?

pA x p*
Now yA = = A A
p p
yA p (0.35) (600 Torr)
Therefore p*A = = = 300 Torr
xA (0.70)
yB p (0.65) (600 Torr)
Similarly, p*B = = = 1 300 Torr
xB (0.30)

Example 4.9.4 At 323 K, the vapour pressures of pure n-hexane and n-heptane are 54.4 and
18.8 kN m–2, respectively. Assuming ideality, determine:
(a) The amount fraction of n-hexane in a solution in equilibrium with a vapour in
which the amount fraction of n-hexane is 0.85.
138 A Textbook of Physical Chemistry

(b) The molar entropy change when this solution is formed from pure components
at 323 K.

Solution The given data are

p*A = p*n-hexane = 54.4 kN m -2 p*B = p*n-heptane = 18.8 kN m -2

xA = xn-hexane = ? yA = yn-hexane = 0.85
DSmix = ?

pA xA p*A
(a) Now yA = =
p p*B + ( p*A - p*B )xA

yA p*B
Therefore xA =
p*A - ( p*A - p*B )yA

Substituting the values, we get

0.85 ¥ 18.8 kN m -2
xA = -2
= 0.662
54.4 kN m - (54.4 kN m -2 - 18.8 kN m -2 ) ¥ 0.85

(b) Now D mix S/R = - xA ln xA - xB ln xB

Substituting the values of xA and xB, we get

D mix S/R = - 0.662 ¥ 2.303 ¥ log (0.662) - 0.338 ¥ 2.303 ¥ log (0.338)
= 0.273 1 + 0.366 7 = 0.639 8

Hence DSmix = (0.639 8) (8.314 J K -1 mol -1 ) = 5.319 J K -1 mol -1

Example 4.9.5 At 303 K, the vapour pressure of pure toluene and pure benzene are 36.7 and 118.2
Torr, respectively, and the two liquids form a nearly ideal solution, (a) For a solution
containing 50.0 mass % of toluene, calculate the total vapour pressure and the amount
fraction of each compound in the vapour phase. (b) Determine the composition of a
solution of benzene and toluene that will boil at 303 K at a pressure of 50.0 Torr.

Solution The given data are

p*toluene = p*t = 36.7 Torr p*benzene = p*b = 118.2 Torr

(a) From the given data, we have

nt (50 g/92 g mol -1 )

xt = = = 0.459
nt + nb (50 g/92 g mol -1 ) + (50 g/78 g mol -1 )

pt = xt p*t = 0.459 ¥ 36.7 Torr = 16.85 Torr

pb = xb p*b = (1 - 0.459) ¥ 118.2 Torr = 63.95 Torr

p = pt + pb = 16.85 Torr + 63.95 Torr = 80.80 Torr
pt 16.85 Torr
Now yt = = = 0.21 and yb = 1 - yt = 0.79
p 80.80 Torr
 Solutions 139

(b) We have

p = pt + pb = xt pt* + xb p*b = xt p*t + (1 - xt )p*b = p*b + ( p*t - p*b )xt

p - p*b
Thus xt =
p*t - p*b

Substituting the given data, we get

50.0 Torr - 118.2 Torr

xt = = 0.84
36.7 Torr - 118.2 Torr
xb = 1 - xt = 0.16

4.10 VAPOUR PRESSURE-COMPOSITION DIAGRAM OF A BINARY LIQUID SOLUTION

Application of the Since the number of components in a binary mixture are two, according to the
Phase Rule phase rule, we have
F =C -P +2=4-P (4.10.1)
The variance of the system will depend on the number of phases present
in the system.
System consisting of only one Phase If the system has only one phase (liquid
or gaseous), then it is trivariant. This means that the values of three variables
will have to be stated in order to define the state of the system completely. These
are temperature, pressure and composition. If one of them is held constant, say
temperature, then the values of other two variables, namely, pressure and
composition, will have to be stated in order to describe the system completely.
The state of such a system can be represented by a point in a two-dimensional
plot of pressure versus composition at a given temperature. In Fig. 4.9.1, we have
plotted the total vapour pressure of a binary liquid mixture against the amount
fraction of the constituent A (or constituent B as xA + xB = 1) in the liquid phase.
Since the total pressure is an equilibrium vapour pressure, it is obvious that
the system would consist of only liquid phase if it is subjected to a pressure
greater than its equilibrium vapour pressure. Hence a point anywhere above the
total vapour pressure line in Fig. 4.9.1 represents the system in the liquid phase.
Similarly, a point anywhere below the total pressure line in Fig. 4.9.2 represents
the system in the vapour phase.
System consisting of two phases If the system has two phases in equilibrium,
namely, liquid and vapour, then the variance of the system is two. This means
that the values of only two variables will have to be stated in order to describe
the system completely. Any two of the three variables, temperature, pressure and
composition, can be stated. The third one automatically will have a definite
value. For example, if temperature and composition are stated, then the vapour
pressure of the system will have a definite value. The straight line of Fig. 4.9.1
and the curved line of Fig. 4.9.2 represent the two phases, liquid and vapour,
in equilibrium with each other.
140 A Textbook of Physical Chemistry

Depiction of the The two states, namely, liquid and vapour, can be shown in one diagram when
Diagram the plots of Figs 4.9.1 and 4.9.2 are drawn together in one graph. This is shown
in Fig. 4.10.1. The upper curve is called the liquidus curve since this represents
the line above which only liquid phase exists. A point anywhere on this line
represents the two phases, liquid and vapour, in equilibrium with each other.
Similarly, the lower curve is called the vaporous curve since it represents the
curve below which only vapour exists. Along this line also the two phases, liquid
and vapour, are in equilibrium with each other.

Fig. 4.10.1 Vapour

pressure-composition
diagram

A point anywhere in the region between the two curves represents the
system in which both liquid and vapour coexist in equilibrium with each other.
It is for this reason, this region is known as the liquid-vapour region. For a given
composition, the points on the liquidus and vaporous curves represent,
respectively, the maximum and the minimum pressures within which the
two phases can exist in equilibrium with each other. The above facts can be
summarized as follows:
(i) If psystem > pmax; only liquid phase exists.
(ii) If psystem < pmin; only vapour phase exists.
(iii) For pmax > psystem > pmin; the liquid and vapour phases are in
equilibrium with each other.
Tie Line As indicated above, the region between the liquidus and vaporous curves of
Fig. 4.10.1 represents a region where both the phases exist in equilibrium with
each other. For this region, P = 2 and thus F = 2. Since the temperature is fixed,
one other variable (any one of p, xA and yA) is sufficient to describe the system
completely. For instance, if p is chosen, then the amount fractions of the
component A in the liquid and vapour phases are represented by the intersection
points of a horizontal line, known as the tie line, drawn from the given p with
those of liquidus and vaporous curves, respectively. If xA is chosen as the
describing variable, then the intersection of a vertical line from xA with the
 Solutions 141

liquidus curve yields the value of p and a horizontal line from p cutting the
vaporous curve gives the vapour composition yA.
The Lever Rule A point within the liquid and vapour curves represents two phases, liquid and
vapour, in equilibrium with each other. For the point a shown in Fig. 4.10.2, the
amount fraction of the constituent A in the liquid phase is given by the point
b (i.e. xA) and that in the vapour phase is given by the point c (i.e. yA).

Fig. 4.10.2 The lever

rule

Qualitative introduction of the lever rule In fact, any point a on the tie line
bc represents the same compositions of liquid and vapour phases, namely, xA and
yA, respectively. The only difference that exists from point to point is the relative
amounts of the two phases. If a coincides with b then the vapour phase has just
started forming with amount fraction yA and if it coincides with c, then the last
drop of liquid phase with amount fraction xA is just going to be converted into
the vapour phase. As we move from b to c, more and more of the liquid phase
is converted into the vapour phase, keeping the amount fractions of the two
phases equal to xA and yA, respectively. Thus if the point a is nearer to b, the
system will consist of a larger amount of liquid and a relatively smaller amount
of vapour; but if it is nearer to c, then the amount of liquid present is relatively
small as compared with the amount of vapour present. As a moves from b to c,
more and more of the vapour is formed, thus the distance ba represents the
amount of vapour formed. Similarly as a moves from c to b, more and more
of the liquid is formed and thus the distance ac represents the amount of liquid
formed. Taking these together, we have
distance ab amount of the vapour formed
distance ac amount of the liquid formed
Taking the ratio, we have
ab Amount of the vapour formed
= (4.10.2)
ac Amount of the liquid form
med
142 A Textbook of Physical Chemistry

Equation (4.10.2) is knows as the lever rule.

Quantitative derivation of the lever rule The amount fraction XA corresponding
to the point a represents the amount fraction of the component A in the entire
system consisting of liquid and vapour phases, i.e.
nA(1) + nA(v)
XA = (4.10.3)
nA(1) + nA(v) + nB(1) + nB(v)

From Fig. 4.10.2, we have

nA(1)
(ab) = X A - xA = X A - (4.10.4)
nA(1) + nB(1)
nA(v)
(ac) = yA - X A = - XA (4.10.5)
nA(v) + nB(v)

Multiplying Eq. (4.10.4) by nA(1) + nB(1) and Eq. (4.10.5) by nA(v) + nB(v), we
have
(nA(1) + nB(1) ) (ab) = (nA(1) + nB(1) )X A - nA(1) (4.10.6)

(nA(v) + nB(v) ) (ac) = nA(v) - (nA(v) + nB(v) ) X A (4.10.7)

Subtracting Eq. (4.10.7) from Eq. (4.10.6), we get

(nA(1) + nB(1) ) (ab) - (nA(v) + nB(v) )(ac)

= X A (nA(1) + nB(1) + nA(v) + nB(v) ) - (nA(1) + nA(v) )

which on making use of Eq. (4.10.3) becomes

(nA(1) + nB(1) ) (ab) - (nA(v) + nB(v) (ac) = 0

Ê ab ˆ nA(v) + nB(v)
or ÁË ˜¯ =
ac nA(1) + nB(1)

Ê ab ˆ Amount in the vapour phase

i.e. ÁË ˜¯ = (4.10.8)
ac Amount in the liquid phase

In words, the ratio of the amount of vapour to the amount of liquid is given
by the ratio of lengths of the line segments connecting a to b and a to c. Thus
if a lies very close to b, then ab is very small and, therefore, nv << n1, i.e. the
system consists mainly of liquid phase. If a lies very close to c, then nv >> n1
and thus the system consists mainly of vapour phase.

Example 4.10.1 At 353 K, the vapour pressures of pure ethylene bromide and propylene bromide are
22.93 and 16.93 kN m–2, respectively, and these compounds form a nearly ideal solution.
3 mol of ethylene bromide and 2 mol of propylene bromide are equilibrated at 353 K
and a total pressure of 20.4 kN m–2. (a) What is the composition of the liquid phase?
(b) What amount of each compound is present in the vapour phase?
 Solutions 143

Solution The given data are

p*A = p*ethylene = 22.93 kN m -2 p*B = p*propylene = 16.93 kN m -2

bromide bromide

nA = 3 mol nB = 2 mol p = 20.4 kN m -2

(a) We have

p = pA + pB = xA p*A + xB p*B = p*B + ( p*A - p*B )xA

p - p*B
Therefore xA =
p*A - p*B

Substituting the given data, we have

20.4 kN m -2 - 16.93 kN m -2
xA = = 0.578
22.93 kN m -2 - 16.93 kN m -2
xB = 1 - 0.578 = 0.422

pA x p* 0.578 ¥ 22.93 kN m -2
(b) Now yA = = A A = = 0.649 7
p p 20.4 kN m -2

Let nA and nB be the amounts of vaporized ethylene bromide and propylene bromide,
respectively, when p = 20.4 kN m–2. Hence we have

nA
yA = = 0.649 7
nA + nB
3 mol - nA 3 mol - nA
xA = =
(3 mol - nA ) + (2 mol - nB ) 5 mol - (nA + nB )
3 mol - nA
= = 0.578
5 mol - nA /0.649 7

Ê nA ˆ
or (3 mol - nA ) = 0.578 Á 5 mol - ˜
Ë 0.649 7 ¯

3 mol - 0.578 ¥ 5 mol

Therefore nA = = 0.996 7 mol
1 - 0.578/0.649 7

nA
Since = 0.649 7, we, therefore, have
nA + nB

nA Ê 1 ˆ (0.996 7 mol)(0.350 3)
- nA = nA Á -1 =
Ë 0.649 7 ˜¯
nB =
0.649 7 (0.649 7)
= 0.537 4 mol
144 A Textbook of Physical Chemistry

Example 4.10.2 For the preceding problem, use the lever rule to obtain the amount of each compound
in the vapour phase.

Solution Now, we know

Amount in the liquid phase y – XA

= A
Amount in the vapour phase X A – xA

where XA is the amount fraction of ethylene bromide in the overall system. Substituting
the values of xA, yA and XA, we have

Amount in the liquid phase 0.6449 7 - (3/5) 0.049 7

= =
Amount in the vapour phase (3/5) - 0.578 0.022
= 2.259

Adding one on both sides and taking inverse, we get

Amount in the vapour phase 1

=
Amount in the (liquid + vapour) phase 1 + 2.259

1
Amount in the vapour phase = (5 mol)
(1 + 2.259)

Ê 5 mol ˆ Ê 5 mol ˆ
Therefore nA = yA Á
Ë 3.259 ¯˜
= (0.649 7) Á
Ë 3.259 ¯˜
= 0.996 8 mol

Ê 5 mol ˆ Ê 5 mol ˆ
nB = yB Á
Ë 3.259 ˜¯
= (0.350 3) Á
Ë 3.259 ˜¯
= 0.537 4 mol

4.11 ISOTHERMAL FRACTIONAL DISTILLATION OF AN IDEAL BINARY SOLUTION

Underlying Principle Isothermal distillation of an ideal binary solution is based on the fact that
whenever a liquid phase is in equilibrium with the vapour phase, the latter
is relatively richer in the more volatile component. This can be proved from
Eq. (4.9.4). We have
xA p*A yA 1
yA = or = (4.11.1)
xA p*A + xB p*B xA xA + xB ( p*B /p*A )

If the constituent A is more volatile than the constituent B, i.e. pA* > pB*,
then pB*/pA* will be less than one and so also the denominator of Eq. (4.11.1),
since xA + xB can only be equal to one. The result of this is that the right side
of Eq. (4.11.1) is greater than one and hence yA > xA, i.e. the amount fraction
of the component A, the more volatile one, in the vapour phase is larger than
that present in the liquid phase.
Effects of Isothermal Before we discuss the procedure that is employed for isothermal distillation, we
Decrease in Pressure will discuss the effects which are produced when the pressure of the system is
reduced isothermally.
 Solutions 145

Fig. 4.11.1 Effect of

reducing pressure at
constant temperature on
the ideal binary mixture

Let us start with the liquid phase as shown by the point a in Fig. 4.11.1.
Let the pressure of the system be reduced, while its temperature remains constant.
The effects to be observed are summarized as follows.
The state of the system will move along the vertical line aa a .
The system will remain of one phase (i.e. liquid) till the pressure corresponding
to the point b is reached.
At the state b of the system, the vapour phase just starts forming. Its
composition will correspond to the point c. The obtained vapour phase is
more rich in the component A (which is more volatile) as compared to the
liquid phase b.
Removal of more of the component A in the vapour phase makes the liquid
phase more rich in the component B with the result that the composition of
liquid phase moves along bb .
If the vaporization is to be continued, the pressure of the system must be
lowered. The overall state of the system will still move along the same
vertical line as shown, for example, by the point a .
At the point a , the compositions of the liquid and vapour phases are given
by the points b and c , respectively. The relative amounts of the two phases
as given by the lever rule are
Amount in liquid phase a ¢c ¢
=
Amount in vapour phase a ¢b ¢
Continued reduction of pressure brings the state point to c where only a
negligible trace of liquid b is left behind and the vapour phase has the
composition X which is the same as that of starting liquid (represented by
the point a).
146 A Textbook of Physical Chemistry

As the pressure is further reduced, the two-phase system is converted into

one-phase system consisting of the vapour phase.
To illustrate the above changes, we take up a specific example of a binary
liquid solution with pA* = 200 Torr and p*B = 100 Torr at a temperature T. Let us
have, for example, a solution of 1 mol of constituent A and 2 mol of constituent
B.
The total vapour pressure of the system would be

p = xA p*A + xB p*B = (1/3) (200 Torr) + (2/3) (100 Torr)

= 133.33 Torr
If the pressure on the system is higher than this value, no vapour phase can
exist and the system consists of only liquid phase. This may be represented
by the point a in Fig. 4.11.1.
Let the pressure on the system is lowered to a value just less than 133.33 Torr
(point b). At this pressure, a bubble of vapour will appear whose composition
would be

pA x p* (1/3) (200 Torr)

yA = = A A = = 0.50
p p (133.33 Torr)

The state representing this vapour phase is represented by the point c

in Fig. 4.11.1.
As the pressure on the system is gradually lowered, more and more of liquid
evaporates and the vapour phase becomes more rich in the component B.
As the last drop of the liquid evaporates, the composition of the vapour
phase approaches the composition of the entire system and thus yA = (1/3)
mol. The composition of last trace of liquid to be evaporated can be calculated
by using the expression

pA xA p*A xA p*A
yA = = =
p xA p*A + xB p*B xA p*A + (1 - xA ) p*B

Rearranging this expression, we get

p*B yA
xA =
p*A + ( p*B - p*A ) yA

Substituting the values, we get

(100 Torr)(1/3)
xA = = 0.20
(200 Torr) + (100 Torr - 200 Torr)(1/3)
The total pressure of the system at point b is
p = xA p*A + xB p*B = (0.20)(200 Torr) + (0.80)(100 Torr) = 120 Torr
 Solutions 147

The system will consist of two phases between the pressure range 120 Torr
– 133.33 Torr. The composition of liquid and vapour phases at any pressure
can be computed using the following expressions.

p - p*B
(i) p = xA p*A + (1 - xA )p*B fi xA =
p*A - p*B

pA x p* xA p*A
(ii) yA = = A A =
p p p*B + ( p*A - p*B )xA

For example, if p = 125 Torr, then

125 Torr - 100 Torr

xA = = 0.25
200 Torr - 100 Torr

xA p*A (0.25)(200 Torr)

yA = = = 0.40
p (125 Torr)

The individual amounts in liquid and vapour phases can be determined by

using the level rule.

Amount in liquid phase a ¢c ¢ y -X 0.40 - (1/3)

= = A = = 0.80
Amount in vapour phase a ¢b ¢ X - xA (1/3) - 0.25

Adding one to both sides and taking the inverse, we get

Amount in vapour phase 1

=
Amount in liquid and vapour phases 1.80

Thus Amount in vapour phase = (1/1.80) (3.0 mol) = 1.67 mol

Amount in liquid phase = 3.0 mol – 1.67 mol = 1.33 mol
Now Amount of A in liquid phase = xAn1 = (0.25) (1.33 mol) = 0.33 mol
Amount of B in liquid phase = 1.33 mol – 0.33 mol = 1.00 mol
Amount of A in vapour phase = yAnv = (0.40)(1.67 mol) = 0.67 mol
Amount of B in vapour phase = 1.67 mol – 0.67 mol = 1.00 mol

Example 4.11.1 (a) A liquid mixture of benzene and toluene is composed of 1 mol of benzene and 1
mol of toluene. If the pressure over the mixture at 300 K is reduced, at what pressure
does the first vapour form? Given: p*t = 4.274 kN m–2 and pb* = 13.734 kN m–2, where
the subscripts t and b stand for toluene and benzene, respectively.
(b) What is the composition of the first trace of vapour formed?
(c) If the pressure is reduced further, at what pressure does the last trace of liquid disappear?
(d) What is the composition of the last trace of liquid?
(e) What will be the pressure, the composition of the liquid and the composition of the
148 A Textbook of Physical Chemistry

vapour, when 1 mol of the mixture has been vaporized?

Solution (a) The first vapour will be formed when the external pressure becomes equal to the
vapour pressure of the system. Thus, the required pressure is

p = xt p*t + xb p*b
1 1
= (4.274 kN m -2 ) + (13.734 kN m -2 ) = 9.004 kN m –2
2 2
(b) Composition of the first vapour can be calculated using the equation

pt x p* (0.5)(4.274 kN m -2 )
yt = = t t = = 0.237 3
p p 9.004 kN m -2
yb = 1 - yt = 0.762 7

(c) The last trace of liquid will disappear when the composition of the vapour phase
becomes
1 1
yb = and yt = (i.e. practically whole of the liquid has vaporized)
2 2
The pressure at which this occurs can be calculated from the expression

p*b p*t
p= (Eq. 4.9.7)
p*t + (p*b - p*t )yt
(13.734 kN m -2 ) (4.274 kN m -2 )
=
(4.274 kN m -2 ) + (13.734 kN m -2 - 4.274 kN m -2 ) (0.5)
= 6.519 kN m -2
(d) Composition of the last trace of the liquid can be calculated using the expression

yt p (0.5) (6.519 kN m -2 )
xt = = = 0.762 6
p*t 4.274 kN m -2

Therefore xb = 1 – xt = 0.237 4
(e) Let nb be the amount of benzene present in 1 mol of the mixture that has been
vaporized.
Thus yb = nb /1 mol
The amount fraction of benzene in the remaining liquid phase will be
1 mol - nb
xb =
1 mol

Now from the expression p = p*t + ( p*b - p*t )xb , we get

p - p*t
xb = (1)
p*b - p*t

pb x p*
Also yb = = b b (2)
p p
 Solutions 149

Substituting the values of xb and yb in Eqs (1) and (2), we have

1 mol - nb p - p*t
= (3)
1 mol p*b - p*t

(1 mol - nb ) p*b
and nb = (4)
p

Rearranging Eq. (4) for nb, we have

(1 mol) p*b
nb = (5)
p + p*b

Substituting this in Eq. (3), we get

p*b p - p*t
1- = (6)
p + p*b p*b - p*t

Rearranging the above equation, we have

p= p*t p*b

Substituting the given values of p*t and p*b , we get

p = {(4.274 kN m -2 ) (13.734 kN m -2 )}1/2 = 7.662 kN m -2

Substituting p in Eq. (3), we get

1 mol - nb (7.662 kN m -2 ) - (4.274 kN m -2 ) 3.388
= -2 -2
=
(1 mol) (13.734 kN m ) - (4.274 kN m ) 9.460
Ê 3.388 ˆ 6.072
or nb = Á 1 - ˜ mol = mol = 0.642 mol
Ë 9.460 ¯ 9.480
Thus yb = nb /mol = 0.642 and yt = 1 - yb = 0.358

Example 4.11.2 The vapour pressures of two pure liquids, A and B, that form an ideal solution are 300
and 800 Torr, respectively, at temperature T. A mixture of the vapours of A and B for
which the amount fraction of A is 0.25 is slowly compressed at temperature T. Calculate
(a) the composition of the first drop of the condensate, (b) the total pressure when this
drop is formed, (c) the composition of the solution whose normal boiling point is T. (d)
the pressure when only the last bubble of vapour remains, and (e) the composition of
the last bubble.

Solution The given data are

p*A = 300 Torr p*B = 800 Torr yA = 0.25

pA xA p*A xA p*A
(a) We have yA = = =
p xA p*A + xB p*B p*B + ( p*A - p*B )xA
150 A Textbook of Physical Chemistry

yA p*B
Therefore xA =
p*A - ( p*A - p*B )yA

Substituting the given data, we have

(0.25) (800 Torr)

xA = = 0.470 6
300 Torr - (300 Torr - 800 Torr) (0.25)

(b) We have

p = xA p*A + xB p*B = xA p*A + (1 - xA )p*B

Substituting the given data, we get

p = 0.470 6 ¥ 300 Torr + 0.529 4 ¥ 800 Torr

= 141.18 Torr + 423.52 Torr = 564.7 Torr

(c) For the normal boiling point, we have

p = 760 Torr = xA p*A + (1 - xA ) p*B

760 Torr - p*B

Therefore xA =
p*A - p*B

Substituting the given data, we have

760 Torr - 800 Torr

xA = = 0.08
300 Torr - 800 Torr
Thus xB = 1 – 0.08 = 0.92

(d) Here, the amount fraction of A in the liquid phase will be the same as that of A in
the original vapour phase, i.e. xA = 0.25

Hence p = xA p*A + xB p*B = 0.25 ¥ 300 Torr + 0.75 ¥ 800 Torr

= 75 Torr + 600 Torr = 675 Torr
(e) In this case, we have

xA pA* 0.25 ¥ 300 Torr

yA = = = 0.111
p 675 Torr
yB = 1 - yA = 0.889

Example 4.11.3 The vapour pressure of two pure liquids A and B which form an ideal solution are 300
and 800 Torr, respectively, at temperature T. A liquid solution of A and B for which the
amount fraction of A is 0.60 is contained in a cylinder closed by a piston on which the
pressure can be varied. The solution is slowly vaporized at temperature T by decreasing
the applied pressure, starting with a pressure of about 1 atm. Calculate (a) the pressure
at which the first bubble of vapour is formed, (b) the composition of the vapour in this
bubble, (c) the composition of the last droplet, and (d) the pressure when only this last
droplet of liquid remains.
 Solutions 151

Solution The given data are

p*A = 300 Torr p*B = 800 Torr xA = 0.60

(a) The pressure at which first bubble of vapour is formed

We have

p = xA p*A + xB p*B = 0.6 ¥ 300 Torr + 0.4 ¥ 800 Torr

= 180 Torr + 320 Torr = 500 Torr
(b) Amount fractions of components in the first bubble of vapour
We have

pA xA p*A 0.60 ¥ 300 Torr

yA = = = = 0.36
p 500 Torr 500 Torr

Thus yB = 1 – 0.36 = 0.64

(c) Amount fractions of components in the last drop of liquid

Here we will have yA = 0.60 (as most of the liquid has vaporized).

pA xA p*A xA p*A
Now yA = = =
p xA p*A + xB p*B p*B + ( p*A - p*)
B xA

Substituting the given data, we get

xA (300 Torr)
0.60 =
800 Torr + (300 Torr - 800 Torr)xA

Solving for xA, we have

xA = 0.80
Thus xB = 1 – xA = 0.20
(d) Pressure when the last droplet of liquid remains

We have p = xA p*A + xB p*B = 0.80 ¥ 300 Torr + 0.2 ¥ 800 Torr

= 240 Torr + 160 Torr = 400 Torr

Procedure of Suppose the vapour which is formed over the solution is removed and is condensed
Isothermal separately. This new liquid which is formed will be richer in the more volatile
Fractional constituent. Now, let again the vapour which is formed over this new solution
Distillation be removed and recondensed. the new liquid which is formed will be still richer
in the more volatile constituent. Let this procedure of removing the vapour from
the newer solution and condensing them be repeated several times. Ultimately, a
stage will come when the vapour consists only of the more volatile constituent and
the liquid that of the less volatile constituent. Thus a separation of constituents
has been achieved.
152 A Textbook of Physical Chemistry

The above method is useful for those mixtures which would decompose
if distilled by ordinary methods. However, it is very inconvenient and is used
only when the other method of separation is not available.
Konowaloff’s Rule From Eqs (4.11.1) and (4.9.3), we have drawn the following two conclusions.
(i) If pA* > p B*, the amount fraction of the component A in the vapour phase
is larger than in the liquid phase. In other words, the vapour phase is
richer in the component A than the liquid phase.
(ii) If pA* > p B*, the component A is more volatile than the component B. In a
system where component A is more volatile, the total vapour pressure of
the system increases with increase in the amount fraction xA of the more
volatile component. In other words, if we add more of the component A
in the liquid phase, the total vapour pressure of the system is increased.
We can combine the above two conclusions in a statement given below.
The vapour phase is richer in the component whose addition to the liquid mixture
results in an increase in total vapour pressure.
The above statement is, in fact, the Konowaloff’s rule, which we shall
derive more rigorously in Section 4.15.

4.12 TEMPERATURE-COMPOSITION DIAGRAM OF A BINARY LIQUID SOLUTION

Qualitative We have already seen that if the two phases are in equilibrium in a binary
Description system, then its variance is two. Thus fixing the values of any of the two variables
amongst temperature, pressure and composition, completely defines the system.
The third variable automatically has a fixed value. For example, if temperature
and composition are chosen, then the equilibrium pressure of the system has a
fixed value. Mathematically, this can be stated as
p = f (temperature, composition) (4.12.1)
If the temperature is held constant, then p depends only on the composition
of the mixture. Thus
p = f (composition) (T constant) (4.12.2)
Likewise, if pressure and composition be chosen as the independent variables,
then the temperature becomes the dependent variable, i.e.
T = f (pressure, composition) (4.12.3)
If the pressure is kept constant for a series of solutions of different
compositions, then
T = f (composition) (p constant) (4.12.4)
that is, temperature at which the given system has the equilibrium pressure p
will depend on the composition of the system.
Equations (4.12.2) and (4.12.4) may be understood by taking an example
of liquid-vapour equilibrium of an ideal binary liquid system. From Raoult’s
law, the total vapour pressure p of the system is given by
 Solutions 153

p = pA + pB = xA p*A + xB p*B = xA p*A + (1 - xA )p*B

= p*B + ( p*A - p*B )xA (4.12.5)

Thus p depends on xA, the composition of the solution and on the values
of pA* and pB*, the vapour pressures of the pure constituents. Since pA* and
pB* depend only on temperature, it follows that p is a function of temperature
and composition. Now if the temperature is kept constant (i.e. pA* and pB* are
constant), then p depends only on the composition of the solution. Figure 4.9.1
shows the dependence of p on composition of an ideal binary liquid system at
a constant temperature. Now suppose we want to keep the equilibrium pressure
p to a constant value. For a system, this given value of p can be obtained by
varying the temperature of the system. This time pA* and pB* are being changed
so that the value of p as calculated from Eq. (4.12.5) becomes equal to the
given value of the pressure. The temperature at which this equality is obtained
will depend upon the composition of the system.
Dependence of The boiling point of a liquid (or a solution) is the temperature at which the vapour
Boiling Point of a pressure of the liquid (or the total vapour pressure of the solution) becomes equal
Solution on its to that of the external pressure. If the external pressure is 1 atm, the boiling point
Composition is known as the normal boiling point. A liquid which has a higher vapour
pressure will have a lower boiling point since less heating will be required to
attain vapour pressure equal to the external pressure. Similarly, a liquid with low
vapour pressure will have a high boiling point. The boiling point of a solution
will have a definite relation with the composition of the solution. The relation
connecting these two may be determined with the help of Clausius-Clapeyron
equation.
Let TA* and T B* be the normal boiling points of constituents A and B,
respectively. Let T be the normal boiling point of a solution of known composition
and let pA* and pB* be the vapour pressures of pure constituents at temperature T.
Applying Clausius-Clapeyron equation separately to both the constituents, we have

Ê p* ˆ D vap H m, A Ê 1 1ˆ
ln Á A ˜ = Á - ˜
Ë 1 atm ¯ R Ë TA* T ¯

p*A ÏÔ D vap H m, A Ê 1 1 ˆ ¸Ô
or = exp Ì Á - ˜˝ (4.12.6a)
atm ÔÓ R Ë TA* T ¯ Ô˛

Ê p* ˆ D vap H m, B Ê 1 1ˆ
ln Á B ˜ = Á * -T˜
Ë 1 atm ¯ R Ë TB ¯

p*B ÏÔ D vap H m, B Ê 1 1 ˆ Ô¸
or = exp Ì Á - ˜˝ (4.12.6b)
atm ÔÓ R Ë TB* T ¯ Ô˛
Now the total vapour pressure of the solution of known composition is
p = xA p*A + xB p*B
154 A Textbook of Physical Chemistry

and this, by definition, is equal to 1 atm (the external pressure). Thus, we have

Ê p* ˆ Ê p* ˆ
1 = xA Á A ˜ + xB Á B ˜
Ë atm ¯ Ë atm ¯
ÔÏ D vap H m, A Ê 1 1 ˆ Ô¸ ÔÏ D vap H m, B Ê 1 1 ˆ Ô¸
= xA exp Ì Á - ˜ ˝ + xB exp Ì Á - ˜˝
ÔÓ R Ë TA* T ¯ Ô˛ ÔÓ R Ë TB* T ¯ Ô˛
ÏÔ D vap Sm, A Ê T * ˆ ¸Ô ÏÔ D vap Sm, B Ê T * ˆ ¸Ô
= xA exp Ì Á 1 - A ˜ ˝ + xB exp Ì Á 1- B ˜˝
ÓÔ R Ë T ¯ ˛Ô ÓÔ R Ë T ¯ ˛Ô
(4.12.7)

where vapSA,m and vapSB,m are the molar entropy changes for the liquid to
vapour conversion for the components A and B, respectively. Assuming that the
liquids follow Trouton’s rule ( vapSm = vapSm, A = vapSm, B = 88 J K–1 mol–1),
we have

ÏÔ D vap Sm Ê T * ˆ ¸Ô ÏÔ D vap Sm Ê T * ˆ ¸Ô
1 = xA exp Ì Á 1 - A ˜ ˝ + xB exp Ì Á 1- B ˜˝
ÔÓ R Ë TA ¯ Ô˛ ÔÓ R Ë T ¯ Ô˛

Ê D vap Sm ˆ ÏÔ D vap Sm Ê TA* ˆ ¸Ô ÏÔ D vap Sm Ê TB* ˆ ¸Ô

or exp Á - = xA exp Ì- Á ˜ ˝ + xB exp Ì- ˝
Ë R ¯ ˜
ÓÔ R Ë T ¯ ˛Ô ÔÓ R ÁË T ˜¯ ˛Ô
(4.12.8)

Thus, knowing TA*, T B* and xA (or xB, since xA + xB = 1), we can solve the
above equation for T, the boiling point of the solution.

Composition of Composition of vapour at temperature T can be determined as usual from the

Vapour at a Given relations
Temperature
ÔÏ D vap Sm Ê T * ˆ Ô¸
xA exp Ì Á 1- A ˜˝
xA ( p*A /p∞) ÔÓ R Ë T ¯ Ô˛
yA = =
xA ( p*A /p∞) + xB ( p*B /p∞) 1

ÔÏ D vap Sm Ê T * ˆ Ô¸
xB exp Ì Á 1- B ˜˝
xB ( p*B /p∞) ÓÔ R Ë T ¯ ˛Ô
and yB = = (4.12.9)
xA ( p*A /p∞) + xB ( p*B /p∞) 1

where pº is the unit pressure.

Depiction of the Figure 4.12.1 shows the graph of boiling point versus composition for the ideal
Diagram solution corresponding to Fig. 4.10.1.
 Solutions 155

Fig. 4.12.1 Graph of

boiling point versus
amount fraction corres-
ponding to Fig. 4.10.1

Qualitative Features Neither the liquidus nor the vapourous curve is a straight line. This follows
of the Diagram immediately from the forms of Eqs (4.12.8) and (4.12.9).
The lower region of the figure represents the liquid phase as this phase
is stable at lower temperatures. Thus, the lower curved line represents the
liquidus curve. Similarly, it can be concluded that upper region of the figure
represents the vapour phase as this phase is stable at higher temperatures.
Thus, the upper curved line represents the vaporous curve.
The normal boiling point TB* of the constituent B is higher than that of the
constituent A, i.e. TA*. This follows immediately from the fact that the vapour
pressure of the constituent A is higher than that of the constituent B.
The central region between the two curved lines represents the liquid-vapour
equilibrium.
Effects Produced on Now we can examine the sequence of events that takes place when a given liquid
Heating a System mixture under a constant pressure is heated from a lower temperature to a
high temperature. Let us start with a system represented by the point a in
Fig. 4.12.1.
On increasing the temperature at constant pressure, the state of the system
will move along the vertical line aa a .
The system will remain of one phase till the temperature T is reached where
the liquid just starts boiling with the vapour composition corresponding to
the point c.
The vapour phase is richer than the liquid in the component A, the lower
boiling component. Removal of more of the component A in the vapour phase
makes the solution more rich in the second component with the result that
the composition of the solution moves along bb .
156 A Textbook of Physical Chemistry

If the boiling is to be continued, the temperature of the system must be

increased; there occurs an increase in the boiling point of the solution.
The overall state of the system at any temperature will be represented by a point
on the vertical line aa a . For example, at point a , the compositions of liquid and
vapour phases are represented by the points b and c , respectively. The relative
amounts of these two phases as given by the lever rule are
Amount in liquid phase a ¢c ¢
=
Amount in vapour phase a ¢ b¢
The increase in temperature will eventually bring the system to the point c
where only a last trace of liquid of composition b is left and the vapour
phase has the composition X.
If the temperature of the system is slightly increased the liquid phase disappears
completely and the system becomes of one phase comprising of the vapour
phase.

Example 4.12.1 The boiling points of pure benzene and toluene are 353.25 K and 383.75 K under
1 atm pressure. By employing appropriate equations, determine the compositions of the
liquid mixture and its vapour when the former just starts boiling at 368.15 K. Assume
that Trouton’s law is applicable to both the constituents.
Solution We know from Eq. (4.12.8) that

Ê D vap Sm ˆ ÏÔ D vap Sm Ê Tb* ˆ ¸Ô ÏÔ D vap Sm Ê Tt* ˆ ¸Ô

exp Á - ˜ = xb exp Ì- Á ˜ ˝ + xt exp Ì- Á ˜˝ (1)
Ë R ¯ ÔÓ R Ë T ¯ Ô˛ ÔÓ R Ë T ¯ Ô˛

where, according to Trouton’s law, vapSm/R = 10.6

Now Tb* = Tbenzene
* = 353.25 K Tt* = Ttoluene
* = 383.75 K
T = 368.15 K xt = 1 - xb
Substituting these in Eq. (1), we get

{ Ê 353.25 ˆ
exp( - 10.6) = xb exp - 10.6 Á
Ë 368.15 ˜¯ } { Ê 383.75 ˆ
+ (1 - xb ) exp - 10.6 Á
Ë 368.15 ˜¯ }
–5 –5 –5
2.576 × 10 = xb(3.908 × 10 ) + (1 – xb) (1.629 × 10 )

2.576 ¥ 10 -5 - 1.629 ¥ 10 -5
or xb = = 0.415
3.908 ¥ 10 -5 - 1.629 ¥ 10 -5
xt = 1 – xb = 1 – 0.415 = 0.585
Composition of the issuing vapour can be calculated using the expression
ÏÔ DSm Ê Tb* ˆ ¸Ô
yb = xb exp Ì Á1 - ˜ ˝ (Eq. 4.12.9)
ÓÔ R Ë T ¯ ˛Ô
Substituting the data, we get

{ Ê
yb = 0.415 ¥ exp 10.6 Ë 1 -
353.25 ˆ
368.15 ¯ }
= 0.415 ¥ exp (0.429)

= 0.637
Thus yt = 1 – yb = 0.363
 Solutions 157

4.13 ISOBARIC FRACTIONAL DISTILLATION OF AN IDEAL BINARY SOLUTION

Underlying Principle The isobaric process of distillation in which the external pressure is kept constant
instead of temperature is more convenient and is often employed for the separation
of constituents of a binary liquid system. The principle of separation of
constituents using the isobaric fractional distillation may be explained with the
help of temperature-composition diagram shown in Fig. 4.13.1.

Fig. 4.13.1 Principle of

isobaric distillation

Let the starting composition of the solution to be distilled be represented by

the point a. Let the temperature of the solution be raised till it starts boiling.
At this stage, the vapour pressure of the solution is equal to the external
pressure, which is kept constant throughout the distillation process. Usually
the atmospheric pressure of 1 atm is employed for this purpose. The vapour
which appeared at the boiling point T is represented by b . Since the latter is
richer in the constituent A (the more volatile constituent), the residual liquid
will become richer in the constituent B and will boil at a slightly higher
temperature.
Let the vapour formed at T be removed and condensed separately to yield
distillate b. Let this new distillate be heated till it starts boiling, the vapour
which now emerges is represented by c and is still richer in the constituent
A.
If the above sequence of collecting the vapour, condensing them to give a
new distillate and heating the new distillate to its boiling point is repeated
several times, the vapour will continue to contain more and more of the
constituent A and ultimately a stage would be reached where it would
contain only this constituent.
158 A Textbook of Physical Chemistry

The residual liquid at any stage can be mixed with the previous residual
liquid and can be treated in the same way. The residual liquid continues to
contain lesser and lesser of the more volatile constituent and thus more and more
of the lesser volatile constituent. When the process is repeated several times, a
stage would be reached when the residual liquid would contain only the lesser
volatile constituent.
Thus, we see that by carrying out the above fractional distillation process,
it is possible to separate the two constituents of a binary liquid mixture; vapour
containing more volatile constituent and the liquid containing less volatile
constituent.
Theoretical Plate Each horizontal line in the zig-zag steps shown in Fig. 4.13.1 is known as the
theoretical plate. For example, in going from liquid of composition a to c, we have
two theoretical plates.

Example 4.13.1 The vapour pressures of two liquids A and B that form an ideal solution are given by
the equations:
5 100 K
log( pA / Torr) = − + 16.24
T
4 530 K
log( pB / Torr) = − + 13.38
T
Draw the temperature-composition phase diagram for solutions of A and B at a total
pressure of 1 atm. How many theoretical plates in the fractionating column will be present
in going from liquid composition xA = 0.03 to xA = 0.96?
Solution Boiling points of the two liquids These can be obtained by substituting pA = pB =
760 Torr in the given expressions

5 100 K
log( pA / Torr) = - + 16.24
T
4 530 K
log( pB / Torr) = - + 13.38
T
5 100 K 5 100 K 5 100 K
Thus TA* = = = = 381.7 K
16.24 - log( pA / Torr) 16.24 - log(760) 16.24 - 2.880 8
4 530 K 4 530 K 4 530 K
TB* = = = = 413.4 K
13.38 - log( pB / Torr) 13.38 - log(760) 13.38 - 2.880 8

Compositions of the solution and vapour at different temperatures For a given

temperature, pA* and p B* can be obtained from the given relations

5 100 K
log( p*A / Torr) = - + 16.24 (1)
T
4 530 K
log( p*B / Torr) = - + 13.38 (2)
T
Let xA be the amount fraction of liquid A in the solution. The amount fraction of
liquid B will be equal to (1 – xA). Since the two liquids form an ideal solution, the
partial vapour pressures of the two liquids can be obtained by using Raoult’s law, i.e.
 Solutions 159

pA = xA p*A
pB = xB p*B = (1 - xA )p*B
Since the total pressure is 760 Torr, therefore
p = pA + pB = xA p*A + (1 - xA )p*B = 760 Torr

760 Torr - p*B

or xA = (3)
p*A - p*B
The composition of constituent A in the vapour phase is given by
pA xA p*A (4)
yA = =
p 760 Torr
The values of p*A, p*B, xA and yA as calculated from Eqs (1) to (4) at different temperatures
are given below.

760 Torr - p*B xA p*A

T/K p*A / Torr p*B / Torr xA = yA =
p*A - p*B 760 Torr
385 1 000 39.81 0.750 0.986
390 1 445 58.88 0.506 0.962
400 3 090 114.8 0.217 0.882
410 6 310 213.8 0.089 0.743
420 12 590 398.1 0.030 0.491
425 17 380 573.0 0.029 0.255

On plotting temperature versus composition, we get a graph as shown in Fig. 4.13.2.

The number of theoretical plates in a column in going from xA = 0.03 (point b3) to
xA = 0.96 (point c1) are two since there are two horizontal lines present in the zig-zag steps.

Fig. 4.13.2 The

required temperature
versus composition plot
160 A Textbook of Physical Chemistry

Example 4.13.2 A liquid mixture containing 50 mol per cent of liquid A in Example 4.13.1 was heated
gradually. Answer the following from the phase diagram thus obtained:
(i) What is the normal boiling point of the mixture?
(ii) What is the composition of the vapour that appears at the normal boiling point?
(iii) Indicate whether the boiling point of the remaining liquid mixture increases or
decreases.
(iv) What are the compositions of liquid and vapour at temperature 410 K? What are
their relative amounts?
(v) What is the composition of the last drop of the liquid to be vaporized?
(vi) If the given mixture of 50 mol per cent of liquid A is distilled without removing
the distillate till the temperature of residue is 410 K, what will be the composition
of the resultant distillate?

Solution (i) Normal boiling point of the mixture = 391 K

(ii) Composition of vapour issuing at 391 K (near the point c1);

yB = 0.045 and yA = 0.955

(iii) Boiling point of the remaining liquid mixture increases.

(iv) Compositions at 410 K are
Composition of liquid (point b2): xA = 0.09, xB = 0.91

Composition of vapour (point c2): yA = 0.74, yB = 0.26

Amount of liquid mixture ac y - 0.5 0.24

= 2 = A =
Amount of vapour b 2a 0.5 - xA 0.41

0.41
Amount % of vapour = ¥ 100 = 63.08
0.24 + 0.41

Amount % of liquid = 100 – 63.08 = 36.92

(v) Composition of the last drop of the liquid to be vaporized (near the point b3);

xA = 0.035 and xB = 0.965

(vi) The composition of the resultant distillate will be the mean of the initial composition
of vapour (which appears when the composition of liquid mixture is 50 mol per
cent in A) and the final composition of vapour (when the temperature of the residue
is 410 K). The two compositions are:

(yA )initial = 0.955 and (yA )final = 0.743

Hence, the amount fraction of A in the resultant distillate will be

0.955 + 0.743
= 0.743 0.85
2

The Fractionating The process of fractional distillation is extremely tedious and involves more time
Column and labour as the separation is carried out in batches and in a discontinuous
manner. However, these difficulties can be overcome by employing a fractionating
 Solutions 161

column, which essentially carries the distillation in a continuous manner. Figure

4.13.3 displays one such column commonly employed in industry. This is known
as the bubble-cap column. It consists of a long tube carrying a large number of
bubble-cap plates and is attached to a boiler at the bottom and to a condenser at
the top. Each plate can hold a thin layer of liquid and has an overflow mechanism
through which the excess liquid can pass to the plate just below it. It also has
many bubble-caps through which the vapour passes upward after bubbling through
the liquid. There is a temperature gradient along the length of the column, the
top being cooler than the bottom. The various plates are thus situated at different
temperatures and also hold the liquid at that temperature.
Principle Underlying The principle of bubble-cap column can be illustrated very nicely with the help
Fractionating Column of temperature-composition diagram (Fig. 4.13.4).
Let the liquid be boiled at the bottom, say at temperature T0. The vapour
issuing has composition v0. When this vapour is passed through the first plate,
it is cooled to temperature T1 and thus its state is moved to the point a. At this
state, some of the vapour condenses to form liquid of composition l1 and the

Fig. 4.13.3 Bubble-cap distilling column Fig. 4.13.4 Scheme of redistribution of constituents
in the distilling column
162 A Textbook of Physical Chemistry

remaining vapour has composition v1. The liquid formed contains more of the
less volatile constituent. Next, the vapour of composition v1 is passed through
the second plate whose temperature is T2(T2 < T1). Here the vapour is cooled to
T2 and thus the state of system is moved from v1 to b. At this state, again part
of the vapour is condensed to give liquid of composition l2 and the remaining
vapour has composition v2. Now the vapour has become more enriched in the
more volatile constituent. This happens at every plate of the column as is also
shown in Fig. 4.13.4. As the vapour moves up the column, it is being cooled;
this cooling condenses the less volatile component preferentially, so that the
vapour becomes increasingly enriched in the more volatile component as it
passes upward from one plate to another.
Similarly, as the liquid flows down, its temperature is increased and again
there is a redistribution of the constituents. For example, the liquid of composition
l3 has flown from the plate 3 to plate 2. The liquid has been heated from T3 to
T2 and thus the state of the system has moved from l3 to b . Thus part of the
liquid vaporizes to yield vapour of composition v2 containing more of the
more volatile constituent. The resultant liquid has a composition of l2 and thus
contains more of the less volatile constituent. This happens at every plate of the
column as shown in Fig. 4.13.4. As the liquid moves down the column, it is
being heated; this heating vaporizes the more volatile constituent preferentially,
so that the liquid becomes increasing enriched in the less volatile component
as it moves downward from one plate to another.
If sufficient number of plates are used, it is possible to separate the two
constituents of a binary liquid mixture; the more volatile constituent in the
vapour form is collected from the top of the distilling column and that of lesser
volatile constituent from the bottom of the column. The vapour from the top of
the column is fed into a condenser where it is liquefied. Part of this liquid is
drawn off and the rest is returned to the column in order to maintain the stock
of essentially pure distillate on the upper plates. In order to make the separation
continuous, the preheated liquid mixture is introduced somewhere within the
column as shown in Fig. 4.13.3.

4.14 NONIDEAL SOLUTIONS OF LIQUID IN LIQUID

Nonideal Solutions It was pointed out earlier that an ideal binary liquid solution is formed only
when two liquids having more or less identical intermolecular forces of attraction
are mixed together, so that the environment around any particular molecule of
either of the two liquids is identical to that existing in the liquid mixture. This
condition is, however, not satisfied for most liquid pairs and thus they form
nonideal solutions. These solutions show deviations from Raoult’s law. The
nature and the extent of deviation depends upon the types of liquids that are
being mixed up. Two types of deviations are observed as describe below.
Positive Deviation If the forces of attraction between unlike molecules (i.e. between A and B) are
weaker than those between like molecules (i.e. between either A and A or B and
B), the solution shows positive deviation from Raoult’s law. In this case, the
vapour pressure curves of the constituents and the mixture lie above those of
ideal lines (Fig. 4.14.1).
 Solutions 163

Fig. 4.14.1 Pressure-

composition curves of a
typical nonideal solution
exhibiting positive
deviation from ideality

The positive deviation arises from the fact that the tendency of molecules
of each kind to escape from the solution to vapour is greater in nonideal
solution than that prevailing in an ideal solution. The extent of positive deviation
depends upon many factors. Some of them are: (i) difference in polarity of the
molecules; (ii) difference in the length of hydrocarbon chain or analogous
grouping of the molecules; (iii) difference in the intermolecular forces of
attraction; and (iv) association of either of the constituent in the liquid state.
The deviation is larger if the two liquids differ greatly in respect to the above
factors in which cases a maximum in the plot of total vapour pressure versus
composition of solution is observed.
Examples of Examples of solutions showing positive deviation are numerous. In fact, most
Positive Deviation liquid pairs fall into this category. Some of these are:
(i) Carbon tetrachloride and heptane at 323 K: This solution shows small
deviations from Raoult’s law as both the constituents are nonpolar and involve
low forces of attraction.
(ii) Ethyl ether and acetone at 293 K and 303 K: Deviations here are bit
larger as the components differ appreciably in the intermolecular attraction forces.
(iii) Heptane and ethyl alcohol at 323 K: This solution shows very large
deviations as the two liquids differ appreciably in all the above four factors,
namely, polarity, chain length, intermolecular forces of attraction and the
association of alcohol in the liquid state.
Negative Deviation If, on the other hand, the forces of attraction between unlike molecules (i.e.
between A and B) are stronger than those between like molecules (i.e. between
164 A Textbook of Physical Chemistry

either A and A or B and B), then the solution shows negative deviation from
Raoult’s law. Here the vapour pressure curves of the constituents and the
mixture lie below those of the ideal lines. In this case, the tendency of molecules
of each kind to escape from the solution into the vapour is weak relative to
that found in an ideal solution. This is primarily due to the stronger interactions
between the unlike molecules. Figure 4.14.2 exhibits pressure-composition curves
of a typical solution exhibiting negative deviation from ideality. The deviation
is larger if the two constituents form partial compound in the solution and in
such cases a minimum in the plot of total vapour pressure versus composition
of solution is observed.
Examples of Examples of solutions showing negative deviation are not very common. A few
Negative Deviation examples are:
(i) Pyridine and formic acid (or acetic or propanoic acid): One of the
constituents is basic and the other one is acidic.
(ii) Mixture of halomethane (e.g., chloroform) with an oxygen or nitrogen
compound (e.g., a ketone, ether, ester or amine): In this case, there occurs a
partial association between the molecules through the hydrogen bonding.
(iii) An aqueous solution of a strong volatile acid such as halogen acids,
nitric acid and perchloro acids: In this case, non-volatile ions are formed with
the interaction of ions of the acid with water.
Ideally Dilute There is one common feature in Figs 4.14.1 and 4.14.2 that the partial pressure
Solution curves of each component approaches the ideal ones asymptotically as the
amount fraction of the component approaches one. This is to be expected since
at this stage, the solution is very dilute and hence behaves ideally. This dilute
solution is known as ideally dilute solution. Thus, we can say that Raoult’s law
is a limiting law for the solvent (major component as xA 1 or xB 1) in
very dilute solutions. Mathematically, it may be expressed as

Êp ˆ Êp ˆ
lim Á A ˜ = p*A and lim Á B ˜ = p*B (4.14.1)
xA Æ 1 Ë xA ¯ xB Æ 1 Ë xB ¯

It was shown earlier that if Raoult’s law is applicable to the major component
(solvent) over a certain region of concentration, then Henry’s law is followed by
the minor component (solute) over the same region of concentration. It is thus
expected that the partial vapour pressure curve of each of the two components
should also approach linearity asymptotically, as the amount fraction of the
component approaches zero. In fact, it is found to be so and thus the linearity
observed at x 0 represents the limiting behaviour of Henry’s law as applicable
to the solute. Mathematically, the linearity may be expressed as

Êp ˆ Êp ˆ
lim Á A ˜ = kH(A) and lim Á B ˜ = kH(B) (4.14.2)
Ë xA ¯
xA Æ 0 Ë xB ¯
xB Æ 0

where kH(A) is a constant for a given solute (A) in a particular solvent (B) and
is not equal to pA*. Likewise, kH(B) is also constant and will not be equal to pB*.
 Solutions 165

Fig. 4.14.2 Pressure-

composition diagram of a
typical system exhibiting
negative deviation

In general, the slope of the limiting Henry’s law line is greater than that of
the limiting Raoult’s law line in case of positive deviation from ideality and is
smaller in case of negative deviation from ideality.

Expression of Raoult’s Law for a Nonideal Solution

For an ideal solution, Raoult’s law is expressed as
pi = xi pi* (4.14.3)
For the ith constituent in a nonideal solution, Raoult’s law may be expressed as
pi = ai p*i (4.14.4)
where ai is the activity of ith constituent in the solution.† In terms of amount
fraction, we have
pi = (xig i ) pi* (4.14.5)
where γi is the activity coefficient of ith constituent in the solution. From
Eq. (4.14.5), it follows that
pi
ai = xig i = (4.14.6a)
pi*
pi ( pi )real
or gi = = (4.14.6b)
xi p*i ( pi )ideal

†
See Annexure I at the end of Chapter 8 for the concept of activity.
166 A Textbook of Physical Chemistry

For a solution exhibiting positive deviation from ideality, we have

( pi )real > ( pi )ideal i.e. gi > 1 (4.14.7)

and for a solution exhibiting negative deviation

( pi )real < ( pi )ideal i.e. gi < 1 (4.14.8)

From Figs 4.14.1 and 4.14.2, it is obvious that the activity coefficient γi will
vary as the amount fraction of ith constituent in the solution is varied. But
there is one common feature that γi 1 as xi 1, since (pi)real approaches
( pi)ideal asymptotically as the amount fraction of the constituent approaches one.
The typical variations of activity coefficient with mole fraction for positive and
negative deviations are of the type shown in Fig. 4.14.2.

Fig. 4.14.3 Typical

variations of
activity coefficient
with amount
fraction

Example 4.14.1 Starting from the fact that for a binary solution exhibiting negative deviation from Raoult’s
law, solute-solvent interactions are strong compared to solute-solute and solvent-solvent
interactions, show that for such a solution
D mix H < D mix H (ideal); D mix S < D mix S (ideal)
D mixG < 0; pA < pA (ideal)
Solution Since solute-solvent interactions are stronger than solute-solute interactions (B B)
and solvent-solvent interactions (A A), we have
DH A ◊ ◊ ◊ B > DH A ◊ ◊ ◊ A and DH A ◊ ◊ ◊ B > DH B ◊ ◊ ◊ B (1)
where HA A , HB B and HA B represent the enthalpies required to separate
A A in the solvent, B B in the solute and A B in the solution, respectively.
For an ideal solution, we have
DH A ◊ ◊ ◊ A (ideal) = DH B ◊ ◊ ◊ B (ideal) = DH A ◊ ◊ ◊ B (ideal) (2)
 Solutions 167

In the solution process, we will be breaking A A and B B interactions and will

be generating 2(A B) interactions, i.e.
D mix H = DH A ◊ ◊ ◊ A + DH B ◊ ◊ ◊ B + 2( - DH A ◊ ◊ ◊ B ) (3)
For an ideal solution, From Eq. (2), we get
D mix H (ideal) = 0
For a nonideal solution which satisfies Eq. (1), we get
D mix H = - ve i.e. D mix H < D mix H (ideal) (4)
that is, heat will be released on mixing solute and solvent to form a solution. mixS of
the solution process will always be positive as the solute and solvent molecules are more
disordered in solution than in the pure liquids. For an ideal solution, mixS will have a
maximum value as there exists no interaction terms. If A B interactions are strong, there
will be some ordering in the solution, which make mixS smaller than mixS(ideal), i.e.
D mix S < D mix S (ideal) (5)

mixG will be given by

D mixG = D mix H - T D mix S
Now mixH is negative; tending to make mixG more negative than for an ideal solution.
But T mixS is less positive than T mixS(ideal), which tends to make – T mixS and
mixG less negative. Though the final mixG is negative, but its value relative to the ideal
solution depends on the relative magnitudes of mixH and T mixS.
Finally, because of A B interactions, A will not be as free to vaporize as in the
ideal solution. Thus, we will have
pA < pA (ideal) (6)

4.15 THE DUHEM-MARGULES EQUATION

Thermodynamic A quantitative relation between the partial vapour pressures of the two
Derivation constituents of a binary liquid system and their corresponding amount fractions in
liquid phase can be derived thermodynamically. We start with the Gibbs-Duhem
equation for a system of two components A and B, such that
nA dm A + nB dm B = 0
or nA dm A = - nB dm B
Dividing both sides by nA + nB, we have
nA nB
dm = - dm (4.15.1)
nA + nB A nA + nB B
or xA dm A = - xB dm B
where xA and xB are the amount fractions of components A and B, respectively.
Dividing throughout by dxA, we get
dm A dm
xA = - xB B (4.15.2)
dx A dx A
Since xA + xB = 1, therefore
dxA + dxB = 0
168 A Textbook of Physical Chemistry

or dxA = - dxB
Substituting the above relation in Eq. (4.15.2), we get
dm A dm
xA = xB B (4.15.3)
dx A dx B
The chemical potential of any constituent of a liquid mixture is given by
mi (sol) = m*i + RT ln ( p/p∞) (4.15.4)
where p is the partial vapour pressure of that constituent. In deriving the above
expression, it is assumed that the vapour behaves as an ideal gas. For the
component A, the above equation on differentiating with respect to xA at constant
temperature and total pressure gives
dm A d ln ( pA /p∞)
= RT (4.15.5)
dx A dx A
Similarly, for the component B, differentiation with respect to xB gives
dm B d ln ( pB /p∞)
= RT (4.15.6)
dxB dx B
Multiplying Eq. (4.15.5) by xA and Eq. (4.15.6) by xB and equating the resultant
expressions (Eq. 4.15.3), we get
d ln ( pA /p∞) d ln ( pB /p∞)
xA = xB
dx A dx B
d ln ( pA /p∞) d ln ( pB /p∞)
or = (4.15.7)
d ln xA d ln xB
Equation (4.15.7) is known as the Duhem-Margules equation. It relates the partial
pressures of the two constituents with their corresponding amount fractions.
Equation (4.15.7) is applicable to both ideal and nonideal liquid mixtures, since
in its derivation nowhere the nature of the liquid mixture is involved. The only
assumption made was that the vapour behaves as an ideal gas.
Application of One of the relations for the partial pressure of the component A in a binary
Duhem-Margules liquid solution is
Equation
pA = p*A xA exp(a xB2 ) (4.15.8a)
and that for the component B is
pB = p*B xB exp(a xA2 ) (4.15.8b)
where p*A and p*B are the vapour pressures of pure liquids A and B, respectively.
The symbol α is a constant which has the same value for both the components.
For ideal solutions α = 0; for nonideal solutions α is positive for solutions
exhibiting positive deviation from ideality, and negative for solutions exhibiting
negative deviation from ideality. Since α is same for both the components, it
 Solutions 169

follows that both components behave in an identical manner. Thus, we have:

(i) If one component behaves in an ideal manner, the other one will also
behave ideally.
(ii) If one component shows positive (or negative) deviation from ideality
so also must the other.
The above conclusions can be derived directly from Eq. (4.15.7) as follows.
When One component behaves ideally Let this component be A. Then, according
to Raoult’s law, we have

pA = p*A xA

or ln ( pA /p∞) = ln ( p*A /p∞) + ln xA

Hence d ln ( pA/pº) = d ln xA

d ln ( pA /p∞)
or =1
d ln xA
Thus, according to the Duhem-Margules relation (Eq. 4.15.7), we must also
have
d ln ( pB /p∞)
=1 or d ln ( pB /p∞) = d ln xB
d ln xB
Integration of the above expression gives

Ú d ln ( pB /p∞) = Ú d ln xB or ln ( pB /p∞) = ln xB + I

where I is the constant of integration. Its value may be determined from the
fact that at xB = 1, pB = pB* and hence
I = ln ( pB*/pº)

Thus ln ( pB /p∞) = ln xB + ln ( p*B /p∞) = ln (xB p*B /p∞)

or pB = xB pB*
that is, the second component also follows Raoult’s law and thus behaves in an
ideal manner.
When one component exhibits positive deviation Let this component be A.
Obviously, we have
pA(real) > pA(ideal) = p*A xA

or ln ( pA(real) /p∞) > ln ( pA(ideal) /p∞) = ln ( p*A /p∞) + ln xA

Therefore
d ln ( pA(real) /p∞) d ln ( pA(ideal) /p∞) 1
> =
dxA dxA xA
170 A Textbook of Physical Chemistry

d ln ( pA(real) /p∞) xA d ln ( pA(ideal) /p∞)

or xA > =1
dx A dxA

d ln ( pA(real) /p∞)
i.e. >1
d ln xA
Thus, according to the Duhem-Margules equation, we must also have
d ln ( pB(real) /p∞)
>1
d ln xB
After integration, we will have
pB(real) > pB(ideal) = p*B xB

that is, the second component also exhibits positive deviation from ideality.
Arguing in a similar manner, it can be shown that if one component
exhibits negative deviation, the other will also do so.
Konowaloff’s Rule A general conclusion regarding the composition of the vapour phase in equilibrium
with any particular solution (ideal or nonideal) can be obtained theoretically
through the Duhem-Margules equation.
From Eq. (4.15.7), we have
d (ln pA /p∞) d (ln pB /p∞) xA dpA x dpB
= or = B (4.15.9)
d ln xA d ln xB pA dxA pB dxB
Since xA + xB = 1 therefore dxA + dxB = 0

or dxB = – dxA
Substituting the above expression in Eq. (4.15.9), we get
xA dpA x dpB
+ B =0 (4.15.10)
pA dxA pB dxA
dp dp dp
Now p = pA + pB , therefore = A + B (4.15.11)
dxA dxA dxA
Substituting dpA/dxA from Eq. (4.15.10) in the above equation, we get

dp x dpB pA dp dp È xB pA ˘
= - B + B = B Í1 - x p ˙ (4.15.12)
dxA pB dxA xA dxA dxA Î A B˚

From Eq. (4.8.1), it follows that the addition of either of the components causes
an increase in the corresponding partial vapour pressure (i.e. dpA/dxA and
dp B/dx B are positive). Hence, the derivative dpB/dx A, which is equal to
– dpB/dxB, must be negative. The change in the total vapour pressure with the
addition of dxA (i.e. the derivative dp/dxA in Eq. 4.15.12) can be either positive
or negative depending upon the sign of the expression within brackets in
Eq. (4.15.12). Thus, we have two alternatives as given below.
 Solutions 171

(i) xB pA > xA pB: In this case dp/dxA is positive. The condition

xB pA > xA pB

can be written as
pA x
> A
pB xB
Using Dalton’s law of partial pressures, we have
yA x
> A (4.15.13)
yB xB
that is, the ratio of amount fractions of A and B in the vapour phase is greater
than the corresponding ratio in the liquid phase. This means that the vapour is
relatively richer in A than is the liquid from which it vaporizes. Thus, the vapour
is richer in the component (here A) whose addition to the liquid mixture results
in an increase in total vapour pressure (i.e. dp/dxA is positive).
(ii) xB pA < xA pB: In this case, dp/dxA is negative or dp/dxB is positive.
The condition
xB pA < xA pB
can be written as
pA x
< A
pB xB
Employing Dalton’s law of partial pressures, we get
yA x yB x
< A or > B (4.15.14)
yB xB yA xA
that is, the ratio of amount fractions of B and A in the vapour phase is greater
than the corresponding ratio in the liquid phase. This means that the vapour
phase is relatively richer in B than is the liquid from which it vaporizes.
Thus, the vapour is richer in the component (here B) whose addition to the
liquid mixture results in an increase in total vapour pressure (i.e. dp/dxB is
positive).
Statement of Hence we have a general conclusion that:
Konowaloff’s Rule
The vapour phase is richer in the component whose addition to
the liquid mixture results in an increase in total vapour pressure,
or alternatively, the liquid phase is richer in the component whose
addition to the liquid mixture results in a decrease in total vapour
pressure.
This rule was stated empirically by D.P. Konowaloff on the basis of his
systematical measurements of total vapour pressure of homogeneous liquid
systems and is, therefore, known as Konowaloff’s rule.
172 A Textbook of Physical Chemistry

Alternative Since the boiling point of a solution is inversely related to its vapour pressure
Statement of (higher vapour pressure means lower boiling point and vice versa), we can state
Konowaloff’s Rule Konowaloff’s rule in terms of boiling point of the mixture:
The vapour phase is richer in the component whose addition to the
liquid mixture causes a decrease in its boiling point, or alternatively,
the liquid phase is richer in the component whose addition to the
liquid mixture causes an increase in its boiling point.

4.16 TEMPERATURE-COMPOSITION DIAGRAMS OF NONIDEAL SOLUTIONS

Based on the extent of deviations, a nonideal solution can be classified into the
following two categories.
A Little Deviation In this case the vapour pressure versus composition curve and the boiling point
from Ideality versus composition curve are very similar to those of an ideal solution
(Figs. 4.10.1 and 4.12.1). The total vapour pressure of the liquid mixture lies
between those of the pure components. It increases or decreases regularly with
the composition of the mixture. Consequently, boiling point of the liquid mixture
also lies in between those of the pure components and it increases or decreases
regularly with the composition.
Very Large In this category, the solution exhibits either maximum or minimum in the pressure
Deviation from versus composition curve. Since boiling point is inversely related to vapour
Ideality pressure, it is expected that the solution will exhibit either a minimum or a
maximum in the boiling point curve at a concentration where maximum or
minimum in the total vapour pressure is observed. It is also expected that the
general appearance of temperature versus composition curve will have one to
one inverse correspondence with that of the vapour pressure versus composition
curve.
An Important The temperature versus composition curve for a given solution can be drawn in
Comment accordance with Konowaloff’s rule. Before doing so, we consider the composition
of the vapour phase relative to that of the liquid phase at a point where maximum
or minimum in the vapour pressure versus composition curve is observed. At
this point, dp/dxA is zero, and hence from Eq. (4.15.12), we have either dpB /dxA
equal to zero or xB pA is equal to xA pB. The former will not be true as it means
that the partial pressure would remain constant in spite of a change in composition
of the solution. The only alternative is that
pA x yA x
xB pA = xA pB or = A or = A (4.16.1)
pB xB yB xB

Thus, the ratio of amount fractions of A and B in the vapour phase is

the same as that in the liquid phase. We conclude that the composition of the
vapour phase is the same as that of the liquid with which it is in equilibrium.
It is, therefore, expected that the vaporous curve and the liquidus curve in
a temperature versus composition diagram meet each other at maximum or
minimum point, so that both the phases have same composition at this point.
 Solutions 173

Depiction of Keeping in mind the above fact and that the vapour phase is stable at higher
Diagrams temperatures, we can readily draw temperature versus composition diagrams for
nonideal solutions as described in the following.
Solution exhibiting a maximum in the total vapour pressure curve corresponding
to Fig. 4.14.1 It will exhibit a minimum in the boiling point and thus the
temperature versus composition curves will have an appearance as given in
Fig. 4.16.1.
Solution exhibiting a minimum in the total vapour pressure curve corresponding
to Fig. 4.14.2 It will exhibit a maximum in the boiling point and thus the
temperature versus composition curves will have an appearance as given in
Fig. 4.16.2.

Fig. 4.16.1 Temperature-composition diagram for Fig. 4.16.2 Temperature-composition diagram for
a system exhibiting a minimum in boiling point a system exhibiting a maximum in boiling point

FRACTIONAL DISTILLATION OF NONIDEAL SOLUTIONS

We now consider the results that are obtained when a nonideal liquid mixture
is subjected to fractional distillation.
A Little Deviation Since the temperature-composition diagram for this type of solution is very
from Ideality similar to that of an ideal solution, it is obvious that the given liquid mixture
on fractionating will yield the pure constituents. During distillation, the liquid
phase becomes richer in the lesser volatile component, the boiling point of
which rises gradually, and the vapour phase becomes richer in the more volatile
component. Thus using a fractionating column, the more volatile constituent
can be removed from the top of the fractionating column and the lesser volatile
one from the bottom of the column.
174 A Textbook of Physical Chemistry

Very Large Devia- Fractional distillation of nonideal solutions exhibiting minimum and maximum
tions from Ideality boiling points yield, in general, only one of the constituents in the pure form,
depending upon the composition of the liquid mixture, as discussed below.

Solutions exhibiting a minimum in the boiling point Consider the distillation

of a liquid mixture of composition, say x1, lying between the points B and M
as shown in Fig. 4.16.1. The liquid mixture will start boiling at temperature T
and the vapour which appeared on boiling will have composition y1. Since the
vapour phase carries relatively more of the constituent A, it is obvious that the
remaining liquid will contain more of the constituent B and will thus boil at
a higher temperature. As the distillation proceeds, composition of the liquid
phase will move along x1B, i.e. towards the pure B, and that of the vapour phase
will move along y1M, i.e. towards the point M. At the point M, the vapour phase
and the liquid phase have identical compositions. Thus, condensing the vapour
and distillating the resultant solution will not yield any further separation of the
constituents. The liquid at this point would boil at a constant temperature, as
if it consisted of a single constituent. Thus, we see that the fractional distillation
of liquid mixture of composition x 1 will yield vapour of composition
corresponding to the point M and the pure liquid B. The former can be collected
from the top of the fractionating column and the latter from the bottom of the
column.
A similar conclusion is reached when the composition of the liquid
mixture lies between A and M (say x2) as shown in Fig. 4.16.1. In this case, as
the distillation proceeds, the vapour phase will contain more and more of B and
ultimately acquire the composition corresponding to the point M and the liquid
phase will contain more and more of A and ultimately yield pure A. Thus, the
fractional distillation of this liquid mixture will yield vapour of composition
corresponding to the point M, which can be collected from the top of the
fractionating column and the liquid of pure constituent A, which can be collected
from the bottom of the column.
Thus, we see that the fractional distillation of a solution exhibiting a
minimum in the boiling point yields:
Distillate A constant boiling liquid mixture of composition corresponding
to the point M.

Residue Pure A (and not B at all) if the composition of the liquid

mixture lies between A and M or pure B (and not A at all) if the composition
lies between B and M.
Solutions exhibiting a maximum in the boiling point Such a solution can be
analyzed in a similar manner. Consider, for example, a liquid mixture of
composition x1 (or x2) as shown in Fig. 4.16.2. When this liquid mixture starts
boiling, the vapour has a composition y1 (or y2). Since the vapour is relatively
richer in the constituent B (or A), the remaining liquid becomes richer in the
constituent A (or B). Thus, during distillation, composition of the liquid phase
moves along x1M (or x2M), the boiling point of which rises gradually and that
 Solutions 175

of the vapour phase moves along y1B (or y2A). Hence the end products of
fractional distillation of a liquid mixture are:
Distillate Pure A (and not B at all) if the composition of the liquid
mixture lies between A and M or pure B (and not A at all) if the composition
lies between B and M.
Residue A constant boiling liquid mixture of composition corresponding
to the point M.
Azeotropic Mixture We have seen that a liquid mixture of composition M corresponding to the
minimum or maximum boiling point, boils at a constant temperature and can
be distilled without any change of composition. Such a liquid mixture is known
as azeotropic mixture or simply azeotrope (Greek: to boil unchanged). For a
given pair of liquids and at a given pressure, the composition of the azeotropic
mixture and the corresponding boiling point are quite definite. Their values vary
as the external pressure is changed. This fact supports that the solution at the
point M is really a mixture of the two liquids and not a liquid containing only
one component formed as a result of definite union of the two liquids. Thus the
compound formation at the point M is excluded. Some examples of azeotropic
mixtures are given in Table 4.16.1.
Table 4.16.1 Some Examples of Azeotropic Mixtures. The boiling Points (B.Pt.; T/K
= θc/ºC + 273) Referred to are at 1 atm External Pressure

Type Components Azeotrope

A B mass % A b.pt./K
Minimum Water (373 K) Ethyl alcohol (351.3 K) 4 351.2
Water (373 K) Ethyl acetate (352.6 K) 11.3 346.4
Carbon Methyl alcohol (337.7 K) 79.49 328.7
tetrachloride (349.8 K)
Chloroform (334.2 K) Methyl alcohol (337.7 K) 87.4 326.4
Maximum Water (373 K) Nitric acid (359.7 K) 68 393.5
Water (373 K) Hydrochloric acid (353 K) 20.22 381.6
Chloroform (334.2 K) Acetrone (329.1 K) 78.5 337.4
Phenol (455.2 K) Aniline (457.4 K) 42 459.2

The variation of the composition and boiling point of azeotropic mixture

of HCl-water and pyridine-formic acid solutions with pressure is given in Table
4.16.2. Since the composition of azeotrope varies with pressure, it indicates that
the azeotrope consists of pure mixture and not a single compound.

4.17 KONOWALOFF’S RULE — REVISITED

Thermodynamic An alternative proof of Konowaloff’s rule can be derived from the quantitative
Derivation relation of shift in the boiling point of the solvent when a volatile solute is
added to it. We will derive the relation on the assumption that both liquid
mixture and vapour behave ideally. This assumption will be applicable only
when the solution is very dilute.
176 A Textbook of Physical Chemistry

Table 4.16.2 Variation of Composition and the Boiling Point of the Azeotropic
Mixture with the External Pressure

HCl–H2O Pyridine + Formic acid

p/Torr mass % HCl b.pt./ºC p/Torr mol % b.pt./ºC
500 20.916 97.578 760 58.4 138.25
700 20.360 106.424 570 58.9 129.4
760 20.22 108.584 380 59.5 117.5
800 20.155 110.007 190 60.2 99.5
120 60.8 87.10

The condition of phase equilibrium between the liquid mixture and the
vapour for one of the components (say solvent) is
m1(1) = m1(v)

where the subscripts 1 and v within the brackets stand for liquid and vapour,
respectively.
If it is assumed that both liquid and vapour mixtures behave ideally, then
we have
m1(1)
* + RT ln x1(1) = m1(v)
* + RT ln y1(v)

Rearranging the above expression, we have

* - m1(1)
m1(v) * D vapG1,* m
R(ln x1(1) - ln y1(v) ) = = (4.17.1)
T T
where vapG*1, m is the molar free energy of vaporization of the pure solvent at
temperature T and pressure p. For p = 1 atm, we have
D vapG1,∞ m = D vap H1,∞ m - T D vap S1,∞ m

and at the normal boiling point T * of the pure solvent

D vap H1,∞ m
D vap S1,∞ m =
T*
Therefore, we have
D vap H1,∞ m Ê T ˆ
D vapG1,∞ m = D vap H1,∞ m - T = D vap H1,∞ m Á 1 - ˜
T* Ë T *¯

Substituting the above expression in Eq. (4.17.1), we get

D vap H1,∞ m Ê T ˆ D vap H1,∞ m ( - DTb )
R(ln x1(1) - ln y1(v) ) = ÁË 1 - ˜¯ =
T T* T T*

(4.17.2)
where Tb = T – T*.
 Solutions 177

Equation (4.17.2) can be simplified under the following approximations.

(i) For a dilute solution, T will be very near to T *, so that the term TT *
may be replaced by T *2.
(ii) For a dilute solution, we have
ln x1(1) = ln (1 - x2(1) ) - x2(1)
ln y1(v) = ln (1 - y2(v) ) - y2(v)
With these approximations, Eq. (4.17.2) reduces to
D vap H1,∞ m ( - DTb )
R( - x2(1) + y2(v) ) =
T *2
Ê y2(v) ˆ D vap H1,∞ m ( - DTb )
or - R x2(1) Á 1 - =
Ë x2(1) ˜¯ T *2

RT *2 Ê y2(v) ˆ
or DTb = x2(1) Á 1 - ˜ (4.17.3)
D vap H1,∞ m Ë x2(1) ¯

Equation (4.17.3) can be written in terms of molality of the liquid solution using
the approximation:
n2(1) n2(1) n2(1) Ê n2(1) ˆ
x2(1) = = =Á M = mM1
n1(1) + n2(1) n1(1) m1(1) /M1 Ë m1(1) ˜¯ 1

Thus, Eq. (4.17.3) modifies to

RT *2 M1 Ê y2(v) ˆ
DTb = m Á1 -
D vap H1,∞ m Ë x2(1) ˜¯

or DTb = K b m(1 - K ) (4.17.4)

where K is the distribution coefficient of the solute between the vapour phase
and the liquid phase and is given by
Amount fraction of the solute in vapour phase
K= (4.17.5)
Amount fraaction of the solute in liquid phase

If in Eq. (4.17.4), K = 0 (i.e. the solute is nonvolatile), it reduces to Tb = Kbm,

an expression which we derived earlier in Section 2.7 for the elevation of boiling
point of the solvent when a nonvolatile solute is dissolved in it.
Application of Tb in Eq. (4.17.4) is equal to T – T * and can have either positive or negative
Eq. (4.17.4) value depending upon the value of K. Hence, we will have the following two
cases.
(i) Tb Positive Provided K < 1 (i.e. y2(v) < x2(1))
In this case, T > T * and an elevation in the boiling point of the solvent
occurs. The presence of (1 – K) factor in Eq. (4.17.4) indicates that the numerical
178 A Textbook of Physical Chemistry

value of Τb is smaller than the corresponding value expected for a solution

containing a nonvolatile solute.
(ii) Tb Negative Provided K > 1 (i.e. y2(v) > x2(1))
In this case, T < T * and a depression in the boiling point of the solvent
occurs.
Agreement with The above two conclusions are, in fact, the statements of Konowaloff ‘s rule as
Konowaloff’s Rule may be seen from the following analysis.
According to Konowaloff’s rule, the vapour phase is richer in the
component whose addition to the liquid mixture causes a decrease in its boiling
point. This is, in fact, the second conclusion which we have derived above.
According to this rule, the depression of boiling point takes place only when
K > 1, i.e. the vapour contains relatively more of the solute than the liquid and
thus the addition of such a solute in the solvent (or solution) will cause a
decrease in the boiling point of the latter.
Alternatively, the liquid phase is richer in the component whose addition
to the liquid mixture causes an increase in its boiling point. This is, in fact, the
first conclusion which we have derived above. According to this rule the elevation
of boiling point takes place only when K < 1, i.e. the vapour contains relatively
lesser of the solute than the liquid (or the liquid contains relatively more of the
solute than the vapour) and thus the addition of such a solute in the solvent (or
the solution) will cause an increase in the boiling point of the latter.
Now the nature of curves depicted in Figs 4.16.1 and 4.16.2 may be
understood qualitatively. Nonideal solutions exhibiting maximum boiling point
are observed whenever molecular attractions between unlike molecules are greater
than those between like molecules. In such cases, the escaping tendencies of
molecules of both the components are weakened with the result that the amount
fraction of the solute in the vapour phase is smaller than the corresponding
amount fraction in the liquid phase. Consequently, KA in B (i.e yA(v) /xA(1), where
A is solute and B is solvent) and KB in A (i.e. yB(v)/xB(1), where B is solute and
A is solvent) are less than one and thus there occurs an elevation in the boiling
point when either B is added to A or A is added to B. Hence the boiling point
versus composition curves exhibit upward trends on either end of the diagram
and thus a maximum at a point where the liquidus and vaporous fragments meet
each other is observed (Fig. 4.16.2).
On the other hand, solutions exhibiting minimum boiling point are observed
whenever molecular attractions between unlike molecules are smaller than those
between like molecules. This results in the increase in the escaping tendencies
of molecules of both the components with the result that the amount fraction
of the solute in the vapour phase is greater than the corresponding amount
fraction in the liquid phase. Consequently, KA in B and KB in A are greater than
one and thus there occurs a depression in the boiling point when either B is
added to A or A is added to B (Fig. 4.16.1). Hence the boiling point versus
composition curves exhibit downward trends on either end and thus a minimum at
a point where the liquidus and vaporous fragments meet each other is observed.
 Solutions 179

4.18 PARTIALLY MISCIBLE LIQUIDS

General Certain pairs of liquids are miscible with each other in limited range of
Considerations concentrations and are known as partial miscible liquids. For example, if a
small quantity of phenol, ether or aniline is added to water at room temperature,
and the mixture is shaken, it is observed that the organic compound dissolves
completely in water. If the addition of the organic compound is continued, a
stage is reached where the compound is no more soluble and thus two solutions
are formed. These are: (i) a saturated solution of the organic compound in water,
and (ii) a saturated solution of water in the organic compound.
These two solutions are in equilibrium with each other and are known
as conjugate solutions. The compositions of these solutions are fixed and are
independent of the relative amounts of the two solutions. Thus, if more of
organic compound is added, it is dispersed into these two solutions in such a
way that the compositions of both the solutions remain unaltered, the only thing
that vary is the relative amounts of the two solutions. As more and more of
organic compound is added, it continues to disperse in these two solutions and
the net effect is that the amount of the solution of organic compound in water
is gradually decreased, whereas that of water in organic compound is gradually
increased. Ultimately, a stage is reached where the solution of organic compound
in water is present in an infinitesimal amount. At this stage, the addition of a very
small amount of organic compound converts the system once again to a single
solution, but this time to a saturated solution of water in organic compound.
The addition of more organic compound simply makes the solution more and
more unsaturated with respect to water.
The above sequence of formation of a single solution followed by two
solutions and once again into a single solution is observed only in case of
those liquids which differ very widely from each other and show large positive
deviations from Raoult’s law.
Theoretical The formation of partial miscible liquid mixtures has a sound theoretical
Consideration background. The extent of positive deviation from Raoult’s law is proportional
to the value of α in Eq. (4.15.8), the deviation increases as the value of α
increases. For a given pair of liquids, the value of α can be increased by
lowering the temperature of the system: the deviations being larger at lower
temperature and smaller at higher temperatures. In general, the partial vapour
pressure curve for each component undergoes the changes of types I, II, III and
IV shown in Fig. 4.18.1, as the temperature of system is lowered (or as α is
increased). Curve I corresponds to a higher temperature where lesser deviations are
observed and curve IV corresponds to a lower temperature where the deviations
are larger. Special interest attaches to curves of types III and IV, where instead of
a smooth curve, a curly shaped curve is obtained. These curves have maximum
and minimum in the curly portion. The composition of solution at maximum
or minimum can be obtained by differentiating Eq. (4.15.8) with respect to x
and setting the resultant equation to zero.
Writing Eq. (4.15.8) without subscripts, we have
p = p*x exp{α (1 – x)2}
180 A Textbook of Physical Chemistry

Fig. 4.18.1 Vapour

pressure-composition
diagram for partial
miscible liquids

Differentiating this with respect x, we get

dp
= p* exp{a (1 - x )2} + p*x { - 2a (1 - x )} exp{a (1 - x )2}
dx
dp
or = p* exp{a (1 - x )2 } {1 - 2a x(1 - x )}
dx
Equating the above expression to zero, we get

1 - 2a x(1 - x ) = 0

or 2a x 2 - 2a x + 1 = 0 (4.18.1)

Solving for x, we have

2a – 4a 2 - 8a
x= (4.18.2)
4a
The roots of Eq. (4.18.2) are real if α > 2 and approaches each other as
α 2. At α = 2, the two roots are identical and for α < 2, they are imaginary.
It can be seen from the curly curve that there are three solutions of
different concentrations which have the same vapour pressure. For example,
on curve IV, the three solutions are represented by the points a, b and c. This
situation, however, is not consistent with the phase rule, according to which,
we have
F =C -P +2=4-P (as C = 2)
or P =4-F
 Solutions 181

If the state of the system is to be defined completely by only one degree

of freedom (i.e. temperature alone), then we can have at the most three phases
in equilibrium with each other. Of these three phases, one is the vapour phase
thus, we are left with only two liquid phases and, therefore, we cannot have
more than two liquid phases in equilibrium with each other. In fact, the curly
shape abc is not found experimentally and one observes a flat portion between a
and c, the liquid phase b having no real existence. The vapour pressure remains
constant between a and c.
Thus, we see that for a binary liquid system exhibiting large deviations
from Raoult’s law, there occurs limited solubility of one liquid into another and
hence two saturated solutions are formed over a certain range of composition.
Beyond this range, the two liquids are completely miscible with each other and
thus there exists a miscible gap in the system.
Temperature- The compositions of the two conjugate solutions in the miscible gap are quite
Composition definite for a given temperature and are independent of the relative amounts of
Diagram the two solutions. This fact is consistent with the phase rule. For P = 2 and
C = 2, we have
F =C -P +2=2
One of these two degrees of freedom represents the external pressure and has a
fixed value. Hence stating the value of one other parameter, namely, temperature
or composition of either of the conjugate solutions, defines the given system
completely. If, for example, temperature is stated then compositions of the two
solutions are fixed. If a graph between compositions of the two solutions and
the corresponding temperature is plotted, we obtain a curve (known as solubility
curve) of the type shown in Fig. 4.18.2.

Fig. 4.18.2 Tempera-

ture-composition
diagram for partial
miscible liquids
182 A Textbook of Physical Chemistry

Critical Solution The compositions of the two solutions become closer as temperature is raised.
Temperature This is due to the increase in mutual solubilities of the two components as the
temperature is raised. At a certain temperature, the compositions of the two
solutions become identical and both the solutions merge into each other, thereby
forming a single solution. This temperature is known as the consolute temperature
or the critical solution temperature (CST). When the temperature is greater
than CST, the two liquids are miscible in all proportions and thus always form
a single solution. In fact, a point outside the curve of Fig. 4.18.2 represents a
single solution, whereas that within the curve represents two conjugate solutions
in equilibrium with each other.
The compositions of the two conjugate solutions at a given temperature
are given by the two points on the solubility curve. Consider, for example, the
point c of composition X A within the curve at temperature θc. At this point, the
system consists of two solutions and (represented by the points a and b,
respectively) of compositions xA( ) and xA( ). In fact, the point c anywhere on
the horizontal line ab represents two solutions of compositions xA( ) and xA( ).
The only thing that varies from point to point is the relative amounts of the
two solutions, which can be calculated by using the lever rule as derived below.

Lever Rule Let the amounts of species A and B at the point c be nA and nB, respectively.
Now at the point c the system contains two conjugate solutions and of
compositions xA( ) and xA( ), respectively. Of the total amount of A, let the
amounts present in these two solutions be nA( ) and nA( ). Similarly, let nB( )
and nB( ) be the amounts of B present in these two solutions. Obviously,

nA nA(a ) + nA(b )
X A¢ = = (4.18.3)
nA + nB nA(a ) + nA(b ) + nB(a ) + nB(b )

nA(a )
Now ac = X A¢ - xA(a ) = X A¢ -
nA(a ) + nB(a )

or (nA(a ) + nB(a ) ) (ac) = (nA(a ) + nB(a ) ) X A¢ - nA(a ) (4.18.4)

nA(b )
and bc = xA(b ) - X A¢ = - X A¢
nA(b ) + nB(b )

or (nA(b) + nB(b ) ) (bc) = nA(b ) - (nA (b ) + nB(b ) ) X A¢ (4.18.5)

Subtracting Eq. (4.18.5) from Eq. (4.18.4), we get

(nA(a ) + nB(a ) )(ac) - (nA(b ) + nB(b ) )(bc)

= (nA(a ) + nB(a ) + nA(b ) + nB(b ) ) X A¢ - (nA(a ) + nA(b) ) (4.18.6)
 Solutions 183

In view of Eq. (4.18.3), the right side of Eq. (4.18.6) is zero. Hence
ac nA(b ) + nB(b )
=
bc nA(a ) + nB(a )
Total amount of substances in solution b
= (4.18.7)
Total amount of substances in solution a

Equation (4.18.7) is the required lever rule.

Application of the We consider below the application of the phase rule to the following three
Phase Rule typical cases.
A point outside the solubility curve Here we have
P =1 and C =2
Therefore
F =C -P +2=3
Since the pressure is kept constant (usually 1 atm), the values of two variables,
namely temperature and composition of the solution, should be stated in order
to define the system completely.
A point inside the solubility curve Here we have
P =2 and C =2
Therefore
F =C -P +2=2
Once again, since pressure is constant, we would have to state the value
of one variable (usually temperature) in order to define the system completely.
As stated earlier, the compositions of the two solutions will have fixed values
and will be represented by the two points on the solubility curve corresponding
to the given temperature.
At critical solution temperature At this point, we have one restricted condition
of identical compositions of the two solutions. Thus, we have
F = (C - r ) - P + 2 = (2 - 1) - 2 + 2 = 1
Since p is kept constant, the system is invariant, i.e. the critical solution temperature
and the corresponding composition on the curve have fixed values for a given
value of pressure (usually 1 atm is chosen for this purpose).
Examples A few examples of pairs of liquids showing partial miscibility along with their
critical solution temperatures and the corresponding compositions are given in
Table 4.18.1.
Effects of Changing Let us have a system represented by a point X in Fig. 4.18.2. This represents an
the Composition unsaturated solution of B in A. Now if more of B is added, it continues to
dissolve till the point a is reached. At this point, the single solution just splits
into two; a saturated solution of B in A of composition xA( ), which is presents
184 A Textbook of Physical Chemistry

Table 4.18.1 Examples of Pairs of Liquids showing Partial Miscibility

System CST/ ºC Composition

Water-Phenol 65.9 66 mass % of water
Aniline-Hexane 59.6 48 mass % of aniline
Methyl alcohol-Cyclohexane 49.1 29 mass % of methyl alcohol
Methyl alcohol-Carbon disulphide 40.5 20 mass % of methyl alcohol

in the large amount and a saturated solution A in B of composition xA( ), which

has just started forming. Now as more of B is added, system continues to possess
the above two solutions till the point b is reached. The only change that is
observed during this interval is that the relative amounts of the two solutions
vary; the amount of the solution of B in A gradually decreases whereas that of
A in B gradually increases. The relative ratio at any stage can be determined
with the help of the lever rule. At point b, the solution of B in A is just going
to disappear, and, therefore, is present in a very small amount. Further addition
of B gives rise once again to a single solution, but this time an unsaturated
solution of A in B (point Y). We can also go from the point X to Y without going
through the formation of two solutions. This can be done as follows:
(a) Raise the temperature of the solution represented by the point X to a
point above the critical solution temperature.
(b) Add more of B till the desired composition of A in B, corresponding
to the point Y, is obtained.
(c) Cool the resultant solution till the point Y is reached.
The above procedure is also shown in Fig. 4.18.2.
Effect of Changing Let us have a system respresented by the point c (Fig. 4.18.2). This represents
the Temperature two solutions of B in A and A in B with compositions xA( ) and xA( ), respectively.
If the temperature of the system is increased, the state of the system is moved
vertically, the composition of the solution of A in B changes along bM and that
of B in A along aM . The relative amounts of the two solutions also vary; the
amount of B in A is gradually increased whereas that of A in B is gradually
decreased. The system continues to have two solutions till the point M is reached
where the solution of A in B is present in vanishing amount. In fact, the system
of two solutions becomes a single saturated solution of B in A. The temperature
at which this happens is known as the mutual solubility temperature (MST).
When the temperature is further increased, we get an unsaturated solution of
B in A. Obviously, critical solution temperature is the maximum of all mutual
solubility temperatures.
Lower Consolute There are some binary liquid mixtures which show increase in the mutual solubilities
Temperature as the temperature is decreased. Such systems, therefore, are expected to have
temperature-composition curve just reverse of the curve of Fig. 4.18.2. This is
shown in Fig. 4.18.3. The system now has a lower consolute temperature and
thus liquids are completely miscible with each other in all respects so long as
the temperature is below the lower consolute temperature. Systems showing the
 Solutions 185

Fig. 4.18.3 The lower

consolute temperature

lower CST almost invariably consist of either a hydroxy-compound and an

amine or a hydroxy-compound and a keto grouping (or an ether grouping). It
is, therefore, expected that the two components partially associate through the
hydrogen bonding

The extent of such association depends upon the temperature of the system and
it decreases as the temperature is raised. This probably is the reason why their
mutual solubilities are decreased as the temperature is increased.
A few examples of pairs of liquids showing lower consolute temperature
are given in Table 4.18.2.
Table 4.18.2 Examples of Systems showing Lower CST

System Lower CST/ ºC

Triethylamine-water 18.5
γ -Collidine-water 6
Glycerol-m-toluidine 6.7

Lower and Upper It is found that the mutual solubilities do not continue to decrease as the
Consolute temperature is increased. After a certain temperature the solutions behave in a
Temperatures normal manner and the solubilities again start increasing with rise in temperature
It is, therefore, expected that such solutions will also show the upper critical
solution temperature. The solubility curve for such systems consists of a closed
curve and is shown in Fig. 4.18.4. At any point within the closed loop, two liquid
phases are present, while that lying outside the loop represents a single solution.
The first case of this type to be established was the nicotine-water system, the
186 A Textbook of Physical Chemistry

Fig. 4.18.4 Tempera-

ture-composition curve of
a system having both
upper and lower CST

upper CST being at 208 °C and the lower one at 60.8 °C. Thus nicotine and
water are completely miscible in each other at temperatures greater than 208 °C
and less than 60.8 °C.
The upper critical solution temperatures for most liquids pairs are very
high and are realized only under high pressures. In many cases, it has not been
possible to attain this upper CST experimentally as this lies above the respective
critical temperatures of the liquids with the effect that the system volatalizes
much before CST is reached.
In few cases such as the ethyl acetate-water mixture and the ether-water
mixture, it has not been possible to attain experimentally both the upper and the
lower critical solution temperatures. In the above two systems, theoretically one
would expect the lower critical solution temperatures since the solubilities of ethyl
alcohol and ether in water decrease with increasing temperature. However, the
critical solution temperatures for both the above systems lie below the freezing
point of water. Thus water freezes completely before these temperatures are
reached. Similarly, the upper CST for chloroform-water mixture has not been
realized experimentally; here the upper CST lies above the critical temperature
of chloroform. Thus, it is obvious that one would not observe experimentally
the critical solution temperature when (i) the upper CST lies above the critical
temperature of either of the two liquids, and (ii) the lower CST lies below the
freezing point of either of the two liquids.
Effect of Pressure It was shown earlier with the help of phase rule that the CST of partially miscible
on CST liquids has a definite value for a given value of the external pressure. Thus, it
is expected that the CST will vary as the external pressure is varied. Since the
 Solutions 187

mutual solubilities of the two components invariably increase with increase in

external pressure, it is, therefore, expected that the upper CST will decrease
whereas the lower CST will increase as the external pressure is increased. This
is shown in Fig. 4.18.5. In fact, it is found to be so experimentally. The area of
the loop thus becomes smaller and smaller with increase in pressure, ultimately,
a stage is reached when the area is just reduced to a point. At this stage, the
two liquids become miscible with each other in all proportions and thus form
a single liquid solution.

Fig. 4.18.5 Effect of

pressure on CST; dotted
curve at low pressure,
solid curve at high
pressure

Effect on Impurities The impurities have a marked effect on the critical solution temperature, the
on CST nature of the effect depends whether the added substance is soluble in one liquid
or in both the liquids.
If the substance is soluble only in one liquid, it will effect the solubility
of the other liquid in this liquid. In general, this solubility is decreased, i.e.
the mutual solubilities of the two liquids are decreased and, consequently, the
CST is raised as shown by the dotted curve I in Fig. 4.18.6. For example, the
addition of 0.1 mol of KCl per dm3 of water raises the CST of the phenol-water
mixture by about 8 K whereas the addition of 0.1 mol of naphthalene per dm3
of phenol raises the temperature nearly by 20 K.
If the added substance is soluble in both the liquids, it increases the
mutual solubilities of the two liquids and, consequently, the CST is lowered as
shown by the dotted curve II in Fig. 4.18.6. This probably is due to the fact
that the added substance will distribute itself between the two conjugate liquid
mixtures in a definite manner and is being continuously exchanged between
them. Thus,
188 A Textbook of Physical Chemistry

Fig. 4.18.6 Effect

of impurities on CST

a stage of dynamic equilibrium exists. This to and fro movement of molecules of

the added substance acts as a cementing force between the two conjugate liquid
mixtures and hence brings about more solubility of the two liquids. For example,
when succinic acid is added to the phenol-water mixture, its CST is lowered.

DISTILLATION OF PARTIALLY MISCIBLE LIQUIDS

Qualitative Features A complete temperature-composition diagram of a binary mixture of partially
miscible liquids also includes the vapour phase and gives a curve of the type
shown in Fig. 4.18.7. The liquid-vapour curves will show a minimum as the
two liquids show large positive deviations from Raoult’s law. The upper and
lower portions of the diagram shown in Fig. 4.18.7 can be discussed separately
as we did earlier. If distillation of a binary mixture of partially miscible liquids
is carried out at a low pressure, the temperature at which the mixture starts
boiling is lowered. Consequently, the boiling point-composition curves in Fig.
4.18.7 are shifted downwards. If the pressure is low enough, a stage will be
reached where the boiling point curves will intersect the liquid-liquid solubility
curve. The nature of the resultant diagram depends on the corresponding vapour
pressure-composition curves. Three types of vapour pressure-composition curves
and hence also temperature-composition curves are possible. These are shown
in Figs 4.18.8 to 4.18.10. The behaviour of the mixture during distillation will
depend upon the characteristics of these curves.
Distillation Involving Examples of such a system are aniline-water, ethyl acetate-water, and isobutyl
no Azeotropic alcohol-water mixtures. As usual, the curved lines AE and BE in Fig. 4.18.8b
Mixture represent the vaporous curves and the lines AC and BD represent the liquidus
curves. The horizontal line CD represents systems where two liquid phases C
and D and the vapour phase E are in equilibrium with one another. The lines
 Solutions 189

Fig. 4.18.7 A complete

temperature-composition
diagram of a mixture of
partially miscible liquids

below the horizontal line CD represent the region of partial miscibility within
which the two liquid phases are formed. The behaviour of the system during
distillation can be described as usual. Consider, for example, a solution represented
by the point a. This consists of a single unsaturated solution of B in A. If
temperature of this solution is increased, it will start boiling at temperature t1,
the vapour which issues here has composition v . The vapour phase is relatively
richer in the component B (in accordance with Konowaloff’s rule, the vapour is
richer in the component whose addition to the mixture lowers the boiling point)
and thus the remaining liquid will be richer in the component A. Consequently,
composition of the liquid will move along bA and thus will boil at higher
temperatures. If fractional distillation is carried out, it will eventually yield the
pure component A. Now if the vapour which is formed at t1 is cooled to the
original temperature, it will form a mixture of two liquid phases c and d. If
the temperature of this mixture is gradually increased, compositions of the two
liquids will move along cC and dD, respectively. At temperature t2, this mixture
will start boiling with the vapour composition given by the point E. Since the
vapour contains relatively more of B in comparison to the overall composition of
liquids (point C ) and since the distillation at this stage takes place at a constant
temperature, it follows that the overall composition of the remaining liquids
will move along C C. Thus during distillation, the relative amounts of the two
liquid phases vary, the amount of liquid phase D gradually vanishes. The mixture
continues to have two phases till the point C is reached. Further distillation
beyond this stage completely vanishes the liquid phase of A in B and the
composition of the liquid phase C moves along CA. The sequence of further
distillation is the same as described earlier. Thus, we see that the end products
of fractional distillation will consist of:
190 A Textbook of Physical Chemistry

Fig. 4.18.8 (a) Vapour pressure-composition and (b) temperature-composition diagrams for partial miscible
liquids with no azeotropic mixture

Residue The pure component A in the liquid form and can be collected
from bottom of the column.
Distillate The vapour corresponding to the composition E, which can be
collected from top of the column. This distillate cannot be fractionated further.
Similar results would be expected if the composition of the original
solution lies at a . Here the residue will consist of pure component B and the
distillate of composition E. Thus, we see that the fractional distillation of this
type of system will not give a complete separation of the two components, only
one of them can be obtained in the pure form depending upon the original
composition of the solution; pure A if the composition of the system lies left
to the point E, and pure B if it lies right to the point E. It may, however, be
noted that none of the two constituents can be obtained in pure form if the
original composition of the mixture lies exactly on the point E, since the total
composition of the liquid is the same as that of vapour with which it is in
equilibrium.
Distillation Involving Examples of such a system are water-phenol, ethyl methyl ketone-water and
Azeotropic Mixture triethylamine-water mixtures. The end products obtained in the fractional
distillation of a mixture exhibiting Fig. 4.18.9b can be analyzed following the
principles described above. Consider, for example, a solution as represented by
the point a. This mixture will start boiling at temperature t1. Since the vapour
which issues here contains relatively more of B (point c in comparison to the
point b), the composition of the remaining liquid will move along bD and hence
 Solutions 191

its boiling point will rise. At point D, the single liquid splits into two liquids
C and D, the former being present in a smaller amount. At this stage, distillation
proceeds at a constant temperature and the vapour which appears has composition
E. The vapour is relatively richer in B in comparison to either of the two liquid
layers. Thus, in the remaining two liquid layers, the concentration of B decreases
faster than that of A. In other words, the state of the mixture will move along
DC. The net effect that is produced here is that the liquid layer D gradually
decreases, whereas that of C gradually increases. At point C, practically entire
liquid layer D has disappeared. Further distillation will change the liquid
composition along CA and ultimately to pure A. Thus, the end products of the
fractional distillation of the system are:
Residue The residue consists of pure liquid A and can be collected from
bottom of the fractionating column.
Distillate The distillate consists of the azeotropic mixture of composition
corresponding to the point M and can be collected from top of the fractionating
column.
If in the beginning the composition of the solution lies to right of the
point M, the end products would be
Residue Pure liquid B.
Distillate The azeotropic mixture of composition corresponding to the
point M.

Fig. 4.18.9 (a) Vapour pressure-composition and (b) temperature-composition diagrams for partial miscible
liquids exhibiting azeotropic mixture
192 A Textbook of Physical Chemistry

Distillation Involving Examples of such a system are isopentane-nitrobenzene, isopentane-dichloroacetic

Complete acid, and nicotine-water mixtures. In this case, complete separation of the two
Separation components is possible in spite of the formation of two layers during the course
of fractional distillation (Fig. 4.8.10). The residue will consist of pure A in the
liquid form and the distillate consisting of pure B in the vapour form.

Fig. 4.18.10 (a) Vapour pressure-composition and (b) temperature-composition diagrams for partially miscible
liquids exhibiting complete separation of its constituents

4.19 COMPLETELY IMMISCIBLE LIQUIDS (STEAM DISTILLATION)

If the two liquids are completely immiscible with each other, each one will
behave independently of the other and will exert its own vapour pressure. The
total vapour pressure of the system will be sum of vapour pressures of the two
liquids. Thus

p = p*A + p*B

This total pressure will remain constant as long as both the liquids are present
and will be independent of the relative amounts of the two liquids.
Principle Underlying The boiling point of a liquid system is a temperature at which its vapour pressure
Boiling of becomes equal to the external pressure. Since the total vapour pressure of a
Immiscible Liquids mixture containing immiscible liquids is greater than that of either of the pure
constituents, it follows that the mixture will boil at a temperature which is lower
than boiling points of either of the pure constituents. Moreover, since the total
vapour pressure is independent of the relative amounts of the two constituents,
the boiling point will remain constant as long as both the layers are present.
 Solutions 193

The composition of vapour can be calculated by using Dalton’s law of

partial pressures. Thus, we have

p*A yA n m /M mA M p*
= = A = A A or = A A (4.19.1)
p*B yB nB mB /M B mB M B p*B

The masses of the constituents in the distillate are thus proportional to their
respective molar masses and vapour pressures.
Process of Steam The process of distillation of immiscible liquids is generally utilized for the
Distillation purification of those liquids which either boil at too high temperatures or
decompose when heated to their normal boiling points. In laboratory and also
in industry, water is used as one of the immiscible liquids and the process
of distillation is known as steam distillation. The immiscible liquid is heated
either directly along with water or by passing steam through it. Generally,
the process of passing steam is preferred as it keeps the system agitating and
thus equilibrium between the vapour and the two liquids is rapidly attained.
The distillate is condensed and separated in the pure forms. It is evident from
Eq. (4.19.1) that distillation of an immiscible mixture of an organic compound
with water will yield a distillate containing a high proportion of compound
provided the molar mass of the compound is larger and has appreciable vapour
pressure at temperature near and just below the boiling water of water.
The process of steam distillation is often employed for the partially
miscible mixtures. In this case, the efficiency of the process is slightly less than
the theoretical value.

Example 4.19.1 The steam distillation of chlorobenzene is observed to occur at a temperature of 90.6 °C
when the total pressure is 1.0 atm. Assuming complete immiscibility of these liquids,
calculate the mass of chlorobenzene in 0.1 kg of distillate. The vapour pressure of water
at 90.6 °C is 538.9 Torr.
Solution Total vapour pressure = 760 Torr
Molar mass of chlorobenzene, MA = 112.5 g mol–1
Vapour pressure of water at 90.6 °C = 538.9 Torr
Vapour pressure of pure chlorobenzene, pA* = (760 – 538.9) Torr = 221.1 Torr
Substituting the above data in the expression mA /mB = p*A M A / p*B M B ,

mA (22.1 Torr) (112.5 g mol -1 ) mB 1

we get = = 2.56 or =
mB (538.9 Torr) (18 g mol -1 ) mA 2.56
Adding one on both sides, we have
mA + mB 1 3.56 mA 2.56
= +1= or = = 0.72
mA 2.56 2.56 mA + mB 3.56
For 100 g of distillate, we have

mA = (0.72)(mA + mB ) = (0.72)(100 g) = 72 g
194 A Textbook of Physical Chemistry

Example 4.19.2 When a liquid that is immiscible with water was steam distilled at 95.2 °C at a total
pressure of 747.3 Torr, the distillate contained 1.27 g of the liquid per gram of water.
Calculate the molar mass of the liquid. The vapour pressure of water is 638.6 Torr at
95.2 °C.
Solution We are provided with
ptotal = 747.3 Torr
p*B = p*water = 638.6 Torr
p*A = p*liquid = 747.3 Torr - 638.6 Torr = 108.7 Torr

and mA /mB = 1.27 g / 1 g.

We have

mA p* M Ê m ˆ Ê p* M ˆ
= A A or MA = Á A ˜ Á B B ˜
mB p*B M B Ë mB ¯ Ë p*A ¯

Substituting the given data, we get

È (638.6 Torr) (18 g mol -1 ) ˘ -1

M A = (1.27) Í ˙ = 134.3 g mol
Î (108.7 Torr) ˚

4.20 DISTRIBUTION OF A SOLUTE BETWEEN TWO IMMISCIBLE LIQUIDS — THE

NERNST DISTRIBUTION LAW
If a solute A is added in a system containing two immiscible liquids and (or
Distribution Law slightly miscible liquids) and if the solute is soluble in both the liquids, then it
distributes itself between the two liquids in a definite manner, such that
[A]a
= Kd (4.20.1)
[A]b
where [A] and [A] are the equilibrium molar concentrations of the solute A
in the liquid phases and , respectively and Kd is a constant known as the
distribution coefficient or the partition coefficient. The value of the constant Kd
depends only on the temperature of the system and is independent of the relative
amounts of the two layers and also that of the solute. Equation (4.20.1) is the
defining equation for the distribution law or the partition law.
Phase Rule Applied The distribution law is in agreement with the phase rule requirements. We have
to Distribution Law P = 2 and C = 3
Thus F =C -P +2=3
Of the three degrees of freedom, the two degrees of freedom, namely, temperature
and pressure, are held constant. Thus stating the value of any third variable is
sufficient to define the system completely. This implies that if the concentration
of the solute in one of the layers is stated, then its value in the other layer will
have a definite value and thus the ratio of the two concentrations will have a
constant value.
 Solutions 195

Thermodynamic Derivation for Ideal Solutions. The condition of equilibrium of the solute A
Derivation of the between the two layers is
Distributuon Law m A(a ) = m A(b )

where μA( ) and μA( ) are the chemical potentials of the solute A in the two
liquids and , respectively. If these liquids behave ideally, we have

m A(a ) = m*A(a ) + RT ln xA(a ) and m A(b ) = m*A(b ) + RT ln xA(b )

Substituting these in the previous expression, we get

m*A(a ) + RT ln xA(a ) = m*A(b ) + RT ln xA(b )
xA(a ) 1
or ln = (m*A(b ) - m*A(a ) )
xA(b ) RT
At a given temperature and pressure, the right side of the above equation
has a constant value. Thus, we have
xA(a ) xA(a )
ln = constant or = constant
xA(b ) xA(b )
If the solutions are dilute, the amount fractions can be replaced by the
corresponding molar concentrations. Thus, we have
[A]a
= constant = Kd (Eq. 4.20.1)
[A]b
Derivation for Ideally For ideally dilute solutions, we have
Dilute Solutions
m A (α ) = m*A (α, hs) + RT ln xA (α )
m A (β ) = m*A (β, hs) + RT ln xA (β )

The condition of equilibrium of A between the two phases gives

μA( ) = μA( )

i.e. m*A(α, hs) + RT ln xA (α ) = m*A(β, hs) + RT ln xA (β )

xA(α ) È m*A(β, hs) - m*A(α, hs) ˘

Hence Kd = = exp Í ˙
xA(β ) ÍÎ RT ˙˚

Since m*A(α, hs) = m*A(v) + RT ln (kH, A(α ) / p∞)

and m*A(β, hs) = m*A(v) + RT ln (kH, A(β ) / p∞)

xA(α ) kH, A(β )
we get Kd = =
xA(β ) kH,A(α )

Thus, the amount of fraction of A in phase is inversely proportional to its

Henry’s law constant in phase .
196 A Textbook of Physical Chemistry

Limitation of the The distribution expression as given by Eq. (4.20.1) will be strictly true provided
Distribution Law (i) the solutions are ideal and dilute, (ii) the presence of solute does not change
the mutual solubility of the two layers, and (iii) the solute has the same molar
mass in both the layers.
A few examples which follow distribution law are the distribution of iodine
between water and carbon tetrachloride (or chloroform or carbon disulphide),
phenol between water and amyl alcohol, and bromine between water and carbon
disulphide.
It was pointed out by Nernst that the distribution law as given by
Eq. (4.20.1) is applicable only when the solute has the same molecular form
(i.e. same molar mass) in both the layers. In some cases, solute does not have
the same molar mass in the two solutions. This results because of association
or dissociation or any other such changes which the solute can undergo in the
solution. One of such examples is the distribution of benzoic acid in water and
benzene. Benzoic acid in water is present in a partially ionized form whereas
in benzene, it undergoes dimerization. Thus, we have
C6H5COOH C6H5COO– + H+ in water
and 2C6H5COOH (C6H5COOH)2 in benzene
If the total concentrations of benzoic acid in the two layers are substituted
in Eq. (4.20.1), it is found that the ratio does not remain constant as the amount
of benzoic acid dissolved in both the layers is varied. According to Nernst, the
distribution law will be applicable if the concentrations of the species common
to both the layers (i.e. undissociated benzoic acid) are employed.

[A]aq - xd
Thus Kd = (4.20.2)
[A]org - 2xa

where ξd and ξa are the extent of dissociation and association reaction, respectively.

DISTRIBUTION LAW UNDER DIFFERENT CONDITIONS

A suitable modification in the original distribution law as given by Eq. (4.20.1)
can be made in order to account for the association, dissociation, hydrolysis or
any such changes which a solute undergoes in the solution. Some of these are
described below.
Normal Existence In liquid , solute A is present as it is, thus its concentration is [A] . In liquid
in and Association , it associates according to the equation
in
nA An (4.20.3)

Let [A] , total be the total concentration of A in liquid and ξa be its extent of
association, then we have

[A]b, free = [A]b, total - nxa

 Solutions 197

Substituting these in the equilibrium expression corresponding to the association

reaction, we get

[A n ]β xa
Keq = = (4.20.4)
[A]βn, free ([A]β, total - nxa )n

1/n
Ê x ˆ
or [A]β, free = [A]β, total - nxa = Á a ˜
Ë Keq ¯

If the solute A in liquid is almost present in the associated form, then

ξa = [A] , total/n. Thus, we have

1/n
Ê [A]b, total ˆ
[A]b, free = [A]b, total - nξa = Á ˜
Ë nKeq ¯

Substituting [A] and [A] , free in the distribution law, we get

[A]a [A]a
Kd = =
[A]b, free ([A]b, total /n Keq )1/n

[A]a Kd
or 1/n
= (4.20.5)
([A]b, total ) (n Keq )1/n

At a given temperature, Keq has a constant value. Since n is a constant for

a given association reaction, it follows that the right side of Eq. (4.20.5) also
has a constant value. Thus, we have

[A]a
= constant = Kd¢ (4.20.6)
([A]b, total )1/n

where Kd is known as the apparent distribution coefficient.

The value of n can be determined by plotting a graph between
log{[A] /cº} and log{[A] , total/cº}, the slope of the resultant line is equal to
1/n. Thus knowing n, the value of Kd can be determined. For benzoic acid in
benzene, n is equal to 2. Thus, it dimerizes in benzene layer.
Alternatively, the value of n can be determined from the given two sets
of data as shown in the following.

[A]a [A]a /c∞ Kd¢

Since = Kd¢ or = (4.20.7)†
1/n
([A]b, total ) ([A]b, total /c∞) 1/n
(c∞)(n -1)/n

†
Division by cº (= unit concentration) makes different quantities unitless.
198 A Textbook of Physical Chemistry

Therefore

Ê Kd¢ ˆ Ê [A]a ˆ 1 Ê [A]b, total ˆ

log Á ˜ = log Á ˜ - log ÁË c∞ ˜¯ (4.20.8)
Ë (c∞)(n -1)/n ¯ Ë c∞ ¯ n

Representing [A] /cº and [A] , total/cº for the two sets of data as x1, y1 and x2
and y2, we get
1 1
log Kd¢¢ = log x1 -
log y1 and log Kd¢¢ = log x2 - log y2
n n
From these two expressions, we get
1 1
log x1 - log y1 = log x2 - log y2
n n
log y1 - log y2
or n= (4.20.9)
log x1 - log x2

Example 4.20.1 An organic substance X has a normal molar mass in water but gives abnormal molar
mass in benzene. The following data were obtained during a distribution experiment.
I II III
[X]water/g dm–3 0.01 0.12 0.24
[X]benzene/g dm–3 1.848 × 10–5 2.661 × 10–3 1.089 × 10–2
Find without using the graphical method, the degree of complexity of the substance in
benzene.
Solution We know that the degree of complexity is given by
log (y1/g dm -3 ) - log (y2 /g dm -3 )
n=
log (x1/g dm -3 ) - log (x2 /g dm -3 )
From the first two readings, we have
log (1.848 ¥ 10 -5 ) - log (2.661 ¥ 10 -3 ) 5.266 7 - 3.425 1
n= = = 1.999 2
log (0.01) - log (0.12) 2.000 0 - 1.079 2
Taking the second two readings, we have
log (2.661 ¥ 10 -3 ) - log (1.089 ¥ 10 -2 ) 3.425 1 - 2.037 0
n= = = 2.033
log (0.12) - log (0.24) 2.000 0 - 1.079 2
Taking the first and the third readings, we have
log (1.848 ¥ 10 -5 ) - log (1.089 ¥ 10 -2 ) 5.266 7 - 2.037 0
n= = = 2.007
log (0.01) - log (0.24) 2.000 0 - 1.380 2

The value of n is equal to 2. Thus, the organic substance exists as dimer in benzene layer.

Values of true distribution coefficient and equilibrium constant Equation

(4.20.4) can be written as
[A n ]b
Keq = (4.20.10)
[A]bn, free
 Solutions 199

The total concentration of A in liquid is given by

[A]b, total = [A]b, free + n[A n ]b

Making use of Eq. (4.20.10), we get

[A]b, total = [A]b, free + n K eq [A]bn, free

Now employing the distribution expression

[A]a
Kd =
[A]b, free
n
[A]a Ê [A] ˆ
we get [A]b, total = + nKeq Á a ˜
Kd Ë Kd ¯

[A]b, total 1 nKeq

or = + [A]an-1 (4.20.11)
[A]a Kd Kdn

Thus by plotting [A] , total/[A| versus [A] n–1, we can get 1/Kd and
nKeq/K nd as intercept and slope, respectively. From these, the values of Kd and
Keq can be determined.
Normal Existence in Let the solute dissociate in Liquid according to the following scheme.
and Dissoication
A B+C
in
Let ξ be the extent of reaction. We will have
[A]b, free = [A]b, total - x

[B] = [C] = x
Substituting these in the equilibrium expression corresponding to the above
dissociation, we get
[B][C] x2
Kdiss = =
[A] [A]b, total - x

x2
Thus [A]b, free = [A]b, total - x =
Kdiss
Hence, the distribution law becomes
[A]a [A]
Kd = = 2 a (4.20.12)
[A]b, free x /Kdiss

Dissociation in In this case, we have

and Dimerization
in [A]a , total - xd
Kd = (4.20.13)
[A]b, total - 2xa
200 A Textbook of Physical Chemistry

Normal Existence in Let the reaction between the solute and the liquid be represented as
and Undergoes a A+n A n
Reaction with
Its equilibrium constant is given by
[A ◊ nb]
Keq = (4.20.14)
[A]b, free [b]n

The total concentration of A in liquid is given by

[A]b, total = [A]b, free + [A ◊ nb]

Making use of Eq. (4.20.14), we get

[A]b, total = [A]b, free + Keq [A]b, free [b]n

[A]b, total
Hence, [A]b, free = (4.20.15)
1 + Keq [b]n

Substituting Eq. (4.20.15) in the distribution law, we get

[A]a [A]a
Kd = =
[A]b, free [A]b, total /(1 + Keq [b]n )

[A]a Kd
or = (4.20.16)
[A]b, total 1 + Keq [b]n

For a given temperature, Keq has a constant value. Since liquid is present in
a very large amount, the concentration of practically remains constant. Thus,
we have

[A]a
= constant (4.20.17)
[A]b, total
Study of Equilibria Distribution measurements have been used to determine the equilibrium constants
by Distribution of various reactions such as complex formation, hydrolysis of ions, etc. In such
Measurement studies, the second solvent which is generally chosen is the one that can dissolve
one of the reactants or products of the reaction under study so that the distribution
of this species occurs between the two layers. The underlying principle can be
explained by taking a typical example of the complex formation between I2 and
KI. In aqueous solution, we have
KI + I2 KI3
We choose a solvent in which I2 is soluble, it may be carbon tetrachloride or
carbon disulphide. First of all, the distribution coefficient Kd of I2 in water and
CCl4 is determined, such that
[I 2 ]CCl4
= Kd
[I 2 ]water
 Solutions 201

Now the equilibrium of I2 between KI solution and CCl4 is studied. If

[I2]aq, total and [I2]CCl4 are the concentrations of iodine in aqueous and CCl4
layers, respectively, then we have:
[I 2 ]CCl4
Concentration of free iodine in aqueous layer, [I 2 ]aq, free =
Kd
Concentration of combined I2 in aqueous layer or the concentration of KI3
= Total I2 in aqueous layer – Free I2 in aqueous layer
[I 2 ]CCl4
= [I 2 ]aq, total -
Kd

Concentration of free KI in aqueous solution, [KI]free

= Total concentration of KI – Concentration of KI3
Ï [I 2 ]CCl4 ¸
= [KI]aq, total - Ì[I 2 ]aq, total - ˝
Ó Kd ˛
The equilibrium constant of the reaction is thus given by
[ I 2 ]CCl4
[ I 2 ]aq, total -
[ KI3 ] Kd
Keq = =
[ I 2 ]aq, free [ KI]free Ê 2 CCl4 ˆ Ê
[ I ] Ï [ I 2 ]CCl4 ¸ˆ
ÁË K ˜¯ ÁË [ KI]aq, total - Ì[ I 2 ]aq, total - ˝˜
d Ó Kd ˛¯

Thus knowing [I2]aq, total, [I2]CCl4, [KI]aq, total and Kd, the value of equilibrium
constant Keq can be determined.

Example 4.20.2 The distribution coefficient of the base p-nitroaniline between benzene and water is 9.0
(in favour of benzene). 0.006 93 mol of p-nitroanilinium chloride was dissolved in one
dm3 of dil HCl solution of molarity 0.043 42 M. To this solution 60 cm3 of benzene
was added and the solution shaken up till the equilibrium was attained. Then 25 cm3 of
benzene solution was withdrawn and was analyzed for the base and thus found to contain
0.108 25 g p-nitroaniline. Calculate the hydrolysis constant of the salt.
Solution Given that

Concentration of p-nitroaniline in benzene layer

= 9.0
Concentration of p-nitroaniline in aqueous layer
(0.108 25 g)
Amount of free base in 25 cm3 of benzene =
(138 g mol -1 )

Ê 0.108 25 g ˆ Ê 60 cm 3 ˆ
Thus in 60 cm3, the amount = Á ÁË 25 cm 3 ˜¯ = 0.001 88 mol
Ë 138 g mol -1 ˜¯

Ê 0.001 88 mol ˆ
Molar concentration of free base = Á = 0.031 33 mol dm -3
Ë (60 /1 000) dm3 ˜¯
202 A Textbook of Physical Chemistry

Using the distribution coefficient, we find that molar concentration of free base in aqueous

(0.031 33 mol dm -3 )
solution = = 0.003 48 mol dm -3
9
The added amount of 0.006 93 mol of p-nitroanilinium chloride will be present in two
forms, namely, (i) unhydrolyzed salt, and (ii) hydrolyzed salt. The hydrolysis reaction is

p-O2 NC6H 4 NH3+Cl - + H 2O p-O2 NC6 H 4 NH 2 + H3O+ + Cl -

Unhydrolyzed salt Hydrolyzed salt
(free base)

Thus, the amount of unhydrolyzed cation

= Total amount of salt added – Total amount of free base
= Total amount of salt added – (Free base in benzene + Free base in water)
= 0.006 93 mol – (0.001 88 mol + 0.003 48 mol)
= 0.001 57 mol
Amount of acid set free because of hydrolysis
= Total amount of free base in benzene and water
= 0.001 88 mol + 0.003 48 mol = 0.005 36 mol
Total amount of acid = Acid already present + Acid set free
= 0.043 42 mol + 0.005 36 mol
= 0.048 78 mol
Thus, the concentrations of various species in water for the reaction
O2NC6H4NH3+ + H2O O2NC6H4NH2 + H3O+
are [O2 NC6 H 4 NH3+ ] = 0.001 57 mol dm -3
[O2 NC6 H 4 NH 2 ] = 0.003 48 mol dm -3
[H3O+ ] = 0.048 78 mol dm -3
and hence

[O2 NC6H 4 NH 2 ][H3O+ ] (0.003 48 mol dm -3 )(0.048 78 mol dm -3 )

Kh = =
[O2 NC6H 4 NH3+ ] (0.001 57 mol dm -3 )
= 0.108 1 mol dm -3

Example 4.20.3 The distribution ratio of ammonia between water and chloroform at 291 K is 25.8.
When a 0.025 mol dm–3 of copper sulphate solution was equilibrated with ammonia and
chloroform, the aqueous and chloroform solutions contained 0.385 mol dm–3 and
0.011 2 mol dm–3 of ammonia, respectively. Determine how much of ammonia is complexed
with the Cu2+ ion and the value of x in the formula Cu(NH3)x2+.

Solution We are provided that

Concentration of NH3 in aqueous solution
= 25.8
Concentration of NH3 in chloroform
Concentration of NH3 in aqueous CuSO4 solution = 0.385 mol dm–3
Concentration of NH3 in chloroform = 0.011 2 mol dm–3.
Using distribution coefficient, concentration of free NH3 in aqueous layer
= (0.011 2 mol dm–3)(25.8)
= 0.289 0 mol dm–3
 Solutions 203

Concentration of combined NH3 = 0.385 0 mol dm–3 – 0.289 0 mol dm–3

= 0.096 0 mol dm–3
[ NH3 ]combined 0.096 0 M
The value of x in Cu(NH3 )2+
x = = = 3.84 4
[CuSO4 ] 0.025 M

Solvent Extraction The Nernst distribution law is the basis for the solvent extraction process in
which the dissolved solute in one solvent is extracted with the help of another
solvent. When a solution containing the solute is shaken with another immiscible
solvent, the solute distributes between the two solutions according to the Nernst
distribution law. From the second solvent, the solute can be separated by simple
processes such as distillation, evaporation, etc. For efficient use of the solvent,
it is advantageous to carry out this process in a series of successive stages. This
can be proved as follows.
Let m be the mass of solute present in volume V1 of the solvent 1 (or
V1 of the solution) and let the volume V2 of the solvent 2 be added each time
till the entire solvent 2 is exhausted. If the solvent 2 is added n times, we have
Total volume of the solvent 2 used for extraction = nV2
Multi-stage If m1 is the mass of the solute that remains unextracted in the solvent 1 after the
Extraction addition of first lot of V2 of the solvent 2, then we have
c1 m1 /V1
= = Kd
c2 (m - m1 ) /V2
Solving for m1, we get
Ê KdV1 ˆ
m1 = Á m (4.20.18)
Ë KdV1 + V2 ˜¯
If m2 is the mass of the solute unextracted after the addition of the second
lot, then
c1¢ m2 /V
= = Kd
c2¢ (m1 - m2 ) /V2
Ê KdV1 ˆ
or m2 = Á m
Ë KdV1 + V2 ˜¯ 1
Substituting m1 from Eq. (4.10.18), we get
2
Ê KdV1 ˆ
m2 = Á m (4.20.19)
Ë KdV1 + V2 ˜¯
Carrying out the above process n times, we will get
n
Ê KdV1 ˆ
mn = Á m (4.20.20)
Ë KdV1 + V2 ˜¯
Thus, the fraction of the solute remaining unextracted in solvent 1 is
n
mn Ê KdV1 ˆ
= Á (4.20.21)
m Ë KdV1 + V2 ˜¯
204 A Textbook of Physical Chemistry

Single-stage If the extraction were carried out in a single stage by adding whole of the solvent
Extraction 2 in one lot, we would have

m¢ Ê KdV1 ˆ
= Á (4.20.22)
m Ë KdV1 + nV2 ˜¯

Comparing Now we proceed to show that the multi-stage extraction is more effective than
the single-stage extraction. Taking the inverse of Eq. (4.20.21), we get
Two Processes n n
m Ê K V + V2 ˆ Ê V ˆ
= Á d 1 = Á1 + 2 ˜ (4.20.23)
mn Ë KdV1 ˜¯ Ë KdV1 ¯
The right side of Eq. (4.20.23) can be expanded by using binominal theorem.
We have
n 2
m Ê V ˆ nV2 n(n - 1) Ê V2 ˆ
= Á1 + 2 ˜ =1+ + ÁË K V ˜¯ + ◊◊◊ (4.20.24)
mn Ë KdV1 ¯ KdV1 2 d 1

The inverse of Eq. (4.20.22) is

m K V + nV2 nV2
= d 1 =1+ (4.20.25)
m¢ KdV1 KdV1

Substituting Eq. (4.20.25) in Eq. (4.20.24), we get

2
m m n(n - 1) Ê V2 ˆ
= + ÁË K V ˜¯ + ◊◊◊
mn m¢ 2 d 1

Therefore it follows that

m m
> or mn < m ¢
mn m¢

that is, the amount of the solute remaining unextracted is less in multi-stage
extraction. In other words, the amount of extracted solute is larger in multi-stage
extraction than in single-stage extraction. Hence the former is more effective for
extraction of solute from a given solution.
It may, however, be mentioned that a complete extraction of the solute
can never be achieved howsoever large number of extractions may be done, as
something will always be left behind in the solution in accordance with the
distribution law.
While calculating m from Eqs. (4.20.21) and (4.20.22), one should be
very careful about the expression for Kd. The latter represents the ratio of the
amount of solute in the solvent in which it is already present to that of the
extracting solvent. Sometimes, the value of Kd is given as the ratio of the solute
in the extracting solvent to that in which it is already present. In such cases,
the reciprocal of the given value of Kd should be employed while using Eqs
(4.20.21) and (4.20.22).
 Solutions 205

Example 4.20.4 A solute A is distributed between two immiscible liquids B and C with the value of the
distribution coefficient, [A]C/[A]B, equal to 10. The concentration units are expressed in
terms of grams of solute per dm3 of solvent. It is desired to remove 99% of the amount
of A from a solution containing 1 g of A in 100 cm3 of B by extraction with successive
10 cm3 portions of solvent C. Calculate the approximate volume of solvent C required
for this purpose.
Solution We have
[A]C 10
=
[A]B 1

[A]B 1
Therefore = = 0.1 = Kd
[A]C 10
Since 99% of A is to be removed from a solution containing 1 g of A per 100 cm3 of
B, we have
mn = 0.01 g m = 1.00 g VB = 100 cm 3 VC = 10 cm 3
The number of times (n) solvent C to be added can be calculated from
n
mn Ê KdVB ˆ
=Á
m Ë KdVB + VC ˜¯
Substituting the given data, we get
n
0.01 g Ê 0.1 ¥ 100 cm 3 ˆ
=Á
1g Ë 0.1 ¥ 100 cm 3 + 10 cm 3 ˜¯
n
Ê 1ˆ
or 0.01 = Á ˜ or log (0.01) = - n log 2
Ë 2¯
or n=7
Hence, volume of C to be used in 7 × 10 cm3, i.e. 70 cm3

Example 4.20.5 An aqueous solution contains 0.20 g aspirin in a 50 cm3 solution. To this solution is added
20 cm3 of ether, and the mixture is shaken and allowed to attain equilibrium at 298 K.
At this temperature, the distribution coefficient of aspirin between ether and water is 4.7.
(i) How much aspirin remains in the aqueous phase?
(ii) If the extraction is carried out with two successive 10 cm3 portions of ether, how
much aspirin remains unextracted?
Solution (i) We have
Aspirin in g cm -3 in ether
Kd = = 4.7
Aspirin in g cm -3 in water
Let m1 and m2 be the respective masses of aspirin in ether and the aqueous phase after
the addition of 20 cm3 of ether in the given 50 cm3 of aqueous solution. It follows that
m1/20 cm 3
= 4.7
m2 /50 cm 3

and m1 + m2 = 0.20 g
206 A Textbook of Physical Chemistry

Solving for m1 and m2, we get

m1 = 0.130 6 g and m2 = 0.069 4 g
Thus, the mass of aspirin remaining in aqueous phase = 0.069 4 g
(ii) For the multi-stage extraction, we have to use the distribution coefficient given below.
Aspirin in water 1
Kd = = = 0.212 8
Aspirin in ether 4.7
We have
n
mn Ê KdV1 ˆ
=Á
m Ë KdV1 + V2 ˜¯
where for the given problem, we have

mn = ? m = 0.20 g V1 = 50 cm 3 V2 = 10 cm 3 n= 2

Substituting the given data, we get

2
Ê 0.212 8 ¥ 50 cm 3 ˆ Ê 10.64 ˆ
2
mn = Á 3˜
(0.20 g) = Á ˜ (0.20 g)
Ë 0.212 8 ¥ 50 cm + 10 cm ¯
3 Ë 20.64 ¯
= 0.053 1 g
Hence
Aspirin remains unextracted = 0.053 1 g
Aspirin extracted = 0.2 g – 0.053 1 g = 0.146 9 g

REVISIONARY PROBLEMS

4.1 (a) Define the terms absorption coefficient α and coefficient of solubility β. Derive
the expression relating α and β.
(b) What is the variance of a system involving a dissolved gas in a liquid?
4.2 Define Henry’s law and show that the volume of an ideal gas dissolved in a given
volume of solvent (measured at the pressure of the experiment) is independent of the
pressure.
4.3 What is the effect of temperature on the solubility of a gas in liquids?
4.4 Show that Henry’s law is a special case of the distribution law and Raoult’s law.
4.5 Prove the statements that:
(i) Raoult’s law may be considered as a special case of Henry’s law; all systems
which obey Raoult’s law must satisfy Henry’s law, but the reverse is not true unless
Henry’s law is applicable over the entire range of concentration.
(ii) Raoult’s law is applicable to the solvent over the range where Henry’s law in
the form x2 = k p2 is applicable to solute.
4.6 What is an ideally dilute solution? Derive the expressions of chemical potential for
solute and solvent in an ideally dilute solution.
4.7 Derive Henry’s law from the viewpoint of kinetic-molecular theory.
4.8 Explain, what do you understand by an ideal solution. Show that for an ideal
solution mixH = 0 and mixV = 0, where mixH and mixV are the changes in enthalpy
and volume on mixing various constituents of the liquid solution. Suggest a possible
reason for mixH and mixV being equal to zero.
 Solutions 207

4.9 (a) Following Raoult’s law, derive an expression for the total vapour pressure of
an ideal binary liquid solution in terms of the amount fraction of either of the two
constituents in the liquids phase. Draw a schematic diagram for the variation of pA
versus xA, pB versus xB and p versus xA (or xB) for a system in which pA* > pB*.
(b) Derive an expression for the total vapour pressure of an ideal binary liquid
solution in terms of the amount fraction of either of the two constituents in vapour
phase. Draw a schematic plot of p versus yA and 1/p versus yA.
4.10 (a) What is the variance of a binary liquid solution? Show that the state of the solution
at a constant temperature can be represented on a two dimensional plot of pressure
versus composition. Draw such a plot and label different regions and lines of the plot.
(b) Explain, why a region instead a point is observed when a binary liquid mixture
is in equilibrium with its vapour.
(c) Predict the sequence of steps that takes place when the pressure on the binary
liquid mixture at a constant temperature is gradually lowered.
(d) What is the lever rule and deduce it from pressure versus composition diagram
for the binary liquid mixture?
(e) Discuss briefly the principle underlying the isothermal fractional distillation of
an ideal binary liquid mixture.
4.11 (a) Draw a plot of temperature versus composition diagram at constant pressure for
an ideal binary liquid mixture. Explain qualitatively why the liquids and the vaporous
curves are not straight lines.
(b) Explain, why you should have a region over which the liquid mixture is in
equilibrium with its vapour.
(c) Predict the sequence of steps that takes place when the temperature of a binary
liquid mixture is gradually increased; hence describe briefly the theory of the isobaric
factional distillation of an ideal binary solution. What are the end products in such
a distillation?
(d) Describe the theory of the bubble-cap fractionating column.
4.12 (a) What are nonideal solutions? How do they differ from ideal solutions? What are
the main criteria for exhibiting positive sand negative deviations from ideality?
(b) Draw a schematic diagram for pA versus xA, pB versus xB and p versus xA(or xB)
of a system showing (i) positive deviation, and (ii) negative deviation. Also, show
in the diagram the limiting Henry’s line and the limiting Raoult’s law line.
4.13 (a) Starting from the Gibbs-Duhem equation, derive the Duhem-Margules equation
as applicable to a binary liquid system. To which type of liquid mixtures (ideal or
nonideal), the Duhem-Margules equation is applicable?
(b) Starting from the Duhem-Margules equation as applicable to a binary liquid system,
show that: (i) if one component behaves ideally, then the other also does so, and
(ii) if one component shows positive deviation (or negative deviation), so also must
the other.
4.14 Konowaloff’s rule states that:
The vapour phase is richer in the component whose addition to the liquid mixture
results in an increase of total vapour pressure.
or
The liquid phase is richer in the component whose addition to the liquid mixture
results in a decrease of total vapour pressure.
Derive the above statements from the Duhem-Margules equation.
4.15 How will you justify the following alternative statements of Konowaloff’s rule.
The vapour phase is richer in the component whose addition to the liquid
mixture causes a decrease in the boiling point or alternatively, the liquid is richer in
208 A Textbook of Physical Chemistry

the component whose addition to the liquid mixture causes an increase in its boiling
point.
4.16 (a) Draw schematic plots of temperature versus composition for nonideal solutions
showing very large positive and negative deviations from ideality.
(b) Show that at the maximum or minimum point of the above plots, the following
relation holds good

yA x
= A
yB xB

that is, the composition of the vapour phase is identical with that of the liquid with
which it is in equilibrium. On this basis justify that the liquids curve must meet with
the vapour curve at the maximum or minimum point.
(c) Show with the help of diagrams that (i) both the components can be separated
from a nonideal solution if the components show a little deviation from ideality, and
(ii) only pure A or pure B and not both of them if the components show very large
deviation from ideality.
(d) What is an azeotropic mixture? Show that it is not possible to separate the
constituents from an azeotropic mixture following the ordinary fractional distillation.
What other methods could be employed for the separation from the azeotropic
mixture? How will you show that an azeotropic mixture is really a mixture and not
a single compound resulted because of the definite union of the two constituents?
4.17 (a) Derive the relation
DTb = K b m (1 - K )

as applicable to a dilute solution of a nonideal binary liquid mixture, i.e. one of the
liquids is present in a very large amount (solvent) and the other one in a very small
amount (solute). In the above expression, Tb is the change in the boiling point of
the solvent as a result of the addition of the volatile solute; Kb is the boiling point
elevation constant, and K is the distribution coefficient of the solute between the
vapour phase and the liquid phase and is defined as

Amount fraction of the solute in the vapour phase

K=
Amountt fraction of the solute in the liquid phase

(b) Show that Tb can be positive or negative depending upon the value of K, and
hence show that the change in Tb is in agreement with Konowaloff’s rule.
4.18 (a) What do you understand by partially miscible liquids? Show that the formation
of partially miscible liquids have sound theoretical background and can be explained
qualitatively from the Duhem-Margules equation.
(b) Using the phase rule expression, show that the compositions of the two conjugate
solutions in the miscible gap are quite definite for a given temperature and are
independent of the relative amounts of the two solutions. Draw a schematic plot
connecting the compositions of the two conjugate solutions at different temperatures.
(c) What is the difference between the critical solution temperature and mutual
solubility temperature?
(d) Show with the help of the phase rule that at a given pressure, the critical solution
temperature is a nonvariant point.
(e) Describe the sequence of steps that takes place when (i) the temperature of a
given overall composition of partially miscible liquids is changed.
 Solutions 209

(f) At a temperature lower than CST, if we sweep from one extreme composition to
the other, we will have to pass through the miscibility gap. Suggest an alternative
path where this miscibility gap could be avoided.
(g) Explain, why certain liquid pairs show lower CST.
(h) Explain, under what circumstances, a liquid pair shows both the upper and the
lower CST. What effect the pressure has on the temperature-composition curve for
such a type of liquid pairs?
(i) Explain why in some cases the CST (upper or lower) is not observed experimentally.
(j) What effects impurities have on the CST?
(k) Describe with the help of appropriate diagram, the end products that are obtained
when the following categories of partially miscible binary liquid mixtures are
subjected to fractional distillation: (i) Partially miscible binary liquid mixtures with
no azeotropic mixture and also showing incomplete separation of constituents, (ii)
Partially miscible binary liquid mixtures showing an azeotropic mixture, (iii) Partially
miscible binary liquid mixtures exhibiting complete separation of constituents.
4.19 Describe the theory of steam distillation.
4.20 (a) State the Nernst distribution law and show that it is in agreement with the phase
rule requirements.
(b) Derive thermodynamically the distribution law. What approximations are made
in deriving this law?
(c) Show that for a solute distributed in two ideally dilute solutions, its solubility in
a solution is inversely proportional to its Henry’s law constant in that solution.
(d) One of the basic requirements of the distribution law as suggested by Nernst is that
the solute must have the same molecular form in both the layers. However, in some
cases the association, dissociation, etc., of the solute takes place. Under such conditions
the original definition of the distribution law can be modified in order to account for
such changes. Derive the following modified forms of the distribution law:
(i) Solute having normal existence in the liquid α and dimerizes in the liquid .
1/2
[A] /([A] , total) = constant

(ii) Solute A having normal existence in the liquid and dissociates (A B + C)

in the liquid
[A]a
= constant
x 2 /Kdiss

(iii) Solute having normal existence in the liquid and undergoes a chemical reaction
with the liquid of the type A + n A n

[A] /[A] , total = constant

(d) Describe how the distribution experiments can be used to determine the equilibrium
constant of each of the following reactions.

(1) KI + I2 KI3 (2) C6H5NH3+ + H2O C6H5NH2 + H3O+

(3) Cu2+ + 4 NH3 Cu(NH3)42+

(e) What is a solvent extraction? Show mathematically that multi-stage extraction is

more profitable than single-stage extraction.
210 A Textbook of Physical Chemistry

TRY YOURSELF PROBLEMS

4.1 Hydrogen sulphide obeys Henry’s law. What does this indicate about H2S dissolved
in water?
4.2 (a) Henry’s law can be written as p = kH x and Raoult’s law as
p = kR x
In general, Henry’s law constant kH is different from Raoult’s law constant kR. Explain
why it is so. Under what conditions the two constants have the same value?
(b) Show that Bunsen absorption coefficient is related to Henry’s law constant by
the expression α = ρ (22 414 cm3 mol–1)/kHM1.
[Hint: p2 = kH x2 = kH n2/(n1 + n2) kHn2/n1
= kH {υ0/(22 414 cm3 mol–1)}/(V1 ρ/ M1]
Hence, α = υ0/(p2V1) = ρ (22 414 cm3 mol–1) / kH M1.]
4.3 (a) Figure 1 shows vapour pressure versus composition plots of a binary liquid
system. Answer the following:
(i) Identify the two curves with the corresponding liquids,
(ii) By drawing limiting Henry’s law and Raoult’s law lines, show the regions of
applicability of these laws.
(iii) How will you obtain the Henry’s law constants for the liquids A and B?
(b) Explain why the types of vapour pressure versus composition plots of a binary-
liquid system shown in Fig. 2 are theoretically not feasible.
(c) What is the difference between ideal and ideally dilute solutions?

4.4 Under what conditions are the following true?

(i) Henry’s law constant = Raoult’s law constant
(ii) Henry’s law constant > Raoult’s law constant
(iii) Henry’s law constant < Raoult’s law constant
4.5 For an ideal binary system, compute mixG and mixS at 298 K for xA = 0.1 to 0.9
with a regular interval of 0.1 and then draw the plots of mixG versus xA and mixS
versus xA. Show mathematically or otherwise that mixG is minimum and mixS is
maximum at xA = 0.5.
4.6 Starting from the fact that for a binary system exhibiting positive deviation from
Raoult’s law, either solvent-solvent interactions or solute-solute interactions are strong
compared to solvent-solute interactions, show that for such a system
D mix H > 0; D mix S < D mix Sideal ; D mixG > D mixGideal ; pA > pA, ideal
(Hint: See Example 4.14.1.)
 Solutions 211

4.7 The chemical potential of a constituent in a nonideal system is given by

mi = m*i + RT ln ai , where ai is the activity of the constituent in the solution and
is related to the amount fraction by the equation ai = xi g i (where γi is the activity
coefficient of the constituent). For a very dilute solution, real solution behaves as
an ideal solution, and, therefore, we have ai Æ xi and g i Æ 1 . Show that for a real
solution

D mixG = RT Â xi ln ai and D mix S = - R Â xi ln ai

i i

4.8 Suppose the distribution coefficient of I2 is studied between an aqueous solution of

NH4Cl and chloroform. Would you expect Kd to be different or same as that between
water and chloroform? (Ans. Kd increases as [I2]NH4Cl(aq) > [I2]water)
4.9 (a) Show that the nonideal binary liquid solutions may be classified into the following
three categories based on the Ks values as defined by Eq. (4.17.5). Designate K as
KA in B, where A is solute and B is solvent, or KB in A, where B is solute and A is
solvent.

System Ks values
(i) Solution with a little deviation KA in B > 1 and KB in A < 1
from ideality Ï or
ÌK
Ó A in B < 1 and KB in A > 1
(ii) Solution with large negative KA in B < 1 and KB in A < 1
deviation from ideality
(iii) Solution with large positive KA in B > 1 and KB in A > 1
deviation from ideality

(b) Rationalize the following facts with the help of Eq. (4.17.5).
(i) The addition of ethyl bromide in ethyl iodide lowers the boiling point of the
solvent whereas the addition of ethyl iodide in ethyl bromide raises the boiling point.
(ii) The addition of n-heptane in ethyl alcohol or ethyl alcohol in n-heptane lowers
the boiling point of the solvent.
(iii) The addition of pyridine in acetic acid or acetic acid in pyridine raises the
boiling point of the solvent.
4.10 Is it possible for one component of a binary solution to behave ideally but not the
other component?
4.11 In aqueous solution of NH3, the following equilibria exist:

Keql Keq2
+ –
NH3 + H2O � � NH3 H2O �
����
�
��� � NH4 + OH
����
�
���
Show that the expression for the distribution of NH3 between water and chloroform
is given by

[NH3 ]total, aq
= Kd (1 + Keq1 + Keq1 Keq2 /[OH - ])
[NH3 ]org
212 A Textbook of Physical Chemistry

For NH4OH solution, Keq1 + Keq2/[OH–] << 1. Hence show that

[NH3 ]total, aq
= constant
[NH3 ]org
4.12 Show that for a given pressure, a binary mixture at the azeotropic point is an
invariant system.
(Hint: Compositions of liquid and vapour phases are identical. Hence
F = (C – r) + 2 – P = (2 – l) + 2 – 2 = l, which is the given pressure.)

NUMERICAL PROBLEMS

Solubility of Gases 4.1 The Bunsen absorption coefficients of O2 and N2 in water at 298 K are 0.028 3 and
0.014 3 atm–1, respectively. If air contains 20% O2 and 80% N2, by volume, how
many cubic centimetre of gas measured at STP will be dissolved in 100 cm3 of
water in equilibrium with air at that temperature? How many, if pressure is 10 atm?
(Ans. 1.71 cm3 and 17.1 cm3)
4.2 Water saturated with air (20% O2 and 80% N2) at 298 K contains 8.9 × 10–3 g
dm–3 of dissolved oxygen. Estimate the solubility of pure oxygen in water at a
pressure of 25 atm and a temperature of 298 K. (Ans. 1.1125 g)
4.3 The solubility coefficient S for CO2 dissolved in water has the following values at
different temperatures.
θc/°C 0 10 20 30 40
S 1.713 1.238 0.943 0.766 0.608
Calculate the mean value of enthalpy of solution of CO2 in water.
(Ans. – 18.12 kJ mol–1)
4.4 Given the following Bunsen absorption coefficients for CO at different temperatures,
calculate the mean value of enthalpy of solution of CO in water.
θc/°C 0 10 20 30 40
S/atm–1 0.035 4 0.028 2 0.023 2 0.020 0 0.017 8
(Ans. – 11.87 kJ mol–1)
Henry’s Law 4.5 The table below lists the vapour pressure of methyl chloride above the mixture with
water at 298 K. Find Henry’s law constant for methyl chloride.
m(CH3Cl)/mol kg–1 0.029 0.051 0.106 0.131
p/mmHg 205.2 363.2 756.1 945.9
(Hint: Convert molalities into amount fractions, plot pressure versus amount
fraction and extrapolate the plot in the dilute solution region up to x = 1.)
(Ans. 40 000 mmHg)
4.6 At 0 °C the Henry’s law constant for argon in water is 2.17 × 104 bar and at 30
°C the constant is 3.97 × I04 bar for p = 1 atm. Find the approximate enthalpy of
solution over this temperature range. (Ans. 13.87 kJ mol–1)
Ideal Solution 4.7 (a) The vapour pressures of n-hexane and n-heptane at 273 K are 45.5 and 11.4
mmHg. What is the composition of a solution of these two substances if its total
vapour pressure at 273 K is 37.3 mmHg? (Ans. 0.759 5)
(b) The amount fraction of n-hexane in the vapour above a solution of n-hexane and
n-heptane is 0.75 at 273 K. What is the composition of the liquid solution?
(Ans. 0.429)
4.8 Calculate the (i) enthalpy, (ii) entropy, (iii) volume, and (iv) Gibbs free energy of
mixing of 1 mol of benzene and 2 mol of toluene at 298 K?
(Ans. (i) 0, (ii) 15.86 J K–1, (iii) 0, and (iv) – 4.732 kJ)
 Solutions 213

4.9 (a) Benzene and toluene form essentially ideal solutions, and a particular mixture
which consists of two moles of benzene and three moles of toluene has a total vapour
pressure of 280 mmHg at 333 K. If one additional mole of benzene is added to
the solution, the new total vapour pressure is now 300 mmHg. Calculate the vapour
pressures of pure benzene and toluene at 333 K?
(Ans. pb* = 400 mmHg and p*t = 200 mmHg)
4.10 At 413 K, the vapour pressure of C6H5Cl is 939.4 Torr and that of C6H5Br is 495.8
Torr. Assuming that these two liquids form an ideal solution, determine the composition
of a mixture of the two which boils at 413 K under 1 atm pressure? What will be
the composition of the vapour at this temperature?
(Ans. For C6H5Cl, x = 0.596, y = 0.736)
4.11 Ethanol and methanol form very nearly ideal solutions. The vapour pressures of
ethanol and methanol are 44.5 Torr and 88.7 Torr, respectively. Calculate:
(a) the amount fraction of methanol in a solution obtained by mixing 100 g of each,
(b) the partial pressures and the total vapour pressure of the solution, and
(c) the amount fraction of methanol in the vapour.
(Ans. (a) 0.59, (b) pethanol = 18.2 Torr, pmethanol = 52.3 Torr,
ptotal = 70.5 Torr, (c) 0.741)
4.12 The normal boiling points of C6H5Cl and C6H5Br are 405.2 K and 429.2 K, respectively.
Assuming that these two liquids form an ideal solution:
(a) Determine the composition of a mixture of the two which boils at 413 K under
1 atm pressure.
(b) What would be the corresponding composition of vapour which is liberated at
413 K?
Assume Trouton’s law is applicable to both the above constituents.
(Ans. For C6H5Cl, x = 0.606, y = 0.74)
4.13 An ideal solution of two components with vapour pressures of 400 mmHg and 300
mmHg when pure contains two moles of the more volatile component and five moles
of the less volatile one. Calculate:
(a) Total vapour pressure of the solution.
(b) Composition of the vapour in equilibrium with a solution of this composition.
(c) Composition of the last drop to vaporize from such a solution when none of the
vapour is withdrawn from contact with the unvaporized mixture.
(d) Composition of the last drop to vaporize when the distillate from such a solution
is continuously condensed elsewhere and is thus withdrawn from contact with the
unvaporized mixture.
4.14 (a) Benzene and toluene form nearly an ideal solution. Their boiling points in pure
state are 80.2 °C and 110 °C, respectively. The temperature-composition data for
them are given below:
xbenzene 0.00 0.24 0.35 0.46 0.90 1.00
ybenzene 0.00 0.44 0.62 0.77 0.95 1.00
b.pt./°C 110 101 93 88 83 82
(i) If a solution with 50 mol per cent in benzene is to be distilled, at what temperature
will the distillation just start? What would be the composition of the distillate which
just issues at the above temperature?
(ii) Suppose that the above distillate is condensed. Predict the temperature at which
this liquid mixture will just start distilling and find out the corresponding composition
of the vapour which issues at this temperature.
214 A Textbook of Physical Chemistry

(iii) A liquid mixture containing 0.9 amount fraction of benzene is distilled without
removing the distillate till it contains 0.24 amount fraction of benzene. What will
be the composition of the resultant distillate?
(b) By employing Eqs. (4.12.8) and assuming Trouton’s law to be applicable to
both the species, calculate boiling point of the solution containing 50 mol per cent
in benzene. After obtaining this value, calculate the composition of the vapour from
Eq. (4.12.9).
4.15 At 363 K the vapour pressure of toluene is 400 mmHg, and that of o-xylene is 150
mmHg. What is the composition of a liquid mixture that will boil at 363 K when
the pressure is 0.5 atm? What is the composition of the vapour produced?
(Ans. xtoluene = 0.92, ytoluene = 0.97)
4.16 Construct the temperature-composition diagram for the system ethanol-ethyl acetate
from the following data available at 760 Torr external pressure.

x(C2H5OH) y(C2H5OH) b.pt./ºC x(C2H5OH) y(C2H5OH) b.pt./ºC

0 0 77.15 0.563 0.507 72.0
0.025 0.070 76.7 0.710 0.600 72.8
0.100 0.164 75.0 0.833 0.735 74.2
0.260 0.295 72.6 0.942 0.880 76.4
0.360 0.398 71.8 0.982 0.965 77.7
0.462 0.462 71.6 1.000 1.000 78.3

From the obtained plot answer the following:

(a) What is the composition of the first vapour to come of from a solution containing
0.8 amount fraction of ethanol? What would be the boiling point of the liquid?
(b) What would be the composition of the last drop of liquid to evaporate?

Nonideal Solution 4.17 The following data were obtained for benzene(A)–ethanol(B) solutions at atmospheric
pressure:
Boiling point/ºC 78 75 70 70 75 80
xA 0 0.04 0.21 0.86 0.96 1
yA 0 0.18 0.42 0.66 0.83 1
(a) Plot the temperature-composition diagram for this system and estimate the
composition and boiling point of the azeotrope.
(b) For a solution containing 20 g of benzene and 50 g of ethanol, estimate the
boiling point and the composition of the vapour first formed at this temperature.
(c) If the solution described in (b) is exhaustively fractionated, which component
will be obtained as a pure substance? Is this component the distillate or residue?
How much of this component will be obtained as a pure substance?
4.18 Given below are the partial vapour pressures of A and B in a binary liquid solutions
at 30 ºC.

xA 0 0.12 0.30 0.60 0.80 1.0

pA / Torr 0 20.0 55.0 140.0 225.0 295.0
pB /Torr 345.0 300.0 230.0 110.0 37.5 0

Calculate the Henry’s law constants for A and B and also the activities and activity
coefficients of A and B at the given compositions.
 Solutions 215

Partial Miscible 4.19 (a) Prepare a liquid-liquid phase diagram for the system of partially miscible liquids
Liquids A and B, where the mass % of B at various temperatures are
θC /ºC 0 10 20 30 40
(mass % B)1 30 37 45 53 64
(mass % B)2 94 90 87 84 80
What is the critical solution temperature?
(b) You are given a system containing 60 mass % of B at 20 °C. What is the nature
of the system, whether it forms a single liquid or two liquids? If two, what are their
compositions and the relative amounts? At what minimum temperature this system
can be converted into the one liquid?
4.20 Methylethyl ketone and water are partially miscible. At 303 K the two layers contain
21.9 and 89.9% by mass of ketone. What will be the mass of each layer when 50 g
each of methylethyl ketone and water are equilibrated at this temperature?
(Ans. 41.3 g methylethyl ketone—rich layer)
Steam Distillation 4.21 If the vapour pressure of water at 363 K is 526 mmHg, what mass of chlorobenzene
will be distilled per gram of water collected in the distillate, if chlorobenzene is
distilled at 363 K at a total pressure of 734 mmHg. (Ans. 8.876 g)
4.22 A mixture of an organic liquid A and water is distilled under one atmosphere pressure
at 372.2 K. What mass of steam would be condensed to obtain 1.0 g of liquid A in
the distillate? The vapour pressure of water at 372.2 K is 739 Torr; molar mass of
A = 123 g mol–1. (Ans. 5.15 g)
4.23 A mixture consisting of an organic liquid A and water (immiscible) distills at 368
K at 756 mmHg. The vapour pressure of H2O at 368 K is 634.6 Torr. Calculate the
molar mass of A, if the distillate contains 65 per cent by mass of the liquid A.
(Ans. 174.8 g mol–1)
Distribution Law 4.24 The following data were obtained when quinine C20H24O2N2 was distributed between
ether and water at 273 K.
(Water layer/g) per 100 cm3 0.0547 0.059 0 0.062 2
(Ether layer/g) per 100 cm3 0.114 2 1.290 1 1.428 1
Quinine exists as a monomer in water. Determine its molecular complexity in ether.
(Ans. Dimeric)
4.25 When different amounts of phenol were equilibrated with a mixture of water (W)
and chloroform (C) at 298 K the concentrations of the two solutions formed in each
case had the following values.
cW/mol dm–3 7.85 × 10–4 1.73 × 10–3 2.64 × 10–3 4.65 × 10–3
cC/mol dm–3 1.64 × 10–3 2.10 × 10–3 1.97 × 10–2 5.77 × 10–2
Phenol dissolved in water is almost completely monomeric.
(a) Is this also true of phenol dissolved in chloroform?
(b) Calculate the value of the distribution coefficient.
(Ans. (a) No, (b) 3.7 × 10–4)
4.26 The distribution coefficient of succinic acid between water and ether is 5.7. How much
ether is required to decrease the concentration of succinic acid in 50 cm3 of water from
5 to 1 per cent? Suppose that the extraction had been done in 10 stages by employing
the volume each time equal to the (V/10), where V is the volume of ether obtained in
the single-stage extraction. How much succinic acid remaining unextracted in water?
(Ans. 1 140 cm3, 0.173%)
216 A Textbook of Physical Chemistry

4.27 Solutions of ammonia in water were shaken with chloroform at 298 K. The following
data were obtained when the equilibrium is reached.
[NH3]water/mol dm–3 0.011 0 0.08 5 0.64 2
[NH3]CHCl3/mol dm–3 0.000 44 0.003 3 0.025 8
What is the distribution coefficient?
(Ans. 25.2 in favour of water)
4.28 Some iodine is dissolved in an aqueous solution of potassium iodide of concentration
0.102 mol dm–3, and the solution is then shaken with carbon tetrachloride until
equilibrium is reached (at 15 °C). The amount of iodine at equilibrium is found to be
0.048 mol dm–3 in the aqueous layer and 0.089 mol dm–3 in the carbon tetrachloride
layer. The distribution coefficient of iodine between carbon tetrachloride and water
is 85. Calculate the equilibrium constant at 15 °C for the reaction
I3–(aq) I2(aq) + I–(aq)
(Ans. 1.23 × 10–3 mol dm–3)
4.29 0.062 4 mol of an amine hydrochloride is present per dm3 of the aqueous solution.
On shaking this solution with one dm3 of benzene, 0.009 64 mol of the free base
is extracted. The distribution coefficient of the free base for benzene and water is
24.1. Calculate the hydrolysis constant for the base hydrochloride.
(Ans. 7.67 × 10–5 mol dm–3)
4.30 An aqueous solution contains 0.20 g aspirin (C9H8O4) in 50 cm3 solution. To this
solution 20 cm3 of ether is added and the mixture is shaken and allowed to come
to equilibrium at 298 K. At this temperature Kd = cether/cwater = 4.7. (a) How much
aspirin remains in the aqueous phase? (b) If the extraction is carried out with two
successive 10 cm3 portions of ether, how much aspirin remains unextracted?
(Ans. (a) 0.000 38 mol, (b) 0.000 29 mol)
4.31 (a) A series of solutions of iodine in chloroform were shaken with water at 298 K
until equilibrium was established. The following results were obtained.
[I2]water/mol dm–3 0.000 25 0.001 20 0.001 84 0.002 42
[I2]CHCl3 mol dm–3 0.033 8 0.154 6 0.231 8 0.320 7
What is the value of the distribution coefficient?
(b) How many times would it be necessary to equilibrate 1 dm3 of a solution of
iodine in water with 10 cm3 samples of chloroform in order to reduce the iodine
concentration to 10–2 of an initial value?
(Ans. (a) 0.007 6, (b) six extractions)
4.32 Parke’s process involves the extraction of silver from the molten argentiferrous
lead with the help of molten zinc. Silver is more soluble in zinc than in lead
(Kd = [Ag]Zn/[Ag]Pb = 300). Zn – Ag has a higher melting point and is thus solidified
first. It is separated and subjected to distillation in a retort when Zn passes over leaving
behind silver. Calculate the mass of Ag that can be separated from 1 000 mL of
argentiferrous lead containing 100 g of silver if 100 mL of Zn is added in (i) one lot,
and (ii) two equal lots of 50 mL. (Ans. (i) 96.77 g, (ii) 99.61 g)
 5 Phase Diagrams of One-Component
Systems

5.1 APPLICATION OF THE PHASE RULE

According to the phase rule, the degrees of freedom of a one-component system
is given by
F = C - P + 2 = 1- P + 2 = 3- P
Thus we have:
System Consisting The value of F becomes
of One Phase
F = 3 - P = 3 -1= 2
that is, the system is bivariant. Therefore, we have to state the values of two
variables in order to define the system completely. These variables are temperature
and pressure. The given component may exist in any of the three phases, namely,
solid, liquid, or vapour.
System Consisting The value of F in this case is
of Two Phases F =3-P =3-2=1
and thus stating the value of either of the two variables (temperature or pressure)
is sufficient to define the system completely. If temperature is stated then the
other variable, namely, pressure, will have a definite value and vice versa. The
two phases in equilibrium with each other may be solid-solid, solid-liquid, liquid
vapour, and solid-vapour.
System Consisting Here
of Three Phases
F =3-P =3-3=0
and thus the system is invariant, i.e. the three phases can exist in equilibrium only
at definite values of temperature and pressure. The three phases in equilibrium with
one another may be solid-liquid-vapour, solid-solid-liquid, and solid-solid-vapour.
It is obvious that for a one-component system, we cannot have more
the three phases in equilibrium as otherwise the variance of the system would
become negative.

5.2 QUALITATIVE DISCUSSION OF A PHASE DIAGRAM

Since the maximum degrees of freedom to define a one-component system are
two, its phase diagram can be drawn in two dimensions by choosing rectangular
218 A Textbook of Physical Chemistry

axes representing temperature and pressure, respectively. A complete phase

diagram of a one-component system will include the following aspects.
Representation of a A single phase will be represented over a region (or area) since the given phase
Single Phase can exist under different conditions of temperature and pressure, i.e. temperature
and pressure can both be varied independently over a range of values without
affecting the existence of the single phase. In general, the solid phase is stable
under conditions of low temperatures and high pressures, the gaseous phase at
high temperatures and low pressures, and the liquid phase in between these two
extreme conditions. Figure 5.2.1 shows the approximate regions of stability of
the three phases.

Fig. 5.2.1 Regions of

stability of the three
phases
Representation of Two phases in equilibrium will be represented on a line since for this type of
Two Phases in equilibrium, one has to state only one variable (say, temperature), the other
Equilibrium variable (say, pressure) has a definite value. Thus, if temperature is stated,
the corresponding equilibrium value of pressure can be determined from the
line and vice versa. The number of lines in a phase diagram will be equal to
the number of two-phase equilibria which the system can possess. The slope
dp/dT of these lines follows the Clapeyron equation, according to which, we
have

dp D H
= trs m (5.2.1)
dT D trsVm

where trs Hm and trsVm are the respective changes in the molar enthalpy and
the molar volume during transformation of one phase into another at the
equilibrium temperature T. In general, the slope dp/dT for solid to liquid
transformation is much steeper than those of solid to vapour and liquid to
vapour transformations, as trsVm for the fusion process is usually very small.
Since trsHm for the fusion process is positive, the sign of the slope dp/dT of
the melting point curve will depend on whether the term trsVm is positive or
 Phase Diagrams of One-Component Systems 219

negative. If the solid is denser than the liquid, as is normally the case, trsVm
is positive and the slope of the melting points curve is positive. If on the other
hand, liquid is more dense than solid, then trsVm is negative and so is the slope
of the melting point curve. If the densities of liquid and solid are identical, the
slope becomes infinite since dp/dT becomes infinite in this case. These three
cases along with the expected curves of solid to vapour and liquid to vapour
equilibria are shown in Fig. 5.2.2.

Fig. 5.2.2 A schematic

plot of three lines
representing solid to
liquid, solid to vapour
and liquid to vapour
equilibria
Representation of Three phases in equilibrium will be represented by a point since both the variables
Three Phases in (i.e. temperature and pressure) for such type of equilibrium have definite values.
Equilibrium The three lines representing solid to liquid, solid to vapour and liquid to vapour
equilibria meet one another at this point. This point is known as the triple point
of the system. In general, we have

D sub H m = D fus H m + D vap H m (5.2.2)

where the subscripts sub, fus and vap stand respectively for sublimation, fusion
and vaporization transformations. Since

D sub H m > D vap H m

it follows from the Clapeyron equation that at the triple point

Ê dp ˆ Ê dp ˆ
ÁË ˜¯ > Á ˜
Ë dT ¯ 1
(5.2.3)
dT s v v

Thus, at the triple point where the three lines representing solid to vapour, liquid
to vapour and solid to liquid equilibria meet one another, the slope of the line
representing solid to vapour transformation will be greater than that of the liquid
to vapour transformation.
220 A Textbook of Physical Chemistry

5.3 PHASE DIAGRAM OF WATER

Experimentation Let an evacuated vessel fitted with a movable piston be placed in a thermostat
whose temperature is well below 0 °C (say, – 20 °C). The position of the piston
can be held anywhere against a set of stops. Let solid water (i.e. ice) be placed
in the vessel. The behaviour of the above system at various stages of temperature
and pressure as depicted in the phase diagram of water (Fig. 5.3.1) is described
below.

Fig. 5.3.1 Phase

diagram of water
system

Solid-Vapour After some time when the system attains equilibrium, it is found that the pressure
Equilibrium within the vessel attains a constant value. This pressure is the vapour pressure
of solid water at – 20 °C. Let the point B in Fig. 5.3.1 represent the above
system of ice in equilibrium with its vapour.
Suppose that the temperature of the system represented by the point B is
raised slowly at constant volume. It is found that the vapour pressure of solid water
also increases. If a plot of vapour pressure of solid water versus temperature is
drawn, the curve BO as shown in Fig. 5.3.1 is obtained. The curve BO, known as
the sublimation curve, describes the various conditions of temperature and pressure
at which solid water and water vapour are in equilibrium with each other. The
slope of the curve at any point as given by the Clapeyron equation is

Ê dp ˆ D sub H m
ÁË ˜¯ =
dT s v T (Vm, v - Vm, s )

The variation of sublimation pressure with temperature (i.e. the curve BO

may be represented by the Clausius-Clapeyron equation:

Ê pˆ D H
ln Á ˜ = - sub m + I
Ë p∞ ¯ RT
 Phase Diagrams of One-Component Systems 221

Solid and Vapour For a given temperature, the equilibrium between solid and vapour exists only at
Phases a specific vapour pressure which can be determined from the curve BO. Now
suppose the volume of the vessel representing system at point B is increased
isothermally by moving the piston in the outward direction. This, in turn will
decrease the pressure of the vapour phase. Since at a given temperature vapour
pressure of solid water has a fixed value, a little bit of ice will sublime to keep
the vapour pressure to a constant value. If the above process of expansion at
constant temperature is continued, more and more of ice sublimes till the entire
solid phase disappears. At this stage, the system contains only the gaseous phase.
The expansion of the latter merely causes a decrease in its pressure.
If the volume of system at point B is decreased isothermally, it will cause
an increase in the pressure of the vapour phase. In order to keep the vapour
pressure to a constant value, a little of vapour will condense to give solid water.
If the above process of compressing the vapour phase is continued, eventually
a stage is reached where the entire vapour phase is condensed and the system
contains only the solid phase. The piston of the vessel will be directly in contact
with the solid phase. The pressure on the solid phase can be increased by putting
weights on the piston.
Thus, it may be concluded that the effect of isothermal increase and
decrease of pressure on the solid-vapour equilibrium is to convert the two-phase
equilibrium to that of one phase comprising of solid and vapour, respectively.
Hence, regions above and below the curve BO represent solid and vapour
phases, respectively.
Melting of Solid If the temperature of the system at point B is slowly increased at constant
Phase (Triple Point) volume, eventually a temperature is reached where the vapour pressure of solid
water becomes equal to that of liquid water maintained at the same temperature.
At this stage, solid water starts melting and the system contains three phases,
viz., solid, liquid and vapour, in equilibrium with one another. According to
the phase rule, as described earlier, the system now becomes invariant, i.e. so
long as the three phases remain intact, the temperature and vapour pressure of
system remain constant. The point O in Fig. 5.3.1 represents such a situation
and is known as triple point. For water, this point lies at 0.007 5 °C and
4.6 mmHg†.
Liquid-Vapour If the system at the triple point is slowly heated at constant volume, its temperature
Equilibrium and vapour pressure do not change unless whole of solid is melted to give liquid. At
this stage, the system contains two phases, viz., liquid and vapour, in equilibrium
with each other. If now the system is gradually heated at constant volume, the
temperature and the vapour pressure of the system change along the curve OA.

†
Note that the pressure 4.6 mmHg is the vapour pressure of solid or liquid at temperature
0.007 5 °C. Since the effect of external pressure on the vapour pressure of solid-liquid
equilibrium is very small, the normal melting point of a substance is very near to its
triple point and, for all practical purposes, the triple point of a substance may be referred
to as its melting point.
222 A Textbook of Physical Chemistry

The curve OA, known as the vaporization curve, represents the various conditions
of temperature and pressure at which liquid and vapour are present in equilibrium
with each other. The slope of the line OA at any point is given by the Clapeyron
equation, such that

Ê dp ˆ D vap H m
ÁË ˜¯ =
dT 1 v T (Vm, v - Vm,1 )

The variation of vapour pressure of liquid phase with temperature (i.e. the
curve OA) may be represented by the Clausius-Clapeyron equation:

Ê pˆ D vap H m
ln Á ˜ = - +I
Ë p∞ ¯ RT

where I is the constant of integration. The curve OA has an upper limit at

point A which represents the critical temperature of water. In accordance with
Eq. (5.2.3), the slope of the line BO (representing solid vapour) at the triple
point is larger than that of line OA (representing liquid vapour).
Liquid and Vapour For a given temperature, the equilibrium between liquid and vapour will exist
Phases only at a specific vapour pressure which can be determined from the curve OA.
Now if the volume of a system anywhere on the line OA is increased at
constant temperature by moving the piston in the outward direction, it will
cause a decrease in the pressure of vapour phase. Since at a given temperature
vapour pressure of liquid water has a fixed value, a little bit of water will
evaporate to keep the vapour pressure to a constant value. If the above process
of expansion is continued, more and more of liquid water evaporates till the
entire liquid phase disappears. At this stage, the system contains only the
gaseous phase. The expansion of the latter merely causes a decrease in its
pressure. Similarly, if the volume of the system is gradually decreased, more
and more of vapour is condensed in order to keep the vapour pressure of liquid
water to a constant value. If the compression is continued, eventually a stage
is reached where the entire vapour phase is condensed and the system contains
only liquid phase. The piston of the vessel will be directly in contact with the
liquid phase. The pressure on the liquid phase can be increased by applying
more pressure on the piston.
Thus, it may be concluded that the regions above and below the curve
OA represent liquid and vapour phases, respectively.
Solid-Liquid If the system containing only solid phase at some high pressure is gradually
Equilibrium heated, its temperature rises till a stage is reached where it starts melting. At
this stage, temperature of the system remains constant till whole of the solid
phase is converted into the liquid phase. The temperature at which solid melts
depends on the pressure on the solid phase. The line OC in Fig. 5.3.1 represents
the various conditions of temperature and pressure at which solid and liquid are
in equilibrium with each other. The slope of this line follows the Clapeyron
equation, such that
 Phase Diagrams of One-Component Systems 223

Ê dp ˆ D fus H m
ÁË ˜¯ =
dT s 1 T (Vm,1 - Vm, s )

Since Vm,1 – Vm,s is small, the slope of the line OC has a comparatively high
value. Consequently, the line OC is nearly vertical. Since for water, Vm,s > Vm,1
the slope dp/dT is negative and hence the line OC is slightly titled towards the left.
Metastable If the system on the line AO is rapidly cooled, it may happen that ice fails to
Equilibrium appear at the triple point and the vapour pressure of liquid continues to move
along OA which now represents metastable equilibrium involving liquid and
vapour phases. Similarly, if the system on the line BO is rapidly heated, liquid
may not appear at the triple point and the vapour pressure of solid continues
along the continuation of the curve BO where metastable equilibrium between
solid and vapour phases exists.
Comparison of Since at the triple point, the slope of the solid-vapour curve is greater than that
Vapour Pressure of of the liquid-vapour curve, the continuation of each of these curves beyond the
Stable and triple point places them above the curve for the stable phase in that temperature
Metastable Phases interval. Consequently, the vapour pressure of the system in the metastable
region is greater than that in the stable system at the same temperature. This
generalization can also be derived thermodynamically as follows.
Since the transformation
Metastable phase Stable phase
is a spontaneous process, we must have
DG = ms - mms = - ve
where μs and μms are the chemical potentials of stable and metastable phases,
respectively. Since in both stable and metastable regions, the substance is in
equilibrium with its vapour, we will have

ms = m vs = m v∞ + RT ln ps

mms = m vm = m v∞ + RT ln pms

where μvs and μvm are the chemical potentials of the vapour phase in stable and
metastable regions, respectively. Hence
ps
DG = ms - mms = RT ln (5.3.1)
pms

Since G is negative, it follows that

pms > ps
that is, the vapour pressure of metastable phase is larger than that of the stable
phase at the same temperature.
Labelling of the Table 5.3.1 describes, in brief, the phase diagram of water (Fig. 5.3.1) in the
Phase Diagram light of above analysis.
224 A Textbook of Physical Chemistry

Table 5.3.1 Description of the Phase Diagram of Water (Fig. 5.3.1)

Location of the system Status of the system Degrees of freedom

Number Kind
BO Sublimation curve 1 T or p
O Triple point where
solid liquid vapour 0
OA Vaporization curve 1 T or p
OC Fusion curve 1 T or p
Area above AO and to the
right of OC Liquid phase 2 T and p
Area above OB and to the
left of OC Solid phase 2 T and p
Area, below the curve AOB Vapour phase 2 T and p
OA Metastable equilibrium
liquid vaour 1 T or p

Example 5.3.1 Suppose solid water-liquid water equilibrium is maintained at triple point temperature
(0.007 5 ºC) and triple point pressure (4.6 mmHg). Calculate how much change in
temperature be made so that the equilibrium is maintained at an external pressure of 1 atm.
Given: ρ (ice) = 0.917 g cm–3, ρ(liquid) = 0.999 87 g cm–3 and fusHm = 6 008.5 J mol–1.
Solution The temperature at which solid-liquid equilibrium is maintained, when the external
pressure is raised from 4.6 mmHg to 1 atm, can be calculated by using the Clapeyron
equation:
dp D fus H m
=
dT T (Vm,1 - Vm,s )
18 g mol -1 18 g mol -1
Now Vm,1 - Vm,s = -3
-
0.999 87 g cm 0.917 g cm -3
= 18.002 cm3 mol -1 - 19.629 cm3 mol -1
= - 1.627 cm 3 mol -1 = - 1.627 ¥ 10 -6 m 3 mol -1
dp 6 008.5 J mol -1
Thus = = - 1.352 ¥ 107 Pa K -1
dT (273.15 K) ( - 1.627 ¥ 10 -6 m 3 mol -1 )
dp
or dT = -
1.352 ¥ 107 Pa K -1

Now dp = 760 mmHg - 4.6 mmHg = 755.4 mmHg

Ê 755.4 ˆ
=Ë ¥ 101.325 ¥ 103 Pa¯ = 1.0
007 ¥ 105 Pa
760
1.007 ¥ 105 Pa
Hence, dT = - = - 0.007 5 K ∫ - 0.007 5 ∞C
1.352 ¥ 107 Pa K -1
Thus, ice will melt at 0 ºC (triple point temperature 0.007 5 °C) when the external
pressure on it is 1 atm. This external pressure may be due to the atmospheric pressure.
Thus, the normal melting point of ice is 0 ºC.
 Phase Diagrams of One-Component Systems 225

Example 5.3.2 Suppose liquid water-water vapour equilibrium is maintained at triple point temperature
and atmospheric pressure of 1 atm. Calculate the vapour pressure of water. Given: Triple
point pressure = 4.6 mmHg.
Solution In the absence of atmospheric gases, the vapour pressure of liquid water ( p*) would
have been 4.6 mmHg. In the presence of air at atmospheric pressure (P2), the vapour
pressure of liquid water (p2) can be calculated by using the expression

p
RT ln = Vm,1 (P2 - p*) (1)
p*
The molar volume of liquid water is

M 18 g mol -1
Vm,1 = = = 18 cm 3 mol -1 = 18 ¥ 10 -6 m 3 mol -1
r 1 g cm -3

The value of p* is

Ê 4.6 mmHg ˆ
p* = Á (101 325 Pa) = 613.28 Pa
Ë 760 mmHg ˜¯

Substituting the values of Vm,1 and p* in Eq. (1), we get

Ê p2 ˆ
(8.314 J K –1 mol –1 ) (273.15 K) ln Á
Ë 4.6 mmHg ˜¯
= (18 ¥ 10 –6 m 3 mol –1 ) (101 325 Pa – 613.28 Pa)

Ê p2 ˆ (18 ¥ 10 -6 ) (100 712)

or ln Á ˜ = = 7.98 ¥ 10 -4
Ë 4.6 mmHg ¯ (8.314) (273.15)

p2
or = 1.0008 or p2 = 4.604 mmHg
4.6 mmHg

5.4 POLYMORPHISM
Sometimes a substance can exist in more than one crystalline form and each form
has its own characteristic vapour pressure curve. Such type of substances are
said to exhibit the phenomenon of polymorphism. Two types of polymorphism
are observed depending upon whether the change from one polymorphic form
to the other can be carried out in either direction or only in one direction. The
former is known as enantiotropy (Greek: opposite change) and the latter as
monotropy (Greek: one change).

ENANTIOTROPY
Two crystalline forms can be interconvertible and this conversion takes place
at a definite temperature for a given external pressure. This temperature is the
transition point and it is the only temperature at which the two solids can
coexist in equilibrium at a given pressure. If the temperature of the system is
greater than this temperature, there occurs a complete transformation of one form
into the other, one being stable below the transition point and the other above
226 A Textbook of Physical Chemistry

it. Suppose, the two enantiotropic modifications are represented by and ,

then we have;
i t >t
α �
����
��� � β
�
t < ti

where -form is stable at lower temperatures while -form is stable at higher

temperatures.
Each polymorphic form has its own vapour pressure curve. The two
vapour pressure curves meet each other at a common point as shown in Fig.
5.4.1. The curve AB is vapour pressure curve of the -form and BC is that of
the -form. The curve AB comes before the curve BC as -form is stable at
lower temperatures. The point B is the intersection point and is the transition
point where both - and -forms are at equilibrium with the vapour. Thus, if
-form is heated very slowly so that the equilibrium between solid and vapour
is always established, the vapour pressure of the system will rise along the curve
AB. When the point B is reached, the -form is transformed into the -form
without any increase in temperature and vapour pressure. Heat supplied to the
system is utilized in carrying out the transformation from the -form to the
form. Once the transformation is complete, the vapour pressure of the system
changes along the curve BC.

Fig. 5.4.1 The

phenomenon of
enantiotropy

Since at the triple point,

D sub H m (solid α ) = D trs H m (solid α - solid β) + D sub H m (solid β)

it follows that
D sub H m (solid α) > D sub H m (solid β)
A direct consequence of the above relation is that the slope of solid
-vapour curve at the triple point is greater than that of solid -vapour curve.
 Phase Diagrams of One-Component Systems 227

Consequently, the metastable extensions of the solid -vapour and the solid
-vapour curves obey Eq. (5.3.1), according to which, the vapour pressure of
component in the metastable form is larger than that in the stable form at same
temperature.
Point C is the melting point of the -form and thus the curve CD is the
vaporization curve. If the heating of the -form is not done slowly, it may be
observed that at B no -form is formed and the vapour pressure of the system
continues along BE. Along this line, we have metastable equilibrium between
-form and its vapour. Similarly, if the liquid is cooled rapidly, then it may be
observed that at C no -form separates and the cooling of the liquid continues
along the line CE, which now represents a metastable equilibrium between
liquid and vapour. The two metastable curves meet each other at the point E,
which represents the melting point of -form.
Examples of substances exhibiting enantiotropy are sulphur, tin, ammonium
nitrate, mercury iodide, carbon tetrachloride, and solid water(ice).

Phase Diagram of Sulphur

Sulphur exists in two enantiotropic forms, namely, rhombic and monoclinic;
the former being stable at lower temperatures. To describe the phase diagram
shown in Fig. 5.4.2, we start with rhombic sulphur placed in an evacuated vessel
maintained at some low temperature. The behaviour of the system at various
stages of temperature and pressure is described below.

Fig. 5.4.2 Phase

diagram of sulphur
228 A Textbook of Physical Chemistry

Rhombic Sulphur- After some time when the system attains equilibrium, the vapour pressure will
Vapour Equilibrium attain a fixed value. Let the point A in Fig. 5.4.2 represent this state of the
system.
Now suppose, the temperature of the system represented by the point A
is raised at constant volume. The vapour pressure of rhombic sulphur is also
increased. If a plot of vapour pressure versus temperature is drawn, we get the
curve AB as shown in Fig. 5.4.2. The curve AB, known as sublimation curve
of rhombic sulphur, describes the various conditions of temperature and pressure
at which rhombic sulphur exists in equilibrium with its vapour.
If a system on the curve AB is subjected to isothermal expansion, more
and more of solid sulphur is converted into sulphur vapour to keep the vapour
pressure of rhombic sulphur to a constant value. Continued expansion will
ultimately lead to the vapour phase only. Similarly, if the original system is
subjected to isothermal compression, more and more of vapour phase is
condensed to give rhombic sulphur. Continued compression will ultimately lead
to only rhombic sulphur. Hence, the phases above and below the curve AB
comprise of solid rhombic sulphur and vapour sulphur, respectively.
Monoclinic Sulphur- If a system on AB is gradually heated at constant volume, eventually a stage is
Vapour Equilibrium reached where the vapour pressure of rhombic sulphur becomes equal to
that of monoclinic sulphur. Consequently, rhombic sulphur starts converting
into monoclinic sulphur and the system contains three phases, viz., rhombic,
monoclinic and vapour, in equilibrium with one another. According to the phase
rule, the system becomes invariant (F = C + 2 – P = 1 + 2 – 3 = 0) and thus
temperature and vapour pressure of the system remain constant so long as three
phases remain intact. The point B in Fig. 5.4.2 represents such a situation which
lies at 95.5 °C and 0.01 Torr.
If the system at point B is slowly heated at constant volume, its temperature
and pressure do not change unless whole of rhombic sulphur is converted into
monoclinic sulphur. At the latter stage, the system contains two phases, viz.,
monoclinic sulphur and vapour, in equilibrium with each other and thus the
system becomes univariant (F = C + 2 – P = 1 + 2 – 2 = 1). If the heating is
continued at constant volume, the temperature and vapour pressure of monoclinic
sulphur change along the curve BC.
The slopes of curves AB and BC at point B are
Ê dp ˆ D sub H m, rhom
ÁË ˜¯ =
dT rhom v T (Vm, v – Vm, rhom )

Ê dp ˆ D sub H m, mono
ÁË ˜¯ =
dT mono v T (Vm, v – Vm, mono )

Now since subHm, rhom = trsHm, rhom mono + subHm, mono, it follows that
D sub H m, rhom > D sub H m, mono
Ê dp ˆ Ê dp ˆ
Hence ÁË ˜¯ > Á ˜
Ë dT ¯ mono
dT rhom v v
that is, the slope of the curve AB at point B is larger than that of the curve BC.
 Phase Diagrams of One-Component Systems 229

If a system on the curve BC is subjected to isothermal expansion and

compression, it will eventually be converted into the system of one phase
comprising of vapour and monoclinic sulphur, respectively. Thus, the system
above and below the curve BC consists of solid monoclinic sulphur and vapour
sulphur, respectively.
Liquid-Vapour At point C, the vapour pressure of monoclinic sulphur becomes equal to that of
Equilibrium liquid sulphur. Consequently, at this point three phases, viz., monoclinic sulphur,
liquid sulphur and vapour sulphur, exist in equilibrium with one another. This
point lies at 119.2 °C and 0.025 Torr.
If the system at the point C is heated gradually at constant volume, more
and more of monoclinic sulphur converts into liquid sulphur. The temperature and
vapour pressure of the system remain constant until whole of solid monoclinic
sulphur is converted into liquid sulphur. If the heating is continued, the temperature
and vapour pressure of liquid sulphur move along the curve CD.
At point C, the slope of the curve BC is larger than that of the curve CD.
This is in accordance with Eq. (5.2.3).
If a system on the curve CD is subjected to isothermal expansion and
compression, it would eventually lead to a system of one phase comprising vapour
(below the curve CD) and liquid sulphur (above the curve CD), respectively.
Rhombic-Monoclinic If a system of solid rhombic sulphur at some high pressure is heated slowly, its
Sulphur in temperature increases till a stage is reached where it starts converting into
Equilibrium monoclinic sulphur. At this stage, temperature of the system remains constant
until whole of rhombic sulphur is converted into monoclinic sulphur. The
temperature at which this transition takes place depends on the pressure of the
system. The line BE in Fig. 5.4.2 represents the various conditions of temperature
and pressure at which the above transition takes place. The slope of this line
is positive since monoclinic sulphur is less dense than rhombic sulphur. On the
left of the line BE, rhombic sulphur exists whereas to its right only monoclinic
sulphur exists.
Monoclinic Sulphur- If the heating of monoclinic sulphur is continued, a stage is reached where it
Liquid in starts melting. This happens when the state point moves on the line CE. The
Equilibrium temperature of the system remains constant until whole of monoclinic sulphur
melts to give liquid sulphur. Thus, on the left and right of the line CE, the
system consists of monoclinic sulphur and liquid sulphur, respectively.
The slope of the line CE is larger than that of BE. Consequently, these two
lines meet each other at point E, which represents a triple point where rhombic,
monoclinic and liquid sulphur are in equilibrium with one another. This point
lies at 151°C and 1 290 atm.
Rhombic Sulphur- If the pressure of the system is higher than the triple point pressure at point E.
Liquid Phases then rhombic sulphur passes directly into liquid sulphur along the line EF.
Metastable If a system on the line AB is heated rapidly, it may happen that monoclinic
Equilibria sulphur does not appear at point B but the vapour pressure of the system continues
along the line BG, which now represents metastable equilibrium between rhombic
sulphur and vapour. Similarly, if a system on DC is cooled rapidly, monoclinic
230 A Textbook of Physical Chemistry

sulphur might not appear at point C and the system continues to move along
CG, which represents metastable equilibrium between liquid sulphur and vapour.
The point G where the curves BG and CG meet each other is another triple point
(metastable) where rhombic, liquid and vapour sulphur are in equilibrium with
one another. This point lies at 114.5 °C and 0.03 Torr.
Similarly, if a system of rhombic sulphur at some high pressure is heated
rapidly, transition to monoclinic sulphur might not occur on the line BE but
the system might pass over directly to liquid phase. The line GE in Fig. 5.4.2
represents such a type of metastable equilibrium.
It may be pointed out here that the stable and metastable transitions are
to be discussed separately. For example, to the left and right of the metastable
equilibrium line GE, rhombic and liquid sulphur exist whereas these regions
actually are of monoclinic sulphur. The equilibrium involving rhombic and
liquid sulphur will exist provided either rhombic sulphur does not pass over to
monoclinic sulphur on the line BE or liquid sulphur does not pass over to the
monoclinic sulphur on the line CE. If these stable transitions are observed, then
the metastable transition involving rhombic to liquid sulphur will not have any
existence. Metastable phases to the left and right of the line GE will have a
tendency to pass spontaneously over to the stable phase, i.e. monoclinic sulphur.
Labelling of the Table 5.4.1 describes, in brief, the phase diagram of sulphur (Fig. 5.4.2) in the
Phase Diagram light of the above analysis.
MONOTROPY
In the phenomenon of monotropy, one of the crystalline forms is stable while
the other one is metastable over the whole range of its existence. In this case,
transformation from one form into another can take place only in one direction;
from metastable to stable form. The vapour pressure curve for the metastable
form lies above that of the stable form as shown in Fig. 5.4.3. The curve AB is

Fig. 5.4.3 The

phenomenon of
monotropy
 Phase Diagrams of One-Component Systems 231

Table 5.4.1 Description of the Phase Diagram of Sulphur (Fig. 5.4.2)

Location of Status of the system Degrees of

the system freedom

AB Sublimation curve of rhombic sulphur 1

B Triple point where 0
Ê rhombicˆ ��� Ê monoclinicˆ ��� Ê vapour ˆ
Ë sulphur ¯ ��� Ë sulphur ¯ ��� Ë sulphur ¯
BC Sublimation curve of monoclinic sulphur 1
C Triple point where 0
Ê monoclinicˆ ��� Ê liquid ˆ ��� Ê vapour ˆ
Ë sulphur ¯ ��� Ë sulphur ¯ ��� Ë sulphur ¯
CD Vaporization curve of liquid sulphur 1
BE Transition line of rhombic sulphur to
monoclinic sulphur 1
CE Fusion line of monoclinic sulphur to
liquid sulphur 1
E Triple point where 0
Ê rhombicˆ ��� Ê monoclinicˆ ��� Ê liquid ˆ
Ë sulphur ¯ ��� Ë sulphur ¯ ��� Ë sulphur ¯
EF Fusion line of rhombic sulphur to liquid sulphur 1
BG Metastable sublimative curve of
rhombic sulphur 1
CG Metastable varporization curve of
liquid sulphur 1
G Metastable triple point where 0
Ê rhombicˆ ��� Ê liquid ˆ ��� Ê vapour ˆ
Ë sulphur ¯ ��� Ë sulphur ¯ ��� Ë sulphur¯
GE Metastable fusion line of rhombic
sulphur to liquid sulphur 1
Area to the left Rhombic sulphur 2
of ABF
Area above CD Liquid sulphur 2
and to the right
of CEF
Area BCEB Monoclinic sulphur 2
Area below ABCD Vapour sulphur 2
Area BGEB Metastable rhombic sulphur 2
Area CGEC Metastable liquid sulphur 2

the vapour pressure curve of the stable -form and the curve CD is that of the
metastable -form. BE is the vaporization curve. The point B is the stable triple
point where we have
-form liquid vapour
The point D is the melting point of the -form which can be obtained by extending
the line EB up to the point D where it meets the curve CD. The system will have
a hypothetical transition temperature which can be obtained by extending the
232 A Textbook of Physical Chemistry

lines AB and CD up to the point F where the two curves meet each other. The
hypothetical transition temperature F has no real existence as it is above the melting
points of the two modifications and the two solids do not exist.
In fact, points D and F are the metastable triple points which respectively
represent
solid liquid vapour
and solid solid vapour
Since the effect of pressure on the melting point and the transition point
is usually very small, the two points D and F may be referred to as the melting
point and the transition point, respectively. Similarly the point B may be referred
to as the melting point of the -form.
Since the -form has higher vapour pressure, it is metastable with respect
to -form and thus -form will pass over to the -form and the reverse of this
process (i.e. -form to -form) will not take place. The -form, however, can be
obtained from the -form by an indirect method. First of all, it may be heated
to get a liquid and then cooling the liquid rapidly will move the system along
the line BD instead of BA and at D, the -form will separate.
Examples of substances exhibiting monotropy are phosphorus, silica, iodine
monochloride and benzophenone.
Example Exhibiting Some substances show both enantiotropy and monotropy. A typical example
both Monotropy which exhibits this behaviour is phosphorus, where we have
and Enantiotropy Monotropy transition White P(both - and -forms) Violet P
Enantiotropic transition White P( -form) White P( -form)
Phase Diagram of Phosphorus
The phase diagram of phosphorus is shown in Fig. 5.4.4. Its description is given
in Table 5.4.2. The vapour pressure curves of unstable phases are shown by
dotted lines.

Fig. 5.4.4 Phase

diagram of phosphorus
 Phase Diagrams of One-Component Systems 233

Table 5.4.2 Description of the Phase Diagram Shown in Fig. 5.4.4.

Location of Status of the System

the system
AO Sublimation curve of stable solid violet phosphorus
OB Vaporization curve of liquid phosphorus
OJ Fusion point curve of violet phosphorus
O Triple point where
solid violet P liquid P vapour P
OCI metastable vaporization curve of liquid phosphorus
DE Sublimation curve of unstable white ( -form) phosphorus
EC Sublimation curve of unstable white ( -form) phosphorus
EF Enantiotropic transition point curve involving unstable white
P( -form) and unstable white P( -form)
CG Fusion point curve of unstable white P( -form)
C Metastable triple point where
solid white P( -from) liquid P vapour P
E Metastable triple point, where
solid white P( -form) solid white P( -form) vapour P
EI Metastable sublimation curve of white P( -form)
I Metastable triple point, where
solid white P( -form) liquid P vapour P
IH Metastable fusion point curve of white P( -form)

Example 5.4.1 Element X exists in three solid allotropic modifications, known respectively, as 1, 2 and
3. In the vicinity of the 1-2-3 triple point,

Sm, 2 > Sm, 3 > Sm, 1 and Vm, 3 > Vm, 1 > Vm, 2

where S and V stand for entropy and volume, respectively. Sketch an arrangement of the
three two-phase equilibrium lines around the 1-2-3 triple point on a pressure-temperature
diagram consistent with the given information. Label all the lines and areas.

Solution From the given information, we have

Ê dp ˆ Ê DS ˆ Sm, 2 - Sm, 1 +ve

ÁË ˜¯ = Á m˜ = = = - ve
dT 1 2 Ë DVm ¯ 1 2
Vm, 2 - Vm, 1 - ve

Ê dp ˆ Ê DS ˆ Sm, 3 - Sm, 1 +ve

ÁË ˜¯ = Á m˜ = = = + ve
dT 1 3 Ë DVm ¯ 1 3
Vm, 3 - Vm, 1 +ve

Ê dp ˆ Ê DS ˆ Sm, 3 - Sm, 2 - ve
ÁË ˜¯ = Á m˜ = = = - ve
dT 2 3 Ë DVm ¯ 2 3
Vm, 3 - Vm, 2 +ve

The possible phase diagram (along with other information) consistent with the information
is given in Fig. 5.4.5
234 A Textbook of Physical Chemistry

Fig. 5.4.5

Example 5.4.2 A certain substance exists in two solid modifications, and , as well as liquid and vapour.
Under a pressure of one atmosphere, is more stable at lower temperatures than , which
melts at a still higher temperature to form the liquid, is denser than the liquid, but is
less dense than the liquid. No metastable equilibria are observed. Sketch the pressure-
temperature phase diagram indicating the significance of each point, line and region. Include
in your diagram every triple point that can be observed.

Solution We are given that

(i) is stable at lower temperatures
(ii) is stable at higher temperatures and also that it melts at some higher temperature
(iii) ρ > ρ1 or Vm, < Vm, 1
(iv) ρ < ρ1 or Vm, > Vm, 1
(v) No metastable equilibria.
Taking points (iii) and (iv) together, we have
ρ > ρ1 > ρ or Vm, < Vm, 1 < Vm,

Since higher temperature favours the form with the greater enthalpy, we must have
Hm, 1 > Hm, > Hm,
Now, we have

Ê dp ˆ Ê DH m ˆ H m, b – H m, a +ve
ÁË ˜¯ = Á = = = +ve
dT a b Ë T DVm ˜¯ a b
T (Vm, b – Vm, a ) +ve

Ê dp ˆ Ê DH m ˆ H m, 1 – H m, a +ve
ÁË ˜¯ = Á = = = +ve
dT a 1 Ë T DVm ˜¯ a 1
T (Vm, 1 – Vm, a ) +ve

Ê dp ˆ Ê DHHm ˆ H m, 1 – H m, b +ve
ÁË ˜¯ = Á = = = –vve
dT b 1 Ë T DVm ˜¯ b 1
T (Vm, 1 – Vm, b ) – ve

The phase diagram consistent with the above information is given in Fig. 5.4.6.
 Phase Diagrams of One-Component Systems 235

Fig. 5.4.6

Description of the The description of various lines, points and regions of Fig. 5.4.6 is given below.
Diagram
(i) Curve AB: -form vapour.
(ii) Curve BC: -form vapour.
(iii) Point B: Triple point where v.
(iv) Point C: Triple point where 1 v.
(v) Curve CD: Liquid vapour.
(vi) Curve BE: .
(vii) Curve CE: 1.
(viii) Point E: Triple point where 1.
(ix) Curve EF: 1.

Example 5.4.3 Show that on the basis of slope sign there are 8 and only 8 possible unique configurations
of the two-phase lines around a triple point in a one-component pressure-temperature
diagram. Draw the sketch also.

Solution The slope of each line may be positive or negative. Labelling the three phases as 1, 2,
and 3, the possible permutations of the signs of lines representing two phases in
equilibrium are given below.

(I) (II) (III) (IV) (V) (VI) (VII) (VIII)

1-2 equilibrium line + + + + – – – –
2-3 equilibrium line + + – – + + – –
1-3 equilibrium line + – + – + – + –

Thus there are, in all, eight possible configurations around the triple point. The corresponding
diagrams are shown in Fig. 5.4.7.
236 A Textbook of Physical Chemistry

Fig. 5.4.7

Example 5.4.4 A substance S has a low-pressure form, S , which melts at about 17 ºC under its own
pressure of about 8 mmHg. It has also a high-pressure form, S , and the phases S , S
and liquid are in equilibrium at about 55 ºC under a pressure of 2 000 atm. The -form
is denser than the -form, but both are denser than the liquid. Draw the phase diagram.
Solution We are given that
(i) Two allotropic form: S is stable at lower pressures, and S is stable at higher
pressures.
(ii) Melting pint of S is 17 ºC at the pressure of 8 mmHg.
(iii) S S S1 at 55 ºC and 2 000 atm.
(iv) ρ > ρ .
(v) ρ > ρ1 and ρ > ρ1.
 Phase Diagrams of One-Component Systems 237

Since higher temperature favours the form with greater enthalpy, we must have
Hm, < Hm, < Hm, 1
Taking point (iv) and (v) together, we have
ρ > ρ > ρ1 or Vm, < Vm, < Vm, 1
Now, we have

Ê dp ˆ Ê DH m ˆ H m, b – H m, a +ve
ÁË ˜¯ = Á = = = –ve
dT a b Ë T DVm ˜¯ a b
T (Vm, b – Vm, a ) – ve

Ê dp ˆ Ê DH m ˆ H m, 1 – H m, a +ve
ÁË ˜¯ = Á = = = +ve
dT a 1 Ë T DVm ˜¯ a 1
T (Vm, 1 – Vm, a ) +ve

Ê dp ˆ Ê DHHm ˆ H m, 1 – H m, b +ve
ÁË ˜¯ = Á = = = +ve
dT b 1 Ë T DVm ˜¯ b 1
T (Vm, 1 – Vm, b ) +ve

The phase diagram consistent with the given information is shown in Fig. 5.4.8.

Fig. 5.4.8

The point B is at 17 ºC and 8 mmHg where S S1 Sv. The point D is at

55 ºC and 2 000 atm where S = S = S1.

Example 5.4.5 From the following data, sketch the phase diagram of N2 at low temperatures.
There are three crystal forms , , and which coexist at 4 650 atm and 44.5 K.
At this triple point, the volume changes ( V ) are
0.165 cm3 mol–1
0.208 cm3 mol–1
0.043 cm3 mol–1
At 1 atm and 36 K, has V = 0.22 cm3 mol–1. The S values for the transition
cited are 1.25, 5.88, 4.59 and 6.52 J K–1 mol–1, respectively.
238 A Textbook of Physical Chemistry

Solution We have

dp DS
Transition V/cm3 mol–1 S/J K–1 mol–1 = μ
dT DV
1.25
0.165 1.25 = 7.58
0.165
5.88
0.208 5.88 = 28.27
0.208
4.59
0.043 4.59 = 106.74
0.043
6.52
0.22 6.52 = 29.64
at 1 atm 0.22
and 36 K

The schematic phase diagram consistent with the above information is shown in
Fig. 5.4.9.

Example 5.4.6 Substance A exists in two allotropic forms: white and red. White A melts at 44 °C and
0.2 mmHg. Red A melts at 490 °C and 43 atm pressure. White A is more dense than
the liquid and the red form is less dense than the liquid. The vapour pressure of white
form is everywhere greater than that of red. Sketch p versus T diagram, label the areas
and explain the stable and unstable triple points.

Solution From the given data, we conclude

Fig. 5.4.9 (i) Melting point of white A: 44 °C at 0.2 mmHg.
(ii) Melting point of red A: 490 °C at 43 atm.
(iii) Vapour pressure of white A > Vapour pressure of red A. This indicates that white
A is unstable with respect to red A.
(iv) ρwhite A > ρ1 or Vm, white A < Vm, 1
Therefore

Ê dp ˆ D fus H m +ve
ÁË ˜¯ = = = +ve
dT white A 1 T (Vm, 1 - Vm, white A ) +ve
 Phase Diagrams of One-Component Systems 239

(v) ρred A < ρ1 or Vm, red A > Vm, 1

Therefore

Ê dp ˆ D fus H m +ve
ÁË ˜¯ = = = - ve
dT red A 1 T (Vm, 1 - Vm, red A ) - ve

(vi) Since ρwhite A > ρ1 and ρ1 > ρred A, it is obvious that

rwhite A > rred A or Vm, white A < Vm, red A

Ê dp ˆ D trs H m +ve
ÁË ˜¯ = = = +ve
dT white A red A T (Vm, red A - Vm, white A ) +ve

The phase diagram consistent with the above information is given in Fig. 5.4.10.

Fig. 5.4.10 The required

phase diagram. The
symbols w, r, 1 and v
stand for white, red,
liquid and vapour,
respectively

Example 5.4.7 A substance X exists in two crystalline modifications, here called A and B. At temperature
below 90 °C, the vapour pressure of the A-form is less than that of the B-form, and above
90 °C, the reverse is true. The A-form is 5% denser than liquid X and the B-form is 10% less
dense than the A-form. There is an A-l-v triple point at 110 °C. Sketch the p-T diagram for X.

Solution From the given data, we conclude

(i) Since A-form is 5% denser than liquid X, we have

rA = 1.05r1 fi Vm, A < Vm, 1

Therefore

Ê dp ˆ D fus H m +ve
ÁË ˜¯ = = = +ve
dT A 1 T (Vm, 1 - Vm, A ) +ve
240 A Textbook of Physical Chemistry

(ii) Since B-form is 10% less dense than the A-form, we have
ρB = 0.9ρA
or ρB = 0.9 × (1.05 ρ1) = 0.945 ρ1
Hence Vm, B > Vm, 1
and thus

Ê dp ˆ D fus H m +ve
ÁË ˜¯ = = = - ve
dT B 1 T (Vm, 1 - Vm, B ) - ve

(iii) At temperature below 90 °C, the vapour pressure of A-form is less than that of
B-form, It implies that the A-form is stable whereas B-form is unstable at temperatures
below 90 °C. On the other hand, the vapour pressure of B-form is smaller than that of
A-form at temperature above 90 °C implies that the B-form is stable. Thus, 90 °C is the
transition point of A-form to B-form. It also follows that the molar enthalpy of B-form
is greater than that of A-form.
(iv) Since ρB = 0.9 ρA, we have
Vm, B > Vm, A
and hence

Ê dp ˆ D trs H m +ve
ÁË ˜¯ = = = +ve
dT A B T (Vm, B - Vm, A ) +ve

(v) The triple point A 1 v exists at 110 °C.

The phase diagram consistent with the above information is shown in Fig. 5.4.11.

Fig. 5.4.11
 Phase Diagrams of One-Component Systems 241

REVISIONARY PROBLEMS

5.1 (a) Determine the variance of a one-component system having number of phases
equal to one, two and three, respectively.
(b) Show that it is not possible to have more than three phases in equilibrium with
each other in a one-component system.
(c) Show how are the following systems represented in a one-component phase
diagram:
(i) System consisting of only one phase.
(ii) System consisting of two phases in equilibrium.
(iii) System consisting of three phases in equilibrium.
5.2 Describe the phase diagram of water with due emphasis on the following facts:
(i) How many triple points does it have?
(ii) Why is the solid-vapour line more steep than the liquid-vapour line at the triple
point?
(iii) Why is the solid-liquid line almost vertical and slightly tilted to the left?
(iv) What is the upper limit of the liquid-vapour equilibrium line?
5.3 Illustrate with examples the meaning of the terms polymorphism, enantiotropy and
monotropy. Describe the type of phase diagram that is expected for the phenomena
of enantiotropy and monotropy.
5.4 (a) Describe the phase diagram of sulphur which exhibits the phenomenon of
enantiotropy. How many triple points are possible in this phase diagram?
(b) The equilibrium line of rhombic sulphur monoclinic sulphur is slightly tilted
to the right. Predict which enantiotropic form is more dense.
(c) The slope of lines representing rhombic sulphur monoclinic sulphur and
monoclinic sulphur liquid sulphur are positive. Predict the slope of the line
representing metastable equilibrium of rhombic sulphur liquid.
5.5 Describe briefly the phase diagram of phosphorus—an example which exhibit both
monotropy as well as enantiotropy.
5.6 Starting from the fact that G of the process
metastable form stable form
is negative (since the process occurs spontaneously), show that the vapour pressure of
the metastable form is greater than that of the stable form at the same temperature.

TRY YOURSELF PROBLEMS

5.1 Justify the phase diagram of I2 as shown in Fig. 1 from the following information.
Solid iodine (A1) is in equilibrium with liquid and vapour at 114 °C and 90 mmHg
pressure. Its second crystalline modification A2 has a vapour pressure 110 mmHg at
114 °C and it has less enthalpy of sublimation than that of A1 . A1 is more dense
than A2 and is less dense than the liquid.
Identify each area, line and point shown in the diagram.
5.2 Figure 2 is the phase diagram of a one-component system. Identify the various points,
lines and areas shown therein. Discuss the slopes of various lines meeting each
other at the points T1, T2, T3, T4 and T5 in terms of Hm and Vm of the involved
transformations.
(Hint: Solid exists in three allotropic forms.)
5.3 Figure 3 is the phase diagram of a one-component system. Identify the various
points, lines and areas shown therein. Discuss the slopes of various lines meeting
242 A Textbook of Physical Chemistry

Fig. 1

Fig. 2

each other at the points T1, T2, T3, T4 and T5 in terms of Hm and Vm of the
involved transformations.
(Hint: Solid has three unstable forms and one stable form.)
5.4 A substance S occurs in two solid modifications: S and S . S has a stable melting
point at about 119 °C (0.05 mmHg). S and S are enantiotropic with respect to each
other and the transition point involving S , S and vapour has the value 95.5 °C
(0.007 mmHg). Phases S , S and liquid are in equilibrium at a triple point 151 °C
and 1290 atm. The transition temperature of the equilibrium S liquid increases
with increase in pressure. Draw the phase diagram.
5.5 Explain why the phase diagram shown in Fig. 4 is not theoretically possible.
(Hint: Slope of s v line at triple point is smaller than that of 1 v line.)
 Phase Diagrams of One-Component Systems 243

Fig. 3

Fig. 4

5.6 Comment on the following statement.

The phase that is stable in equilibrium with the vapour is the phase that has the
lower equilibrium vapour pressure.
5.7 Draw a schematic plot of chemical potential versus temperature for sulphur from the
following information.
At 95.5 °C rhombic sulphur reversibly transforms to monoclinic sulphur.
At 120 °C monoclinic sulphur melts. From the plot, answer the following.
(i) Which has the higher melting point, rhombic or monoclinic sulphur?
(ii) Which form of solid sulphur has greater entropy?
(iii) Which of the two solids will exhibit more ideal solubility at 25 °C in a good
solvent such as diethyl ether?
(iv) Does the melting point of rhombic sulphur lie above or below the rhombic-
monoclinic transition temperature?
(Ans. (i) monoclinic, (ii) monoclinic, (iii) rhombic, (iv) above)
(Hint: Make use of Eq. (2.12.6) for part (iii)).
5.8 At higher pressures, ice is known to exist in six different forms and its phase diagram
has an appearance as shown in Fig. 5. Ice 1 is the common form which exists under
normal conditions. From the figure, answer the following.
(i) How many triple points are present?
(ii) Name the phases which are in equilibrium at each triple point.
244 A Textbook of Physical Chemistry

Fig. 5
(iii) From the slopes of various lines, predict the phase which is more dense than
the other.
(iv) What is the effect of pressure on the melting point of each form of ice?
5.9 Solid ammonium nitrate exists in five crystalline forms with the following triple
point temperatures:
Tetragonal -Rhombic Vapour – 18 °C
-Rhombic -Rhombic Vapour 32 °C
-Rhombic Rhombohedral Vapour 83 °C
Rhombohedral Cubic Vapour 125 °C
Cubic Liquid Vapour 169 °C
-Rhombic -Rhombic Rhombohedral 50 °C
Also, it is known that the order of increasing density is
Liquid < -Rhombic < Rhombohedral < Cubic < -Rhombic < Tetragonal
Sketch a reasonable p-T diagram based on this information.
5.10 Describe the effects produced of (i) isothermal increase and decrease in pressure and
(ii) isobaric increase and decrease in temperature on the following systems of water
(Fig. 5.3.1).
(a) A system on sublimation curve
(b) A system on vaporization curve.
(c) A system on fusion line.
(d) A system at triple point.
(e) A system slightly at the left of fusion line.
(f) A system slightly at the right of fusion line.
(g) A system below the sublimation and vaporization curves.
 6 Phase Diagrams of Two-Component
Systems

6.1 APPLICATION OF THE PHASE RULE

According to the phase rule, the degrees of freedom of a two-component system
is given by
F =C -P +2=4-P
Thus, we have:
System Consisting The phase can be gaseous or completely miscible liquid solution or solid solution.
of One Phase In this case, F = 4 – 1 = 3, thus three variables, namely, temperature, pressure
and composition of the system, will have to be stated in order to define the
system completely.
System Consisting A few typical cases of two-phase equilibrium are given below.
of Two Phases
Liquid-vapour The two constituents will be completely miscible with each
other in the liquid phase.
Liquid-liquid The two liquids will be partially miscible in each other.
Solid-liquid The solid will consist of either of the two constituents or the solid
solution. In the liquid phase, both constituents are completely miscible.
Here since P = 2, we will have F = 4 – 2 = 2. Thus, stating the values
of two variables is sufficient to define the system completely. These variables
are temperature and composition of the liquid phase. All other variables will
have fixed values.
System Consisting A few typical cases of three-phase equilibrium are given below.
of Three Phases
Liquid-liquid-vapour The two constituents will be partially miscible in the
liquid phase.
Solid-liquid-liquid The solid will consist of either of the two constituents or
the solid solution. The two constituents are partially miscible in the liquid phase.
Solid-solid-liquid Both the constituents are present in the solid form and are
completely miscible in the liquid phase.
Here since P = 3, we will have F = 4 – 3 = 1. Thus, stating the value of
only one variable is sufficient to define the system completely.
246 A Textbook of Physical Chemistry

Comment on the Generally various types of equilibria are studied at constant external pressure.
Phase Diagram of Thus, the value of one of the degrees of freedom is already stated, and hence
Condensed Systems their number is reduced by one or alternatively, the degrees of freedom may
be calculated by making use of the reduced phase rule F = C – P + 1. In such
studies, therefore, we have
(i) F = 2 for P = 1,
(ii) F = 1 for P = 2, and
(iii) F = 0 for P = 3.
Since the maximum degrees of freedom to define a two-component system
is two (for p = 1 atm), the phase diagram of such a system can be drawn on
a sheet of paper, choosing the rectangular axes representing temperature and
composition, respectively. A complete phase diagram of a system will have to
include all the three phases, namely, gaseous, liquid and solid. However, it is
more advantageous from the point of view of discussion to draw separately
the phase diagram corresponding to the different types of phase equilibria. The
equilibria involving liquid-vapour and liquid-liquid have already been considered
in Chapter 4. In this chapter, we consider systems involving only solid-liquid
equilibria. Such systems are known as condensed systems. Since in such systems,
the gas phase is absent, the small variation in pressure does not affect the various
solid-liquid equilibria of a system.

6.2 CLASSIFICATION OF DIAGRAMS

Solid-liquid equilibria of varying degree of complexity are known. These may
be analyzed in terms of the following simpler cases.
1. The pure components only crystallize from the solution.
2. The pure components only crystallize from the solution and one of the solids
exists in more than one polymorphic form.
3. The two components form a solid compound stable up to its melting point.
4. The two components form a solid compound which decomposes before its
actual melting point.
5. The two components are completely miscible in the solid phase and form
a complete series of solid solutions.
6. The two components are partially miscible in the solid phase and form stable
solid solutions.
7. The two components form solid solutions which are stable only up to a
transition temperature.
8. The two components are partially miscible in the liquid phase and only pure
components crystallize from the solution.
The above elementary systems are described in Sections 6.4 to 6.11.

6.3 THERMAL ANALYSIS

General Procedure The phase diagram representing different types of solid-liquid equilibria can be
of Thermal Analysis drawn with the method of thermal analysis (or cooling curves). In this method,
a system of known composition is heated so as to obtain it in the molten state.
 Phase Diagrams of Two-Component Systems 247

It is allowed to cool of its own and its temperature after regular interval of time
(say, half a minute) is recorded. A cooling curve of temperature versus time is
made and from the breaks and arrests in the cooling curve, the useful information
regarding the initial and final solidification temperatures are determined. The
above procedure is repeated with different compositions of the system.
For an illustration, we take an example where only pure components
crystallize on cooling the system. The expected types of cooling curve are
described below.
Cooling Curve of a We start with the pure component A (or B) in the liquid state. The rate of cooling
Pure Component of liquid will be smooth till solidification starts. At this stage, the system contains
two phases in equilibrium and, according to the phase rule, it becomes invariant
(F = C + 1 – P = l + 1 – 2 = 0). Thus, solidification of A takes place at constant
temperature in spite of the fact that heat is released during solidification. This is
due to the fact that the rate of liberation of heat during solidification becomes
equal to that of transfer of heat from the system to the surroundings. This gives
rise to what is known as the complete arrest in the rate of cooling. When the
entire liquid has solidified, the system becomes univariant and thus it shows a
smooth cooling of solid phase.
Schematic representation of cooling curve The above pattern of cooling is
shown in Fig. 6.3.1.
a

Cooling of liquid

d
Temperature

c
Solidification ends

Solidification starts
Cooling of solid
e

Fig. 6.3.1 Cooling curve

of a pure component Time

Cooling Curve of a We start with a mixture of B in A of known composition. The system is heated
Mixture to get it in the liquid phase. The degree of freedom of the system in liquid
phase is

F = C + 1- P = 2 + 1-1 = 2
Thus, two variables, viz., temperature and composition of liquid phase, have to
be stated in order to define the system completely. In other words, it may be
248 A Textbook of Physical Chemistry

concluded that the liquid phase of known composition can exist at different
temperatures. Thus, the liquid phase is expected to exhibit smooth cooling until
solid A starts solidifying.
Solidification of A When A starts solidifying, the system becomes univariant,
(F = C + 1 – P = 2 + 1 – 2 = 1). Thus, the temperature at which solid A starts
solidifying from the liquid mixture of known composition will have a fixed value.
This temperature is expected to be lesser than the freezing point of A from pure
liquid A since the addition of B in A lowers the freezing point of the latter.
The separation of A in solid phase changes the composition of liquid phase
and thus the separation of A from this liquid will take place at another fixed
temperature. The latter is expected to be smaller than the previous temperature
as the separation of A increases the molality of B in the solution. Thus, the
system is expected to exhibit cooling during more and more solidification of A.
However, the rate of cooling is retarded owing to the liberation of heat during
solidification of A and thus a break in the cooling curve is observed. The break
point indicates the temperature at which first crystal of A is obtained.
Solidification of both A and B If cooling is continued, the solution may become
saturated with respect to B and hence B also starts solidifying along with A. At
this stage, the system becomes nonvariant (F = C + 1 – P = 2 + 1 – 3 = 0) and
thus solidification from a solution of fixed composition (corresponding to the
saturation solubility of B in A) takes place at constant temperature. This results
in a complete arrest of cooling curve. Since at this temperature the saturation
solubility of B in A has to be maintained, it follows that the composition of
solid phase which separates will have the same composition as that of the liquid
phase. The temperature of the system will remain constant until the entire liquid
phase has solidified. After this, the system will exhibit smooth cooling of solid
phases. Thus, the start and end of horizontal line in cooling curve indicate,
respectively, the start of solidification of both components together and the
complete solidification of the liquid phase.
Schematic representation of cooling cure The above pattern of cooling is
shown in Fig. 6.3.2. The description of Fig. 6.3.2 is also given in Table 6.3.1.

Table 6.3.1 Description of Fig. 6.3.2

Location of system Description Degrees of freedom
ab Cooling of liquid mixture 2
b Start of solidification of A 1
bc Solidification of A continues 1
c B also starts solidifying 0
cd Solidification of A and B continues. 0
The composition of solid mixture
separated here is the same as that of
the liquid phase
d Almost complete solidification of liquid phase 0
de Cooling of solid phases 1
 Phase Diagrams of Two-Component Systems 249

Cooling of liquid
F=2

Solidification starts
b F=1

Solidification

Temperature
continues Solidification ends
c d

Second component Cooling of solid

starts crystallizing mixture
F=0 F=1
Crystallization e
Fig. 6.3.2 Cooling curve of eutectic mixture
of a liquid mixture of a F=0
two-component system Time

Supercooling of liquid In some cases, the separation of solid phase does not
occur readily and thus supercooling is observed. The cooling curve instead of
showing a break continues along a continuation of ab. Since this represents an
unstable state, soon one observes a sudden rise in temperature followed by a
smooth cooling along b c (Fig. 6.3.3). The correct freezing point may then be
obtained by extrapolation back to b as shown in Fig. 6.3.3.
a

b b¢
Temperature

d
c

e
Fig. 6.3.3 Supercooling
phenomenon Time

Comment The pattern as shown in Fig. 6.3.2 is, however, not shown at a particular
composition where on cooling both the components solidify simultaneously. In
this case, the first break is not observed and one gets the cooling curve similar
to that shown in Fig. 6.3.1. The cooling curve of a system in which solid solution
and not the pure component separates on cooling is similar to that given in
Fig. 6.3.2 with the exception that the horizontal portion is replaced by a break.
250 A Textbook of Physical Chemistry

6.4 CRYSTALLIZATION OF PURE COMPONENTS — SIMPLE EUTECTIC PHASE DIAGRAM†

Description of the The general form of the phase diagram along with the expected cooling curves
Phase Diagram of such a system is shown in Fig. 6.4.1.

Fig. 6.4.1 Phase diagram of a system exhibiting crystallization of pure components

From the cooling curves shown in Fig. 6.4.1, the following information can be
derived.
From the cooling curves of pure components, the point A and B representing,
respectively, the freezing points of the pure components A and B are obtained.
From the cooling curves I and II of two systems of A in B, the points b and
i representing, respectively, the start of solidification of B and the points d
and j representing, respectively, the start of solidification of both A and B
together are obtained. Since the addition of a solute in a solvent depresses
the freezing point of the latter, the temperatures corresponding to the points
b and i are smaller than the freezing point of the pure component B.
Similarly, from the cooling curves III and IV of two systems of B in A,
the points b and f representing respectively the start of solidification of A
and the points c and g representing respectively the start of solidification
of both A and B together are obtained.
If a smooth curve passing through the points A, b and f is drawn, we get the
curve AO which represents the start of freezing of pure component A from
liquid solution of different compositions. Similarly, if a line passing through
B, i and b is drawn, we get the freezing point curve of the component B.

†
See Project 1 in vol 6 for the formation of eutectic phase diagram constructed from the
consideration of free energies.
 Phase Diagrams of Two-Component Systems 251

If a line passing through the points c , g , d and j is drawn, we get a horizontal

line CD which indicates the temperature at which both components start
solidifying together from the liquid O irrespective of the original composition
of the liquid phase. The point O where the freezing point curves AO and
BO meet each other also lies on this horizontal line.
Sequence of Effects The labelling of the phase diagram shown in Fig. 6.4.1 can be easily understood
Produced on by first considering the expected behaviour of a liquid solution during its cooling.
Cooling a Liquid If, for example, a liquid solution represented by the point a is cooled, the state
Mixture of the overall system will move vertically downward along abcde, known as
isopleth.
The system will remain in liquid phase till the point b is reached where the
first crystal of B starts appearing.
The removal of solid B from liquid phase makes the composition of liquid
phase less rich in B and thus its composition moves towards the A-axis.
If the crystallization of B is to be continued, the temperature of the liquid
phase has to be decreased since its composition point moves on the line
bfO. Thus on cooling, more and more of B solidifies and the composition
of the liquid phase moves along the curve bfO. For example, if the system
has been cooled up to the overall state point c, the system will consist of
solid B (represented by the point g) in equilibrium with liquid phase whose
composition corresponds to the point f. The point f is the intersection point
of the tie line (horizontal line ) drawn from the point c with the curve
BO. The tie line, by definition, is a line which connects different phases
in equilibrium with one another. In the present case, the two phases in
equilibrium are represented, respectively, by the points g (solid phase B) and
f (liquid phase). The relative amounts of the two phases may be determined
by using the lever rule, such that

Amount of solid B fc
= (6.4.1)†
Amount of liquid phase f cg

During the cooling of the system from b to d, the relative length of the
segment of tie line lying to the left of bcd (i.e. fc) increases indicating that
the relative amounts of the two phases change in favour of solid B, i.e. more
and more B solidifies during the cooling process.
When the system has been cooled to the point d the liquid composition will
move to the point O. Hence, here A also starts crystallizing along with B.
From this, it follows that the yield of pure crystals of B will be maximum
when the cooling of the system is carried out up to a point slightly above
the point d.

†
For derivation of the lever rule, see p. 259.
Throughout the Chapter, a system is represented by an alphabet printed in roman style
while its composition is represented by the same alphabet printed in italics.
252 A Textbook of Physical Chemistry

Maximum amount of B recoverable We can compute the maximum amount

of pure B that can be separated from the liquid a as shown in the following.
The maximum amount of pure B (which can be separated from the starting
liquid a) relative to that of the liquid O is given by

Amount of liquid O dD
= (6.4.2)
Maximum amount of solid B separated Od

Adding one on both sides and inverting the expression, we get

Maximum amount of solid B separated Od Od

= =
Amount of (liquid O + soolid B) Od + dD OD

Hence, the maximum amount of solid B separated

Ê Od ˆ
= Á
Ë OD ˜¯
(amount of starting liquid a) (6.4.3)

At point d, the solid mixture which solidifies has the same composition
as that of the liquid phase, vis-à-vis, the composition of the liquid phase
remains unchanged. The temperature of the system also remains unchanged
till whole of liquid phase is solidified. Since now solid phase contains both
A and B, the point representing solid phases moves from D towards d along
the line Dd as more and more of solid mixture is precipitated. When this
point is reached at d, whole of liquid solution is solidified.
Amount of solid eutectic mixture separated at any point before whole of
liquid is solidified can be computed as follows.

At any point in between D to d (say at j), the amount of liquid O relative

to the total amount of solids A and B, (that has separated from the liquid
a) is given by

Amount liquid O dj
= (6.4.4)
Amount of total solids (A + B) separated Od

Adding one on both sides, we get

Amount of (liquid O + total solids separated) Od + dj Oj

= =
Amount of totaal solids separated Od Od

Taking inverse, we get

Ê Od ˆ Ê amount of startingˆ
Amount of total solids separated = Á (6.4.5)
Ë Oj ˜¯ ÁË liquid a
˜¯
 Phase Diagrams of Two-Component Systems 253

From this amount, if we subtract the pure solid B that has separated on
reaching the point d (as given by Eq. 6.4.3), we get the total amount of solid
mixture that has separated when the liquid is cooled beyond d till the composition
of solid phase is given by the point j. If the composition of solid mixture is
analysed, it will correspond to the point O.
Further cooling from d to e, merely decreases the temperature of the solid
mixture.
Conclusions of From the above analysis, the following conclusions may be drawn.
Phase Diagram
A point within the area BODB represents a system of solid B in
equilibrium with a liquid phase.† The composition of the latter is given by the
intersection point of the tie line drawn from the given point with the curve
BO. The relative amounts of two phases can be determined by using the
lever rule. Similarly, a point within the area ACOA represents a system of
solid A in equilibrium with a liquid solution whose composition lies on the
curve AO.
Along the lines AO and BO and within the areas AOCA and BODB, the
system is univariant (F = C + 1 – P = 2 + 1 – 2 = 1). Thus for a given
temperature, the composition of liquid phase in equilibrium with solid A or
solid B has a fixed value.
A point on the line CD represents an invariant system (F = C + 1 – P =
2 + 1 – 3 = 0). For the point O the temperature is lowest at which any liquid
of A and B will freeze out and, consequently, represents the lowest melting
point of any solution of solids A and B. It is for this reason, the point O is
known as the eutectic point ( Greek: easily melting).
Line AOB is the liquidus curve as it gives composition of the liquid
phase in equilibrium with the solid phase. The line ACODB is known as
the solidus curve; lines AC, COD and DB represent, respectively, solid A,
mixtures of solids A and B in equilibrium with liquid phase of composition
O and solid B. The two curves AOB and ACODB meet each other at point
O.
Cooling of a system on the line CD will result into the solidification of A
and B together from the liquid phase of eutectic composition O. The solid
mixture which separates here has the same composition as that of the liquid
phase.
A system below the line CD represents a solid mixture of A and B.
Labelling of Eutectic Table 6.4.1 describes, in brief, the phase diagram shown in Fig. 6.4.1.
Phase Diagram

†
In general, the two phases in equilibrium within an area are given by the two vertical
end lines of the area. For example, for the area BDOB, the two vertical end lines are
BD and BO. These lines represent solid phase B and liquid solution, respectively. Thus,
within the area BDOB, solid B is in equilibrium with liquid solution whose composition
lies on the line BO.
254 A Textbook of Physical Chemistry

Table 6.4.1 Description of Phase Diagram given in Fig. 6.4.1

Location of Status of the system Degrees of freedom

the system number kind

A Freezing point of A 0 fixed T

B Freezing point of B 0 fixed T
AO Start of crystallization of A 1 T or composition
BO Start of crystallization of B 1 T or composition
O Eutectic point 0 fixed T and fixed
composition
Area above Liquid phase 2 T and composition
AOB
Area below Solid mixture 1 T
COD
Area Solid A in equilibrium with liquid 1 T or composition
ACOA phase whose composition lies on
the curve AO.
Area Solid B in equilibrium with liquid 1 T or composition
BDOB phase whose composition lies on
the curve BO.
COD Systems where both A and B cry- 0 fixed T (eutectic
stallize together from liquid phase temperature) and
O. fixed composition
(eutectic composi-
tion O)

Cooling Patterns We describe below the expected pattern of cooling curves for a few typical
cases.
Pure components
Rapid cooling of Halt; Cooling of
liquid solidification solid compound
of the compound
Composition lying anywhere between AO or BO
Rapid cooling of Break; Slower cooling;
liquid solidification solidification
of A or B continues

Cooling of Horizontal portion;

solid mixture eutectic point
Eutectic composition
Rapid cooling of Horizontal portion; Cooling of solid
liquid eutectic point mixture
These cooling patterns are also shown in Fig. 6.4.1.
 Phase Diagrams of Two-Component Systems 255

Example 6.4.1 The solubility of KBr in water is

θc/°C 0 20 40 60 80 100
g KBr/g H2O 0.54 0.64 0.76 0.86 0.95 1.04
In a one molal solution, KBr depresses the freezing point of water by 3.29 °C. Estimate
graphically the eutectic temperature for the KBr-H2O system.
Solution In one molal solution of KBr, we have 110 g (molar mass of KBr) of KBr in 1 000 g
of water or 0.110 g of KBr per g of water. We are given that ice separates from one molal
solution of KBr at –3.29 °C, since ice separates from pure water at 0 °C. With these two
temperatures, viz., 0 °C and –3.29 °C, we can draw the freezing point curve for ice as
shown by the line AB in Fig. 6.4.2. On the other hand, we can draw the solubility curve
CD from the given data on the solubility of KBr. If the two lines AB and CD are extended,
we get the eutectic point at –13 °C.

90

70

50

30
qc/°C

10
A
B D

–10
–13°C
O

–30
Fig. 6.4.2 Required 0.2 0.4 0.6 0.8 1.0
phase diagram g KBr/g H2O

Example 6.4.2 (a) KBr is recrystallized from water by saturating the solution at 100 °C, then cooling to
20 °C; the crystals obtained are redissolved in water and the solution evaporated until it is
saturated at 100 °C. Cooling to 20 °C produces a second crop of crystals. What is the per
cent yield of pure KBr after these two crystallizations? Use data given in Example 6.4.1.
(b) Two crops of KBr crystals are obtained as follows. A solution saturated at 100 °C is
cooled to 20 °C; after filtering off the first crop, the mother liquor is evaporated until the
256 A Textbook of Physical Chemistry

solution is saturated at 100 °C; cooling to 20 °C produces the second crop. What fraction
of KBr is recovered in the two crops by this method? Use data of Example 6.4.1.
Solution (a) At 100 °C, the solubility of KBr is 1.04 g/g H2O. If this solution is cooled to 20 °C,
solubility becomes 0.64 g KBr/g H 2O. Hence, the mass of KBr crystallized is
(1.04 – 0.64) g, i.e. 0.4 g KBr. Now this 0.4 g KBr is again redissolved to give a saturated
solution at 100 °C. The mass of water which need to be added is
1 g H2O 0.4
¥ 0.4 g KBr = g H2O
1.04 g KBr 1.04
If the resultant solution is cooled to 20 °C, the mass of KBr remaining in the solution
will be equal to

0.64 g KBr Ê 0.4 ˆ 0.64 ¥ 0.4

¥Á g H 2 O˜ = g KBr
1 g H 2O Ë 1.04 ¯ 1.04

Thus, the mass of KBr separated at this stage will be given by

0.64 ¥ 0.4 0.4 ¥ 0.4 0.16
0.4 g - g= g= g
1.04 1.04 1.04
Thus, out of 1.04 g of KBr which we had originally in the solution, (0.16/1.04) g of KBr
has been separated after these two crystallizations. Hence per cent yield of pure KBr is
0.16 100
g¥ = 14.79
1.04 1.04 g
(b) At 100 °C, the solubility is 1.04 g KBr/g H2O. If this solution is cooled to 20 °C, the
solubility becomes 0.64 g KBr/g H2O. Hence the mass of KBr crystallized is (1.04 – 0.64) g,
i.e. 0.4 g KBr. Now the mother liquor is evaporated until the solution is saturated at
100 °C. The mass of water that remained in the above evaporation process is equal to
1 g H2O 0.64
¥ 0.64 g KBr = g H2O
1.04 g KBr 1.04
If the resultant solution is cooled to 20 °C, the mass of KBr that remained in the solution
is equal to

Ê 0.64 g KBr ˆ Ê 0.64 ˆ

ÁË 1 g H O ˜¯ ÁË 1.04 g H 2O˜¯
2

Thus, the mass of KBr separated in the second crop becomes

0.64 ¥ 0.64 0.64 ¥ 0.4
0.64 g - g= g
1.04 1.04
The total mass of KBr separated in the two crops
0.4 ¥ 0.64 0.4 ¥ 1.68
0.4 g + g= g
1.04 1.04
Hence

Ê 0.4 ¥ 1.68 ˆ Ê 100 ˆ

Per cent of KBr recovered Á g˜ Á = 62.15
Ë 1.04 ¯ Ë 1.04 g ˜¯

Theoretical Aspects The curve AO of Fig. 6.4.1 gives the freezing point curve of pure solid A and
of Fig. 6.4.1 thus it tells us the first temperature at which pure solid A precipitates
 Phase Diagrams of Two-Component Systems 257

(alternatively, at which the last solid A melts) for a system whose starting
composition lies between the points C and O. In other words, the curve AO is
the saturation solubility curve for the component A. As mentioned earlier, the
system anywhere on the line AO is univariant indicating that for a given
composition, the temperature at which initial solidification starts has a fixed
value.
For ideal systems, the variation of solubility of a component with temperature
is given by the van’t Hoff relation, which was derived thermodynamically in
Section 2.12. The expression at p = 1 bar is:

D fus H m∞ Ê 1 1 ˆ
ln x = - ÁË - ˜
R T T* ¯

where x is the saturation solubility in amount fraction of the component in ideal

solution at temperature T, and T * is the freezing point of the pure component.
For the component A, we have

∞ AÊ 1
D fus H m, 1 ˆ
ln xA = - Á - ˜ (6.4.1)
R Ë TA TA* ¯

Now xA may have value anywhere between 0 and 1, thus ln xA is negative. Since
*
fusHm, A is positive (fusion is an endothermic process), it follows that TA is
greater than TA, i.e. the temperature at which initial solidification of pure A starts
from the liquid solution is smaller than the freezing point of pure A.
Similarly, the curve BO of Fig. 6.4.1 represents the solubility curve of the
component B. For ideal systems, this solubility curve follows the relation

∞ BÊ 1
D fus H m, 1 ˆ
ln xB = - Á - ˜ (6.4.2)
R Ë TB TB* ¯

where TB is the temperature at which initial solidification of the pure component

B starts from a liquid solution in which the amount fraction of the component
B is xB and TB* is the freezing point of the pure solid B.
At the eutectic point O, the two solubility curves AO and BO meet each
other. At the eutectic temperature Te, Eqs (6.4.1) and (6.4.2) become

∞ AÊ 1
D fus H m, 1 ˆ
ln xA = - Á - ˜ (6.4.3)
R Ë Te TA* ¯

∞ BÊ 1
D fus H m, 1 ˆ
ln xB = - Á - ˜ (6.4.4)
R Ë Te TB* ¯
Eliminating Te, we get
R 1 R 1
- ln xA + =- ln xB +
∞A
D fus H m, TA* ∞B
D fus H m, TB*
258 A Textbook of Physical Chemistry

Since xA + xB = 1, we have
1 1 R R
- = ln xA - ln (1 - xA ) (6.4.5)
T*A T*
B ∞A
D fus H m, ∞B
D fus H m,
Thus knowing TA*, TB*, fusHm,A º and fusHm, º B, Eq, (6.4.5) can be solved for xA
which represents the composition of the liquid mixture at the eutectic point. On
substituting xA in Eq. (6.4.3) or Eq. (6.4.4), we can get the eutectic temperature
of the system.

Example 6.4.3 Sodium chloride-sodium sulphate system exhibits the simple eutectic phase diagram with
the following characteristics:
Melting point (m.pt.) of sodium chloride = 1 074 K
Enthalpy of fusion of sodium chloride = 28.87 kJ mol–1
Enthalpy of fusion of sodium sulphate = 24.06 kJ mol–1
Eutectic composition = 48.2 mol per cent of sodium sulphate. Assuming ideal behaviour,
compute, (i) the m.pt. of sodium sulphate, and (ii) the eutectic temperature of the system,
Solution (i) From Eq. (6.4.5), we get
1 1 R R
- = ln xA - ln xB
*
TA TB * ∞A
D fus H m, ∞ B
D fus H m,
where TA* is the m.pt. of pure A, TB* is the m.pt. of pure B, xA is amount fraction of A
at the eutectic point, fusHm,
º A is the molar enthalpy of fusion of A, and fusH m,
º B is the
molar enthalpy of fusion of B.
Identifying A with NaCl and B with Na2SO4 and substituting the given data in the above
equation, we get
1 1 (8.314 J K -1 mol -1 )
- = ¥ 2.303 ¥ log (0.518)
1 074 K TB* (28 870 J mol -1 )
(8.314 J K -1 mol -1 )
- ¥ 2.303 ¥ log (0.482)
(24 060 J mol -1 )
1
0.000 931 K -1 - = - 0.000 189 4 K -1 + 0.000 252 2 K -1
TB*
1
= 0.000 868 2 K -1
TB*

Thus TB* = 1 152 K

(ii) From Eq. (6.4.3), we get

∞ Ê1
D fus H m,A 1 ˆ 1 R 1
ln xA = - Á - ˜ or =- ln xA +
R Ë Te TA* ¯ Te ∞
D fus H m,A TA*
Substituting the given data, we get
1 (8.314 J K -1 mol -1 ) 1
=- ¥ 2.303 log (0.518) +
Te (28 870 J mol -1 ) 1 074 K
= 0.000 189 4 K -1 + 0.000 931 K -1 = 0.001 120 4 K -1
Hence Te = 892.5 K
 Phase Diagrams of Two-Component Systems 259

Derivation of the The area BODB (or AOCA) in Fig. 6.4.1 represents the region where solid B (or
Lever Rule A) is at equilibrium with the liquid phase whose composition lies on the curve
BO (or AO). The composition of the liquid phase corresponding to the given
point can be obtained by drawing a horizontal line (known as tie line) though the
given point. The point of intersection of the tie line with the curve BO (or AO)
gives the composition of the liquid phase. For example, at the point c shown in
Fig. 6.4.1, the composition of the liquid phase is given by the point f. In fact, a
point anywhere on the line fg represents the liquid phase f in equilibrium with
solid B. The only thing that varies along the line is the relative amount of solid
and liquid phases. For example, at point c, we have
Amount of solid B fc
= (6.4.6)
Amount in the liquid phase gc
Equation (6.4.6) is the expression of the lever rule and can be derived as follows.
Let XB be the amount fraction of B in the overall system at the point c.
Since at c, only B is solidified, we will have
nB(s) + nB(1)
XB = (6.4.7)
nA(1) + nB(s) + nB(1)
If xB is the amount fraction of B in the liquid phase at the point f, we have
nB(1)
xB = (6.4.8)
nA(1) + nB(1)
Now from Fig. 6.4.1, we have
fc = X B - xB (6.4.9)
gc = 1 - X B (6.4.10)
Substituting Eq. (6.4.8) in Eq. (6.4.9), we have
nB(1)
fc = X B -
nA(1) + nB(1)

or {nA(1) + nB(1)} (fc) = {nA(1) + nB(1)} X B - nB(1) (6.4.11)

Multiplying Eq. (6.4.10) by nB(s), we get
nB(s) (gc) = nB(s) - nB(s) X B (6.4.12)

Subtracting Eq. (6.4.12) from Eq. (6.4.11), we get

{nA(1) + nB(1)} (fc) - nB(s) (gc) = X B {nA(1) + nB(1) + nB(s)} - {nB(1) + nB(s)}

According to Eq. (6.4.7), the right side of the above expression is zero.
Hence, we have
(fc) nB(s) Amount of solid B
= =
(gc) nA(1) + nB(1) Amount of liquid phase
which is the required expression of the lever rule (Eq. 6.4.6).
260 A Textbook of Physical Chemistry

Example 6.4.4 What mass of antimony crystallizes from 20 kg of Pb-Sb melt containing 35 mass % Pb
after cooling to a temperature of 400 °C? What is the maximum mass of pure Sb that
can be obtained from the melt? You are provided with the following data: m.pt. of Pb
= 327 °C, m.pt. of Sb = 631 °C. Breaks on the cooling curve in thermal analysis were
found for the following conditions:
Mass % Pb 30 44 66 80 86 (eutectic)
θc/°C 550 500 400 300 250

Solution First of all, the phase diagram of the Pb-Sb system is plotted from the given data. It is
shown in Fig. 6.4.3.

600

500
qc/°C

31 mm 35 mm
400
a b c

300

51 mm 35 mm

Solid Sb + Solid Pb
200
Pb Composition Sb
Fig. 6.4.3
At 400 °C the relative ratio of Sb and the melt in the given system of 35 mass %
Pb is given by

Mass of melt bc 35 mm
= =
Mass of Sb ba 31 mm

Mass of (melt + Sb) 35 + 31

=
Mass of Sb 31

Therefore
Mass of Sb 31
=
Total mass of melt 66

Ê 31 ˆ
Hence Mass of Sb = Á ¥ 20 kg˜ = 9.39 kg
Ë 66 ¯
 Phase Diagrams of Two-Component Systems 261

Since maximum mass of Sb will be obtained just above the eutectic point, we have
Mass of melt 35 mm Mass of Sb 51
= or =
Mass of Sb 51 mm Mass of (Sb + melt) (51 + 35)

51
Hence Mass of Sb = ¥ 20 kg = 11.86 kg
86

Examples A few examples of systems exhibiting simple eutectic phase diagram are given
in Table 6.4.2.
Table 6.4.2 Systems Exhibiting Simple Eutectic Phase Diagrams

System Eutectic Eutectic

A m.pt. B m.pt. temperature composition

ºC ºC ºC
Sodium sulphate 884 Sodium chloride 800 628 48.2 mol %A
Naphthalene 80.0 Benzoic acid 120 67–69 30 mol %B
Naphthalene 80.0 -Naphthol 95.0 54.1 48.7 mol %B
Succinimide 123 -Naphthol 95.0 57.0 70 mass %B
Benzamide 124.8 -Naphthol 92.0 38.1 60 mass %B
Benzamide 124.8 -Naphthol 122.0 54.1 60 mass %B
Urea 131 Benzoic acid 121 76.5 70 mass %B
Acetanilide 112 Benzoic acid 121.4 76.0 42.4 mol %B
Resorcinol 115 Succinic acid 183 100 12.5 mass %B
-Naphthol 95 Cinnamic acid 133 68 37 mass %B
Diphenyl 69.0 Benzophenone 47.7 25.2 60.7 mol %B
Stilbene 120.4 Benzil 94.0 76.6 71.5 mol %B
-Naphthol 121 Cinnamic acid 133 87 47 mass %B
Benzoic acid 121 Cinnamic acid 133 81 43.5 mol %B
Benzoic acid 121.4 Resorcinol 110 86 40 mol %A
Resorcinol 115 Cinnamic acid 133 87 41 mass %B
†
Temperatures mentioned here are the reported temperatures in literature.

6.5 CRYSTALLIZATION OF PURE COMPONENTS AND ONE OF THE SOLIDS EXISTS IN

MORE THAN ONE CRYSTALLINE FORM
Let out of the two components A and B, the component B exist in two crystalline
forms, namely, -form and -form. Let -form be stable at lower temperatures
and -form at higher temperatures. If Ti is the transition temperature, we will
have
t > Ti
a -form �
����
��� � b-form
�
t <T i

The phase diagram of the present system along with the expected cooling
curves is shown in Fig. 6.5.1.
Description of the From the cooling curves shown in Fig. 6.5.1, the following information can be
Phase Diagram derived.
262 A Textbook of Physical Chemistry

Fig. 6.5.1 Simple eutectic phase diagram for a system exhibiting crystalline modification of one of the components

From the cooling curve of pure component A, the point A representing the
freezing point of A is obtained.
From the cooling curve of pure component B, the points B and C representing,
respectively, the freezing point and the transition temperature of B are
obtained.
From the cooling curves I and II of two systems of B in A, the points a
and b representing respectively the start of solidification of A and the points
a and b representing respectively the start of solidification of both A and
B ( -form) together are obtained. Since the addition of B in A lowers the
freezing point of the latter, the temperatures corresponding to the points a
and b are smaller than the freezing point of pure A.
From the cooling curves III and IV of two systems of A in B, the points
c and d representing respectively the start of solidification of B( -form);
the points c and d representing respectively the transition of B( -form) to
B( -form), and the points c and d representing respectively the start of
solidification of both B( -form) and A together are obtained.
From the cooling curves V and VI of two liquid systems of A and B, the
points e and f representing respectively the start of solidification of B( -
form) and the points e and f representing the start of solidification of both
B( -form) and A together are obtained.
If a smooth curve passing through the points A, a and b is drawn, we get
the curve Aab which represents the start of freezing of pure component A
from liquid solutions of different compositions.
Similarly, the curve passing through the points B, c and d, and that passing
through the points e and f give the freezing point curves of B( -form) and
B( -form), respectively.
 Phase Diagrams of Two-Component Systems 263

A horizontal line FG passing through the points a , b , f , e , d and c gives

the temperature at which solid A and solid B( -form) start crystallizing
together.
The lines Aab and ef on extending meet at the point D. This point, which
also lies on the line FG, gives the composition of liquid phase from which
two solids A and B( -form) crystallize together. The overall composition of
the solids (i.e. amount of A plus amount of B) separated is the same as that
of the liquid phase, vis-à-vis, the composition of the liquid phase remains
unchanged during the solidification of A and B( -form). The temperature of
the system remains constant until the entire liquid phase is solidified. This
is revealed by the complete arrest of cooling curves at this temperature.
If a horizontal line passing through the points d , c and C is drawn, we get
the line Cc d over which the transition of B( -form) to B( -form) occurs.
If the lines Bcd, fe and Cc d are extended, they meet at the point E which
gives the composition of liquid phase at the transition temperature.
Sequence of Effects The phase diagram shown in Fig. 6.5.1 can be easily labelled by considering the
Produced on behaviour of a system from which solid B crystallizes on cooling. If, for example,
Cooling Liquid the liquid phase given by the point g is cooled, the state of the overall system
Mixtures is moved vertically downward along the isopleth gchc ic j. The system remains
in liquid phase up to the point c. At c solid B( -form) starts crystallizing. The
separation of B from the liquid phase moves its composition towards A-axis.
If the crystallization of B is to be continued, the liquid phase has to be cooled
so that its composition moves on the line cdE. Thus, as cooling is continued,
more and more of solid B( -form) separates and the composition of liquid phase
moves along cdE. For example, if the system has been cooled up to the overall
state point h, the system now consists of solid B( -form) in equilibrium with the
liquid phase of composition corresponding to the point d. This point is obtained
by drawing a tie line (horizontal line) from the point h which meets the curve
BE at d. The relative amounts of two phases can be determined with the help
of the lever rule.
If the cooling of the system is done up to the point c , the system will
contain three phases, viz., solid B( -form), solid B( -form) and the liquid phase
E, in equilibrium with one another. Continued cooling of the system at c merely
causes the polymorphic change of solid B( -form) into B( -form) without any
change in temperature. This is revealed by an arrest of cooling curve at point
c . Once the transition is complete, the system exhibits cooling during which
more and more of solid B( -form) separates and the composition of liquid phase
moves along ED. When the system is cooled up to the point c , the composition
of the liquid phase has moved up to the point D. Further cooling results into
the solidification of B( -form) and A together from the liquid phase D without
any change in temperature. The composition of overall solids separated is the
same as that of the liquid phase, vis-à-vis, the composition of the liquid phase
remains constant throughout. Once the entire liquid phase has solidified, the
system exhibits cooling of solid mixture of A and B( -form).
264 A Textbook of Physical Chemistry

For the system V (or VI), the system will remain liquid up to the point e
(or f). At this point, solid B( -form) starts solidifying and continues to solidify
till the point e (or f ) is reached. The composition of liquid phase moves
along efD. At e , the liquid composition corresponds to the point D. Here solids
B( -form) and A start crystallizing together.
For the system I (or II), it is the solid A which starts crystallizing when
the system reaches the point a (or b). Solid A continues to solidify till the point
a (or b ) is reached. At a (or b ), solids A and B( -form) crystallize together
from the liquid phase represented by the point D.
Conclusion of the From the above analysis, the following conclusions can be derived.
Phase Diagram
A system within the area ADFA represents solid A in equilibrium with
liquid phase whose composition lies on the line AD. The point at which the
tie line drawn from the given point meets the curve AD gives the required
composition. The relative amounts of the two phases can be determined by
making use of the lever rule.
A system within the area DECGD represents solid B( -form) in equilibrium
with a liquid phase whose composition lies on the line DE.
A system within the area BECB represents solid B( -form) in equilibrium
with a liquid phase whose composition lies on the line BE.
A point within the area ADFA, DECGD and BECB represents an univariant
system (F = C + 1 – P = 2 + 1 – 2 = 1). Thus for a given temperature,
the composition of the liquid phase in equilibrium with solid A or solid
B( -form) or B( -form) has a fixed value.
A point on the line FDG or EC represents a nonvariant system (F = C +
1 – P = 2 + 1 – 3 = 0).
A point below the line FDG represents a mixture of solids A and B( -form).
The point D is the eutectic point at which solids A and B( -form) are in
equilibrium with liquid phase represented by the point D.
Labelling of the Table 6.5.1 describes, in brief, the phase diagram shown in Fig. 6.5.1
Phase Diagram
Cooling Patterns The nature of cooling curve will depend upon the composition of the system. We
now describe the expected pattern of cooling curves for a few typical systems
shown in Fig. 6.5.1.
(i) Composition lying between AD and DE
Rapid cooling Break at the Slower cooling; soldifica-
of liquid phase appearance of solid tion continues

Cooling of Horizontal portion;

solid mixture eutectic point
(ii) Eutectic composition:
Rapid cooling Horizontal portion; Cooling of solid
of liquid phase eutectic point mixture
 Phase Diagrams of Two-Component Systems 265

Table 6.5.1 Description of the Phase Diagram of Fig. 6.5.1

Location of the system Status of the system

A Freezing temperature of A
B Freezing temperature of B
C Transition temperature of B
AD Freezing point curve of A
DE Freezing point curve of B( -form)
BE Freezing point curve of B( -form)
A-axis Solid A up to the point A, and liquid A beyond A
B-axis Solid B( -form) up to the point C, solid B( -form)
from C to B and liquid B beyond the point B
FDG Solids A and B( -form) in equilibrium with liquid
phase D
EC Solids B( -form) and B( -form) in equilibrium
with liquid phase E
Area AFDA Solid A liquid (whose composition lies on AD)
Area DECGD Solid B( -form) liquid (whose composition lies on DE)
Area BECB Solid B( -form) liquid (whose composition lies on EB)
Area above Liquid phase
ADEB
Area below Solid mixtures
FDG

(iii) Composition lying between EB

Rapid cooling Break at the Slower cooling, soldifica-
of liquid phase appearance of tion of solid B( -form)
B( -form) continues

Horizontal portion; Slower cooling; Horizontal portion;

eutectic point appearance of B conversion of solid
( -form) continues B( -form) to B( -form)
Cooling of solid
mixture
(iv) Composition corresponding to the Point E
Repaid cooling Break at the appearance Slower cooling; appearance
of liquid phase of solid B( -form) of solid B( -form) continues

Cooling of solid Horizontal portion;

mixture eutectic point

Examples Examples in which one of the components exhibits more than one crystalline
form are given below.
(i) Solid carbon tetrachloride exists in two forms, with a transition point at
–48 °C. All systems with CC14 as one of the components show a break in the
phase diagram at this transition temperature provided the eutectic temperature
of the system lies below – 48 °C.
266 A Textbook of Physical Chemistry

(ii) Solid ammonium nitrate exists in five crystalline forms with the
following transition temperatures:
Cubic Rhombohedral -Rhombic -Rhombic Tetragonal
125 ºC 48 ºC 32 ºC – 18 ºC

Consequently, four breaks corresponding to these transitions are observed in the

phase diagram of ammonium nitrate-water system.
Theoretical Aspects The entire phase diagram of Fig. 6.5.1 may be constructed by drawing the simple
of Fig. 6.5.1 eutectic phase diagram AO B of the system A – B( ) and then superimosping
on it the simple eutectic phase diagram AOB of the system A – B( ) as shown
in Fig. 6.5.2. In order to construct these two phase diagrams, we should have
data on TA*, fusHm,º A, T *B( ), fusH m,
º B( ), fusH ºm, B( ) and the melting point of
the solid B( ).

B¢

A
E
Temperature

C O
D

Fig. 6.5.2 Construction O¢

of the phase diagram for
a system exhibiting
allotropic modification of
one of the components Pure Composition Pure
A B

6.6 FORMATION OF A COMPOUND STABLE UP TO ITS MELTING POINT

Application of the Let the two components A and B form a stable compound AB. This compound
Phase Rule will have its own characteristic melting point which may be greater or smaller
than the melting points of pure components A and B. Since the compound is
stable and melts only at its melting point, it is obvious that the compound on
heating will remain in the solid phase up to its melting point where it melts to
produce a liquid whose composition is the same as that of the compound. At
 Phase Diagrams of Two-Component Systems 267

this stage, the system becomes nonvariant. This may be proved with the help
of the lever rule:
F = (C - r ) + 1 - P

Here r = 1, since the compositions of solid and liquid phases are identical.
Thus
F = (2 - 1) + 1 - 2 = 0

Hence, the temperature of the system remains constant till the entire solid
compound melts. Such a melting point where both solid and liquid of the same
composition can coexist is known as the congruent melting point.
Conversely, if a liquid of composition AB is cooled, it will exhibit uniform
cooling up to the freezing point of solid AB. At this temperature, solid AB
separates and continues to separate without any change in temperature until
whole of the liquid phase is solidified. After this, the system will exhibit cooling
of solid AB. Thus, the cooling pattern of the liquid phase of composition AB
is similar to that of a pure component.
Description of the The phase diagram of the present system along with the expected cooling curves
Phase Diagram is shown in Fig. 6.6.1.

Fig. 6.6.1 Phase diagram of a system exhibiting a congruent melting point

From the cooling curves shown in Fig. 6.6.1, the following information can be
derived.
From the cooling curve I and II of pure components, the points A and B
representing respectively the freezing points of A and B are obtained.
268 A Textbook of Physical Chemistry

The point C represents the composition of the compound AB. If this

compound is heated, its state point will move vertically along the line C C.
At C, the compound melts to give a liquid of composition AB. Alternatively,
the point C can be obtained from the cooling curve III of a liquid of
composition AB.
The addition of a solute in a solvent depresses the freezing point of the
latter. Keeping this in mind, the following facts are revealed:
(i) From the cooling curves IV and V of two liquid systems of B in A,
the points a and b representing respectively the start of freezing of A
are obtained.
(ii) From the cooling curves VI and VII of two liquid systems of A in B,
the points c and d representing respectively the start of freezing of B
are obtained.
(iii) If the component A or B is added to the liquid of composition AB, it will
depress the freezing point of the compound AB. Thus, from the cooling
curves VIII to XI, the points e, f, g and h representing respectively the
start of freezing of AB are obtained.
If a line passing through the points A, a and b is drawn, we get the freezing
point curve of A.
If a line passing through the points B, c and d is drawn, we get the freezing
point curve of B.
If a line passing through the points C, e and f, and C, g and h are drawn,
we get the freezing point curves of AB.
If the lines Aab and Cef are extended, they meet at the point O which gives
the eutectic point where solid A and solid AB are present in equilibrium
with liquid phase O.
Through the point O, the tie-line DOE can be drawn. A point on this line
represents solid A (point D) and solid AB (point E) in equilibrium with
liquid phase of composition corresponding to the point O.
The lines Cgh and Bcd on extending meet at O which gives the eutectic point
where solid B and solid AB are present in equilibrium with liquid phase O .
Through the point O , the tie line GO F can be drawn. A point on this line
represents solid B (point F), and solid AB (point G) in equilibrium with
liquid phase O
The systems at the arrest of temperature on the cooling curves IV, V, VIII
and IX are shown respectively by the points a , b , e and f on the line DE.
Similarly, the points, c , d , g , and h represent the systems at the arrest of
temperature on the cooling curves VI, VII, X and XI, respectively.

Labelling of the The labelling of the phase diagram shown in Fig. 6.6.1 is described in
Phase Diagram Table 6.6.1

Theoretical Aspects The phase diagram as given in Fig. 6.6.1 may be considered to be made up of
of Fig. 6.6.1 two simple eutectic diagrams placed side by side. To the left of the dividing line
CC , we have the simple eutectic phase diagram of A and AB, whereas to the
right of this line we have that of B and AB. Theoretically, the curves OC and O C
 Phase Diagrams of Two-Component Systems 269

Table 6.6.1 Labelling of Fig. 6.6.1

Location of the system Status of the system

A Freezing point of A
B Freezing point of B
C Freezing point of AB
AO Freezing point curve of A
BO Freezing point curve of B
OC and O C Freezing point curves of AB
O Eutectic point involving solid A, solid AB and liquid O
A-axis Solid A up to the point A, liquid A beyond A
B-axis Solid B up to the point B, liquid B beyond B
CC Solid AB, liquid AB beyond C
O Eutectic point involving solid B, solid AB and liquid O
DOE A system on this line represent solid A and solid AB
in equilibrium with liquid O
GO F A system on this line represents solid B and solid AB
in equilibrium with liquid O
Area AODA Solid A liquid (whose composition lies on AO)
Area BO FB Solid B liquid (whose composition lies on BO )
Area COEC Solid AB liquid (whose composition lies on OC)
Area CGO C Solid AB liquid (whose composition lies on CO )
Area below DOE Solid mixtures of A and AB
Area below GO F Solid mixtures of B and AB
Area above AOCO B Liquid

should meet at C to give a sharp point. Instead, we usually observe rounded

maximum at this point. This is due to the fact that the compound AB is not
very much stable at its melting point. It partly dissociates and the products
of dissociation in the liquid phase depresses the actual melting point of the
compound with the result that the curve has a flattened portion at the point C.
Examples A few examples of the systems exhibiting one compound formation with their
congruent melting points are given in Table 6.6.2.

FORMATION OF MORE THAN ONE COMPOUND

In many cases, two components on combination form more than one compound.
In such cases, the equilibrium phase diagram has a curve analogous to OCO
for each and every compound. Figure 6.6.2 displays one such case where the
two compounds AB2 and A2B are formed. The melting points of the compounds
are given by the points C and D, respectively. This phase diagram may by
considered to be formed by the union of three simple eutectic diagrams. These
are A – A2B, A2B – AB2 and AB2 – B. The interpretation of the diagram can
be carried out as usual and is shown in Fig. 6.6.2.
Examples A few examples of systems exhibiting the formation of more than one congruent
compound are given in Table 6.6.3.
270 A Textbook of Physical Chemistry

Table 6.6.2 Systems Exhibiting Compound Formation with

Congruent Melting Point

System† Com- Congruent Eutectic Eutectic

A m.pt. B m.pt. pound m.pt. temperature composition
ºC ºC ºC ºC
Gold 1 064 Tin 232 AB 425
Calcium Potassium
chloride 777 chloride 776 AB 754
Diphenyl- Benzo-
amine 52.8 phenone 47.7 AB 40.2 34.1 70 mol % A
31.9 25.5 mol % A
Urea 132 Phenol 42.5 AB2 61 60.0 65 mol % B
34.0 90 mol % B
Acetamide 79.4 Phenol 41 AB2 43 29 45 mol % B
30.2 90 mol % B
Urea 133 Resorcinol 110 AB 102.5 86.5 26 mol % B
84 78 mol % B
Benzamide 124.8 Resorcinol 108.5 AB 88.5 76.1 66.5 % B
80.2 34.5 % B
Phenol 42.5 Picric acid 122 AB 86 36.0
80.5

†
Temperatures mentioned here are the reported temperatures in literature.

Fig. 6.6.2 Formation of

two congruent
compounds
 Phase Diagrams of Two-Component Systems 271

Table 6.6.3 System Exhibiting more than One Congruent Compound Formation

System Compound Congruent Eutectic temperatures

A m.pt. / ºC B m.pt./ ºC m.pt./ºC ºC

K 63.6 Sb 613 485; 34.9 %

(A + A3B) of Sb
A3B 812
AB 605
400; 68 % Sb
(B + AB)
Ag 960.5 Sr 757
750
A 4B 781
693
A5B3 760
638
AB 680
645
A2B3 665
436

Example 6.6.1 For the water(A) and ethylene glycol(B) system, the following data were obtained from
the cooling curves of different compositions. The solid phase or phases that first appear
at the break or halt on cooling (that is, at the beginning of freezing processes) are given
in the last column:

Solution composition Freezing point /ºC Solid phases that separate

mol % of ethylene glycol out at the beginning of
freezing process

0 0 A
10.5 –14.1 A
14.1 –20.9 A
18.1 –28.3 A
24.9 –41.8 A
28.0 –51.2 A+B 2A
31.8 –49.6 B 2A
34.1 –49.6 B 2A
44.0 –58.6 B 2A
47.5 –63.3 B 2A + 3B 2A
50.2 –54.6 3B 2A
60.9 –40.7 3B 2A
66.0 –49.4 3B 2A + B
67.8 –45.3 B
75.3 –36.4 B
90.1 –22.4 B
100.0 –12.8 B

Plot the phase diagram and label it.

272 A Textbook of Physical Chemistry

Solution First of all, the points corresponding to the given data were located in a temperature
versus composition phase diagram. After this, the points corresponding to the given two
compounds B 2A and 3B 2A were located on the composition axis and the vertical
lines were drawn from these points as shown in Fig. 6.6.3.
From the given data, we find that the temperature at which solid A (ice) separates out
from the solution decreases as the amount per cent of B (ethylene glycol) in the solution
is increased. This decrease in temperature is continued up to the temperature –51.2 °C
where the solution composition is 28 mol per cent of B. At this temperature, two solids,
viz., A and B 2A, are separated out. On increasing the amount per cent of B from 28
to 31.8, we find that there is a separation of only B 2A and the freezing point of the
solution increases from –51.2 to – 49.6 °C. Obviously, the temperature –51.2 °C is the
lowest temperature where the two solids are separated out and thus must represent eutectic
temperature. So, we draw a horizontal line at this temperature starting from the pure solid
A line to the vertical line of solid B 2A. The solid B 2A has a congruent melting point
as the freezing curve of B 2A has a maximum right above the vertical line of solid
B 2A. A similar analysis indicates that the solid 3B 2A has a congruent melting
point. The temperature –63.3 °C and –49.4 °C where two solid phases separate out are
lowest ones and hence these are the eutectic temperatures. Thus, we draw horizontal lines
through these points meeting vertical lines of solids B 2A and 3B 2A, and solids 3B
2A and pure B, respectively.
Finally a smooth curve passing through the points of temperature versus composition
is drawn. This gives us the phase diagram of the present system. Labelling of different
areas is straightforward and is described in Fig. 6.6.3 itself.

+10

–10 Solution
qc/°C

–30
3B × 2A + solution
B × 2A + solution
A + solution B + solution

–50
Solids
Solids A + B × 2A
3B × 2A + B
B × 2A + 3B × 2A
–70
Fig. 6.6.3 Required Pure B × 2A 3B × 2A Pure
phase diagram A Amount per cent B

6.7 FORMATION OF A COMPOUND WHICH DECOMPOSES BEFORE ATTAINING ITS

MELTING POINT
Sometimes a solid compound formed by the union of two components is not
gruent Melting Point stable up to its true melting point. It decomposes before reaching the true
melting point into another solid, whose composition is different from that of the
 Phase Diagrams of Two-Component Systems 273

compound, and a solution. In fact, the compound does not possess a true melting
point. Whenever this happens, the compound is said to undergo a transition or
peritectic (Greek: melting around) reaction or incongruent fusion which may
be represented as
C2 C1 + soln (or melt)

where C 2 is the compound and C 1 is new solid formed as a result of

decomposition of C2. This new solid may be a new congruent or incongruent
compound or a pure component. Its melting point is always greater than that
of C2. The above reaction takes place at a definite temperature and is reversible
in nature. The composition of the melt is also definite. These facts are in
agreement with the phase rule requirement, as C = 2, P = 3 and F = C – P + 1
= 2 – 3 + 1 = 0. Thus, the system at this stage is invariant. The temperature
at which this reaction takes place is known as the incongruent melting point of
the compound or the peritectic temperature or the transition temperature.
Expected Phase Let the incongruent compound formed from A and B be AB2 and let it undergo
Diagram the following reaction

AB2 B + melt

The phase diagram of a system exhibiting above reaction has an appearance as

shown in Fig. 6.7.1.

Fig. 6.7.1 Phase diagram of a system exhibiting the formation of an incongruent compound AB2
274 A Textbook of Physical Chemistry

Description of the From the cooling curves shown in Fig. 6.7.1, the following information may be
Phase Diagram drawn.
From the cooling curves of pure components, the points A and B representing
respectively the freezing points of A and B are obtained.
From the cooling curves I and II of two liquid systems of B in A, the points
a and b representing respectively the start of freezing of A are obtained.
From the cooling curves III, IV and V of liquid systems of A in B, points
c, d and e representing respectively the start of freezing of B are obtained.
If a line passing through the points A, a and b is drawn, we get the freezing
point curve of A.
If a line passing through the points B, c and d is drawn, we get the freezing
point curve of B.
The point G on the composition axis corresponds to the composition of the
compound AB2. If this compound is heated, it remains in the solid phase
until the point G at temperature tp (peritectic temperature) is reached. At
the point G, the following peritectic reaction occurs:
t > tp
AB2 �
����
��� � B + melt
�
t <t p

Because of the separation of solid B from solid AB2, the melt will be less
rich in B as compared to the compound AB2. Thus, the point representing
the composition of the melt will lie left to the point G, say, at point C. Since
a tie line connects different phases in equilibrium, such a line drawn at the
point G (solid AB2) will have it ends at point C (representing the melt) and
F (representing solid B), respectively. Thus, a point anywhere on the tie line
CGF represents solid AB2 in equilibrium with solid B and the melt C. The
system here will be invariant (F = C + 1 – P = 2 + 1 – 3 = 0).
If heating of the compound AB2 at G is continued, more and more of the
compound decomposes into solid B and the melt C. The temperature of the
system will remain constant till whole of the compound AB2 has decomposed.
At this stage, the system becomes univariant (F = C + 1 – P = 2 + 1 – 2 = 1)
and thus heating will cause an increase in temperature, only solid B exists
in equilibrium with liquid phase. Hence, the curve Bcd which represents the
freezing point curve of B will end at the point C. The cooling curve III, IV
and V will exhibit an arrest of temperature when the respective system reaches
on the line CGF.
The state of the system at a temperature below the peritectic temperature
depends upon the overall composition of the system. We will have either solid
B and solid AB2 or solid AB2 and the liquid phase. This can be explained
on the basis of the peritectic reaction:
t < tp
B + melt �
����
��� � AB2
�
t >t p

The reaction between B and melt proceeds isothermally to form the compound
AB2 until either all the solid B or all the melt has been consumed. Thus,
we have
 Phase Diagrams of Two-Component Systems 275

(i) If solid B is present in excess amount than the requisite quantity that
is required for the formation of the compound with whole of the melt,
then solid B will remain in excess and hence the system will possess this
excess quantity of solid B and the solid compound AB2.
(ii) If solid B is present in deficient amount than the requisite quantity that is
required for the formation of the compound with whole of the melt, then
whole of solid B will disappear and the system will possess the excess
quantity of the melt and the solid compound AB2.
A point on the right of the line GG , i.e. from G to F, represents excess of solid
B and thus on cooling below the peritectic temperature, we would get a mixture
of solid B and solid AB2. The relative amounts of the two at a given point can
be determined with the help of the lever rule. On the other hand, a point between
CG represents the deficiency of solid B and thus on cooling just below the
peritectic temperature, we would get the compound AB2 in equilibrium with the
melt.
From the cooling curves VI and VII of the two liquid systems of compositions
slightly left to the point C, we get the points f and g which represent
respectively the start of freezing of the compound AB2. If a smooth line
passing through the points g and f is drawn, it will meet at the point C
because just below the line CG, we have an equilibrium between solid AB2
and the liquid phase.
If the line Cfg is extended on the other side, it meets the freezing point
curve Aab at the point O. This point represents an eutectic point involving
solid A and solid AB2 in equilibrium with liquid O. A tie line drawn from
the point O will start from the point D (representing solid A) and will end
at the point E (representing solid AB2).
The cooling curves I, II, VI and VII will exhibit an arrest of temperature
(horizontal line) at the eutectic temperature corresponding to the point O.
The cooling curve V besides exhibiting an arrest on the line CG will also
exhibit one more arrest corresponding to the line OE.
Sequence of Effects The phase diagram shown in Fig. 6.7.1 can be easily labelled by considering the
Produced on behaviour of the systems I, III and V during the cooling.
Cooling Liquid
System I The system will remain in the liquid phase till the point a is reached.
Mixtures
Solid A starts crystallizing at a and continues to crystallize till the point a is
reached. At a , both A and AB2 crystallize together from the liquid O.
System III The system will remain in the liquid phase till the point c is reached.
Solid B starts crystallizing at c and continues to crystallize till the point c is
reached. At c , the peritectic reaction starts and continues isothermally till whole
of the liquid C is exhausted. The system now contains solid mixture of B and
AB2 which will show smooth cooling.
System V The system will remain in the liquid phase till the point e is reached.
Solid B starts crystallizing at e and continues to crystallize till the point e is
reached. At e , the peritectic reaction starts and continues isothermally till whole
of solid B has disappeared. The system now contains solid AB2 in equilibrium
276 A Textbook of Physical Chemistry

with the melt C. Further cooling will result in more and more separation of AB2
with the composition of liquid moving along the line CO. This continues till
the point e is reached where the liquid composition corresponds to the point
O. Here, the solid mixture of A and AB2 crystallize isothermally without any
change in the composition of the liquid phase. This continues till whole of the
liquid phase is exhausted. The system now consists of a solid mixture of A and
AB2 which will show smooth cooling.
Labelling of the With the help of above analysis, the phase diagram shown in Fig. 6.7.1 can be
Phase Diagram easily labelled and is described in Table 6.7.1.
Table 6.7.1 Labelling of Fig. 6.7.1

Location of Status of the system

the system
A Freezing point of A
B Freezing point of B
F Peritectic temperature of AB2
AO Freezing point curve of A
BC Freezing point curve of B
CO Freezing point curve of AB2
O Eutectic point involving solid A, solid AB2 and liquid O
C Peritectic point involving solid B, solid AB2 and liquid C
A-axis Solid A up to the point A, liquid A beyond A
B-axis Solid B up to the point B, liquid B beyond B
GG Solid AB2
CGF A point on this line represents solid B and solid AB2 in
equilibrium with liquid C
DOE A point on this line represents solid B and solid AB2 in
equilibrium with liquid O
Area ADOA Solid A liquid (whose composition lies on AO)
Area BCFB Solid B liquid (whose composition lies on BC)
Area COEGC Solid AB2 liquid (whose composition lies on CO)
Area below GF Solid B and solid AB2
Area bellow DOE Solid A and solid AB2
Area above AOCB Liquid

Cooling Patterns The nature of the cooling curve will depend on the composition of the system.
We describe below the expected pattern for a few typical systems.

(i) Composition lying anywhere between AO or OC

Rapid cooling of Break at the appearance Slower cooling;
liquid of solid A or AB2 solidification continues

Cooling of solid mixture Horizontal portion;

of A and AB2 eutectic point

(ii) Eutectic composition

Rapid cooling of Horizontal portion Cooling of the solid
liquid eutectic point mixture of A and AB2
 Phase Diagrams of Two-Component Systems 277

(iii) Composition corresponding to the peritectic point C

Rapid cooling of Break at the appearance Slower cooling; appearance
liquid of solid of more and more of AB2

Cooling of solid mixture Horizontal portion;

of A and AB2 eutectic point
(iv) Composition anywhere between C and G
Rapid cooling of Break; appearance Slower cooling; appearance
liquid of solid B of more and more of solid B

Horizontal Slower cooling Horizontal portion

portion; eutectic appearance of more at the peritectic
temperature and more of AB2 temperature

Cooling of solid
mixture of A and AB2
(v) Composition anywhere between G and F
Rapid cooling Break; Slower cooling;
of liquid appearance of appearance of more and
solid B more of solid B

Cooling of solid Horizontal portion at

mixture of B and AB2 the peritectic temperature
These cooling patterns are also shown in Fig. 6.7.1.

Example 6.7.1 Na and K melt at 98 °C and 65 °C, respectively. They form one compound NaK which
decomposes at 10 °C to give a solid and a melt containing 60 mol % K. There is an eutectic
at – 5 °C and the eutectic composition is 75 mol % of K. Sketch the phase diagram and
level it.

Solution Analysis of data

(i) At 10 °C, the compound NaK decomposes to give a new solid and melt. Thus,
the temperature 10 °C must be a peritectic temperature. This also follows from
the fact that the compositions of the compound (50 mol % K) and the melt
(60 mol % K) are not identical. The new solid phase can be either Na or K. Since
K content of the melt is larger than of the compound NaK, we may conclude
that this new solid phase must be Na. This is also supported by the fact that K
appears at the eutectic point. So we draw a horizontal line at 10 °C from the
Na-axis right up to the melt composition. The vertical line representing NaK
compound will have its end at this horizontal line (Fig. 6.7.2).
(ii) Since K separates out at the eutectic point, we joins the melting point of K
with the point representing eutectic point.
(iii) Since Na appears on decomposition of the compound NaK, we join the melting
point of Na with the peritectic point representing the melt composition at 10 °C.
(iv) Finally, we join the peritectic point representing the melt with the eutectic point
and draw a horizontal line from the NaK-axis to the K-axis passing through the
eutectic point.
Labelling of the obtained phase diagram is straightforward and is included in
Fig. 6.7.2.
278 A Textbook of Physical Chemistry

120
1 Melt
2 Na + melt
90 3 NaK + melt
1 4 Na + NaK
5 K + melt
60 6 NaK + K
q/°C
2
30

5
0 3
4
6

Fig. 6.7.2 Required –30

Na NaK K
phase diagram Composition

Theoretical aspect The curves AO, OC and CB of Fig. 6.7.1 are the solubility curves for substances
of Fig. 6.7.1 A, AB2 and B, respectively. The entire phase diagram shown in Fig. 6.7.1 may
be considered to be made up of two systems, namely, A–B system and incomplete
subsystem A–AB2. Since B does not equilibrate with AB2 at temperatures above
the incongruent melting point Tp of the latter, the solubility curve BC is
determined by its composition in the system A–B. The solubility curves AO and
OC are determined by their compositions in the subsystem A–AB2. In other
words, if the compound AB2 is considered to exist as such in the form of a liquid
at temperatures below Tp, then the composition of A in the solubility curve AO
depends on the AB2 composition and the composition of AB2 in the solubility
curve OC depends on the A composition. Thus from the given data on TA*, TB*,
º A and fusHm,
fusH m, º B we can construct the simple eutectic diagram of the
system A-B and on this diagram we can superimpose the simple eutectic diagram
of the subsystem A–AB2 (after performing the appropriate amount fractions
transformation) constructed from the given TA*, fusHºm, A fusH m, º AB2 and the
* as shown in Fig. 6.7.3.
hypothetical melting point T AB 2

Examples A few examples of systems exhibiting incongruent melting points are given in
Table 6.7.2
Table 6.7.2 System Exhibiting Incongruent Melting Point

System
Compound
A B

Au Sb AB2
KCl CuCl2 2A B
Picric acid Benzene AB
Acetamide (79.9 ºC) Salicylic acid (156 ºC) AB tp = 70 ºC and
44 mol % salicylic acid
NaCl H 2O A 2B
Na2SO4 H 2O A 10B
 Phase Diagrams of Two-Component Systems 279

C
Temperature
A

Fig. 6.7.3 Construction O

of the phase diagram for
a system exhibiting
compound formation O¢
with an incongruent Pure AB2 Pure
melting point A Amount per cent B

Example 6.7.2 The Ca-Al system exhibits the following peritectic equilibrium:
CaAl3 CaAl2 + melt (14 mass % Ca)
Without using the lever rule, predict the nature and the respective masses of the system
just below the incongruent point for the systems: (i) 40 g Ca + 70 g Al, and (ii) 20 g Ca
+ 90 g Al.
Solution At temperature just below incongruent point, we will have either a mixture of solids
CaAl2 and CaAl3 or solid CaAl3 in equilibrium with the melt.
(i) Let the mass x of Ca be present in the form of the compound CaAl2 and let us assume
that the remaining mass of Ca (i.e. 40 g – x) be present in the form of the compound
CaAl3. Thus, the total quantity of Al present in these two compounds is (54/40) x +
(81/40) (40 g – x) and this must be equal to the given quantity of Al, i.e. 70 g. Thus, we
have

Ê 54 ˆ Ê 81 ˆ
Ë 40 ¯ x + Ë 40 ¯ (40 g - x ) = 70 g

Solving for x, we have x = 16.3 g

Thus the given system will consist of a mixture of CaAl2 and CaAl3 just below the
incongruent point with the following compositions.

Ê 54 ˆ
In CaAl2 Ca = 16.3 g Al = Ë ¯ ¥ 16.3 g = 22.0 g
40
280 A Textbook of Physical Chemistry

Ê 81 ˆ
and in CaAl3 Ca = (40 g – 16.3 g) = 23.7 g Al = Ë ¯ ¥ 23.7 g = 48.0 g
40
(ii) Let the mass x of Ca be present in the form of the compound CaAl2 and let us assume
that the remaining mass of Ca (i.e. 20 g – x) be present in the form of the compound
CaAl3. Then the total quantity of Al present in these two compounds is (54/40) x +
(81/40) (20 g – x) and this must be equal to the given mass of Al, i.e. 90 g. Thus, we have
Ê 54 ˆ Ê 81 ˆ
Ë 40 ¯ x + Ë 40 ¯ (20 g - x ) = 90 g
Solving for, x we get x = – 73.33 g
Since x is coming out to be negative, our assumption that the system consists of
CaAl2 + CaAl3 must be wrong. Let us now imagine that the system consists of melt +
CaAl3. Let us again suppose that the mass x of Ca be present in the form CaAl3 and
the remaining in the melt containing 14 mass % Ca. The total quantity of Al present in
these two forms is (81/40) x + (86/14)(20 g – x), and this must be equal to the given
quantity of 90 g. Thus, we have
Ê 81 ˆ Ê 86 ˆ
Ë 40 ¯ x + Ë 14 ¯ (20 g - x ) = 90 g
Solving for x, we get x = 7.98 g
Thus, we have
Ê 81 ˆ
Ca present in CaAl3 = 7.98 g Al present in CaAl3 = Ë ¯ (7.98 g) = 16.16 g
40

Ca present in the melt = (20 g – 7.98 g) = 12.02 g

Ê 86 ˆ
Al present in the melt = Ë ¯ (12.02 g) = 73.84 g
14
Hence the system just below the incongruent melting point consists of solid CaAl3 and
melt.

More than one In some systems, more than one compound exhibiting peritectic temperature is
Incongruent formed. Many systems are known where all the compounds formed have
Compounds incongruent melting points. A few examples are

K 2 SO 4 - CdSO 4 K 2 SO 4 ◊ 2CdSO4 , K 2 SO4 ◊ 3CdSO4

MgSO4 - H 2 O MgSO4 ◊ H 2 O, MgSO 4 ◊ 6H 2 O
MgSO 4 ◊ 7H 2 O, MgSO 4 ◊12H 2 O

Example 6.7.3 Construct a phase diagram of Au-Pb system from the following data:
(a) Melting point of Au = 1 063 ºC; m.pt. of Pb = 327 ºC.
(b) Compound Au2Pb decomposes at 418 ºC to give a liquid 44 mol % of Pb.
(c) Compound AuPb2 has a peritectic at 254 ºC and the melt is 71 mol % of Pb.
(d) Eutectic is at 215 ºC and is 84 mol % of Pb.
(e) No solid solution is formed.
Label the areas of the diagram.
 Phase Diagrams of Two-Component Systems 281

Solution Analysis of data

(i) At 418 °C, the compound Au2Pb (33.3 mol % Pb) decomposes to give a liquid
containing 44 mol % Pb. Since the compositions of solid and melt are different,
the temperature 418 °C must be a peritectic temperature. The solid phase which
appearas at this temperature must not be Pb as the Pb content in the melt is
higher than that in the compound Au2Pb. Since there is no other compound with
Au content larger than in the compound Au2Pb, it follows that this solid phase
must be Au. So, we join the melting point of Au with the point representing
the melt composition at 418 °C (Fig. 6.7.4). We also draw a horizontal line at
418 °C starting from the point representing melt composition to the Au-axis.
The vertical line representing Au2Pb compound must end at this horizontal line.
(ii) At 254 °C, we have a peritectic reaction where the compound AuPb2 decomposes
to give the melt containing 71 mol % of Pb. The solid phase appearing here
will not be pure Pb as the melt contains more of Pb than the compound AuPb2.
This also follows from the fact that Pb appears at the eutectic point. Since in
the composition range AuPb2-Au2Pb, there is no other compound, we conclude
that the new solid phase appearing at 254 °C must be the compound Au2Pb.
So, we join the points representing the two melts at 418 °C and 254 °C. We
also draw a horizontal line starting from the point of the melt at 254 °C to the
vertical line representing the compound Au2Pb. The vertical line representing
the compound AuPb2 must end at this horizontal line.
(iii) It is given that at the eutectic point Pb separates out. The second solid which
separates out here must be the compound AuPb2 as there exists no other compound
between the composition range of eutectic point and the compound AuPb2. So,
we join the melting point of Pb and the melt composition at 254 °C with the
eutectic point. We also draw a horizontal line through the eutectic point starting
from Pb-axis to the vertical line representing the compound AuPb2.
Now the labelling of the phase diagram is straightforward and is included in
Fig. 6.7.4.

Fig. 6.7.4 Required

phase diagram
282 A Textbook of Physical Chemistry

Systems Exhibiting In some systems, more than one compound is formed, some of them have congruent
both Congruent and melting points while others have incongruent melting points. A few examples
Incongruent are given in Table 6.7.3. The phase diagram of such a system will exhibit
Compounds characteristics of both congruent and incongruent melting points.

Table 6.7.3 Systems Exhibiting both Congruent and Incongruent

Compounds Formation

A B Congruent Incongruent
compound compound
Ca Al CaAl2 CaAl3
Mg Ni MgNi2 Mg2Ni
Na Bi Na3Bi NaBi

Figure 6.7.5 displays such a diagram for the Ca-Al systems. The phase diagram
may be considered to be made up of two simple systems of Ca-CaAl2 and
CaAl2-Al. The former shows a simple eutectic whereas in the latter a compound
CaAl3 with the incongruent melting point is formed. This way the labelling of
different areas becomes very simple and is shown in Fig. 6.7.5 itself.

Fig. 6.7.5 Phase diagram of Ca-Al system

 Phase Diagrams of Two-Component Systems 283

Example 6.7.4 A and B form two solid compounds A2B and AB2. The compound A2B melts at 800 °C
to give a liquid having the same composition as that of A2B. The compound AB2 melts
with decomposition at 700 °C to give solid B and a liquid containing 60 mol % of B. The
melting point of A is 500 °C and of B is 1 000 °C. No solid solutions are formed. Sketch
temperature versus amount fraction of the system and label it. Draw cooling curves for
a mixture containing 70 mol % of B.

Solution Analysis of data

(i) The compound A2B is a congruent compound as on melting it produces the
liquid of its own composition.
(ii) The compound AB2 is an incongruent compound as on melting it produces a
melt of composition different from its own composition.
(iii) Since solid B appears on melting AB2 at 700 °C, we join the melting point of
B with the melt composition at 700 °C. We also draw a horizontal line from
this melt composition to the pure B axis. The vertical line representing the
compound AB2 must end at this horizontal line.
(iv) Since the compound A2B melts congruently, on either sides of the vertical line
at A2B composition, we will have the solubility curves of A2B which will pass
through the melting point of the compound A2B.
(v) Since no other compound formation is there, we conclude that the systems A-A2B
and A2B-AB2 form the eutectic pairs. So, we draw the curves characteristic of
eutectic pairs as shown in Fig. 6.7.6.

Fig. 6.7.6

The labelling of the phase diagram is straightforward and is shown in Fig. 6.7.6
itself. The expected cooling curve for the given composition is also shown in the phase
diagram.
284 A Textbook of Physical Chemistry

6.8 FORMATION OF A COMPLETE SERIES OF SOLID SOLUTIONS

A solid may dissolve in another solid to give a solid solution. This solution is
perfectly homogeneous in character. X-ray examination of the lattice of solid
solution reveals that one constituent enters the lattice of the other and is uniformly
distributed throughout. There is no indication of two crystalline lattices as is in
the case of solid mixture and thus only one crystal lattice characteristic of the
solid solution is formed.
Theoretical Aspects Before drawing phase diagram of the present case, we consider the following
two facts regarding the general nature of the diagram.
(A) Shift in the freezing point of the solvent when a solid solution separates
out on cooling the solution An expression for the shift in freezing point of the
solvent when a solid solution separates out can be derived thermodynamically.
If we assume that the solid solution also behaves like an ideal solution, then the
chemical potentials of its constituents will be given by an expression analogous
to that of an ideal gaseous mixture or ideal liquid solution. This expression is
mi = mi* + RT ln xi
where μ *i is the chemical potential of the pure solid (at pressure p, if p = 1 bar,
μ *i º replaces μ *i ) and xi is the amount fraction of the constituent in the solid
solution.
The condition of phase equilibrium between the solid solution and liquid
solution for one of the components (say, solvent) is
m1(s) = m1(1) (6.8.1)
where the subscripts s and 1 within the brackets stand for solid and liquid,
respectively.
Now if it is assumed that both the solutions are ideal, we have
* + RT ln x *
m1(s) 1(s) = m1(1) + RT ln x1(1)

Rearranging the above relation, we have

* - m*
m1(1) D fus m1*
1(s)
R(ln x1(s) - ln x1(1) ) = = (6.8.2)
T T
where fus μ 1* is the molar free energy of fusion of the pure solvent at temperature
T and pressure p. Since
D fus m1* = D fus H1,* m - T D fus S1,* m

and at the normal melting point T1* of the pure solvent

D fus S1,* m = D fus H1,* m /T1*

we have
D fus H1,* m Ê T ˆ
D fus m1* = D fus H1,* m - T = D fus H1,* m Á 1 - (6.8.3)
T*
1 Ë T1* ˜¯
 Phase Diagrams of Two-Component Systems 285

Substituting Eq. (6.8.3) in Eq. (6.8.2), we get

D fus H1,* m Ê
R(ln x1(s) - ln x1(1) ) =
T ˆ * Ê - DTf ˆ
T ÁË 1 - T * ˜¯ = D fus H1, m ÁË T T * ˜¯ (6.8.4)
1 1

where Tf = T – T1*.
Equation (6.8.4) can be simplified under the following approximations.
(i) For a dilute solution, T will be very near to T1* so that the term T T1*
may be replaced by T1*2.
(ii) Again for dilute solution, we have
ln x1(s) = ln (1 - x2(s) ) - x2(s)
ln x1(1) = ln (1 - x2(1) ) - x2(1)

With these approximations, Eq. (6.8.4) reduces to

Ê - DTf ˆ
R( - x2(s) + x2(1) ) = D fus H1,* m Á
Ë T1*2 ˜¯

RT1*2 Ê x2(s) ˆ
or ( - DTf ) = x2(1) Á 1 - (6.8.5)
D fus H1,* m Ë x2(1) ˜¯

This expression can be written in terms of molality of the liquid solution

by using the following approximation.
n2(1) n2(1) n2(1) Ê n2(1) ˆ
x2(1) = = = Á M1 = mM1
n1(1) + n2(1) n1(1) m1(1) /M1 Ë m1(1) ˜¯
Thus, Eq. (6.8.5) modifies to

RT1*2 M1 Ê x2(s) ˆ
– DTf = m Á1 –
D fus H*
1, m Ë x2(1) ˜¯

or – DTf = Kf m(1 – K ) (6.8.6)

where K is the distribution coefficient and is given by

Amount fraction of the solute in the solid phase
K= (6.8.7)
Amount fraction of the solute in the solution
In Eq. (6.8.6), Tf = T – T1*. The value of Tf can be positive or negative
depending upon the value of K. Thus, we have

Condition for Tf to If K < 1, then T < T1* and thus a depression in freezing point of the solvent is
be Negative observed. The presence of 1 – K factor in Eq. (6.8.6) makes the numerical value
of Tf smaller than the value where only the solvent separates on cooling.
286 A Textbook of Physical Chemistry

Condition for Tf to If K > 1, then T > T1* and an elevation in the freezing point of the solvent is
be Positive observed.
These conclusions, in fact, are similar to those derived earlier for the
liquid-vapour system and thus may be regarded as the expressions for the
Konowaloff’s rule as applicable to solid-liquid system. These conclusions may
be stated as follows.
At any temperature, the liquid phase contains relatively more than
solid phase of that component whose addition to the solvent (or
solution) causes a decrease in the freezing point of the latter or
the solid phase contains relatively more than liquid phase of the
component whose addition to the liquid phase causes an increase
in the freezing point of the latter.
(B) Nature of cooling curve when a solid solution is formed Since in a solid
solution, the two components are completely miscible with each other and form
a homogeneous solution, it is obvious that such a solution will always constitute
a single solid phase. Thus, the system at the most can have two phases, namely,
liquid and solid solutions, in equilibrium with each other. According to the phase
rule, this system is univariant (F = C – P + 1 = 2 – 2 + 1 = 1). Thus, the value
of one variable has to be stated in order to define the system completely. This
variable may be temperature or composition of one of the solutions. In other
words, the equilibrium between solid and liquid solutions can exist at different
temperatures. For a given temperature, the compositions of the two solutions in
equilibrium will have fixed values. The cooling curves will exhibit two breaks
corresponding to the start of freezing of solid solution (where P changes from
1 to 2 and F changes from 2 to 1) and the end of freezing of solid solution
(where P changes from 2 to 1 and F changes from 1 to 2), respectively.
If the composition of solid and liquid solutions in equilibrium are identical,
the system becomes nonvariant (F = (C – r) + 1 – P = (2 – 1) + 1 – 2 = 0). Here,
the freezing or melting of solid solution takes place at a constant temperature.
Consequently, the cooling curve will exhibit an arrest at this temperature.
For real systems, Eq. (6.8.6) is expected to be applicable only in very dilute
Phase Diagrams solutions of A in B or B in A. Three types of phase diagrams may be distinguished
depending upon the values of KA in B (i.e. xA(s)/xA(1), A acting as a solute and B
as a solvent) and KB in A (i.e. xB(s)/xB(1), B acting as a solute and A as a solvent).
These are:
Ascending solid solution In this case KB in A > 1 and KA in B < 1 or vice versa.
The freezing point of A (or B) gradually increases as more and more of B (or
A) is added to it whereas that of B (or A) gradually decreases as more and more
of A (or B) is added to it. In such a case, freezing point of a solution containing
different amounts of A and B always lies between those of pure components.
Minimum type solid solution In this case KB in A < 1 and KA in B < 1. The
freezing points of both the components gradually decrease on addition of more
and more of the second component. Thus, the freezing point curves show
 Phase Diagrams of Two-Component Systems 287

downward trends at both ends of the phase diagram and meet each other at a
minimum point, i.e. the freezing point curve of such a system exhibits a minimum.
Maximum type solid solution In this case KB in A > 1 and KA in B > 1. The
freezing points of both the components gradually increase on addition of more
and more of the second component. Thus, the freezing point curves show upward
trends at both ends of the phase diagram and meet each other at a maximum point,
i.e. the freezing point curve of such a system exhibits a maximum.
We now draw the expected phase diagrams for the above three cases and
describe their main characteristics.

ASCENDING TYPE SOLID SOLUTION

Theoretical Aspects Before drawing the expected phase diagram, it is worthwhile to consider a few
general conclusions regarding the nature of liquidus and solidus curves. From
Eq. (6.8.4), we have
Ê1 1 ˆ
R(ln x1(s) - ln x1(1) ) = D fus H1,* m Á -
Ë T T1* ˜¯

Ê x1(1) ˆ D fus H1,* m Ê 1 1 ˆ

or ln Á ˜ = - Á - (6.8.8)
Ë x1(s) ¯ R Ë T T1* ˜¯
x1(1)
or = e- a (6.8.9)
x1(s)

D fus H1,* m Ê 1 1 ˆ
where a= Á -
R Ë T T1* ˜¯
Similarly, for the second component,
x2(1)
= e- b (6.8.10)
x2(s)

D fus H 2,* m Ê 1 1 ˆ
where b= Á -
R Ë T T2* ˜¯
Now in the liquid and solid phases, we will have
x1(1) = 1 - x2(1) (6.8.11)

x1(s) = 1 - x2(s) (6.8.12)

In Eq. (6.8.9), x1(s) may be rewritten in terms of x1(1) with the help of
Eqs (6.8.10), (6.8.11) and (6.8.12). Substituting Eq. (6.8.12) in Eq. (6.8.9), we
get
x1(1)
= e- a
1 - x2(s)
288 A Textbook of Physical Chemistry

In view of Eq. (6.8.10), the above equation becomes

x1(1)
-b
= e- a
1 - x2(l) /e
Now employing Eq. (6.8.11), we get
x1(1)
= e- a
1 - (1 - x1(1) )/e - b
Solving for xl(1), we have

e - a (e - b - 1) (6.8.13)
x1(1) =
e-b - e-a
Substitution of Eq. (6.8.13) in Eq. (6.8.9) gives
x1(1) e-b - 1
x1(s) = = (6.8.14)
e-a e-b - e-a

Finally, we have
e - b (e - a - 1)
x2(1) = 1 - x1(1) = (6.8.15)
e-a - e-b

e-a - 1
x2(s) = 1 - x1(s) = (6.8.16)
e-a - e-b

From Eq. (6.8.13)-(6.8.16), the following conclusions may be drawn:

None of the relationship is linear.
Since the relationship for x1(s) and x1(1) are different, it is evident that the
liquidus and solidus curves do not coincide except at T1* and T2*.
For a case in which T1* T T2*, we will have:
a is negative (thus e–a is greater than one)
and b is positive (thus e–b is less than one).
Hence from Eq. (6.8.13), we get

e - a (e - b - 1) negative
x1(1) = -b -a
= = positive
e -e negative
Similarly from Eqs (6.8.14)-(6.8.16), we get that x1(s), x2(1) and x2(s) all are
positive quantities. The same conclusions are obtained for the case T2* T T1*.
Thus, it may be concluded that if T lies in the interval between the melting
points of the two components, physically meaningful composition of the system
is obtained. Conversely, it follows that if the amount fraction of the system lies
between 0 and 1, then the temperatures of the liquidus and solidus curves lie
between the melting points of the two components.
 Phase Diagrams of Two-Component Systems 289

For a case in which T1* T T2*. Eqs (6.8.9) and (6.8.10) yield
x1(1) x2(1)
>1 and <1 (6.8.17)
x1(s) x2(s)

Similarly for a case T1* T T2*, we have

x1(1) x2(1)
<1 and >1 (6.8.18)
x1(s) x2(s)

Equations (6.8.17) and (6.8.18) demonstrate that the liquid is richer than solid
in the lower melting point component and the solid is richer than liquid in the
higher melting point component.
Depiction of the Keeping in mind the above conclusions the phase diagram of the ascending type
Phase Diagram solution is shown in Fig. 6.8.1.

Liquid
Liquidus B
a a

b b²
b b¢
c¢
Temperature

Temperature
c c² Solidus
d¢
d
d

Fig. 6.8.1 Phase A e

diagram for a system e
exhibiting continuous
series of solid solutions
with no maximum or
Time Pure Composition Pure
minimum A B

Cooling Behaviour The labelling of the phase diagram shown in Fig. 6.8.1 can be easily understood
of a Liquid System by first considering the expected cooling behaviour of the liquid solution
represented by the point a. On cooling, the state of the overall system will
move vertically downward along the isopleth abcde. The system remains in the
liquid phase till the point b is reached where the first crystal of solid solution
b starts appearing. The point b can be obtained by drawing a tie line from
the point b. Since the obtained solid solution is more rich in B as compared
to the liquid phase, the latter becomes less rich in B and thus its composition
point moves towards the A-axis. If the crystallization of solid solution is to be
continued, the temperature of the liquid phase has to be decreased so that its
state point moves on the line bc d A. For example, if the system has been cooled
290 A Textbook of Physical Chemistry

up to the overall state point c, the system now consists of solid solution c in
equilibrium with liquid solution c . The points c and c are obtained by drawing
a tie line from the point c. The relative amounts of solid solution c and liquid
solution c at c can be obtained by making use of the lever rule.
During the cooling of the system from b to d, the relative length of the
segment of tie line lying to the left of bcd increases indicating that the relative
amounts of the two solutions change in favour of solid solution, i.e. more and
more of solid solution solidifies during the cooling process. When the system
has been cooled to the point d, the last trace of liquid solution d remains to
be solidified and thus represents the point where practically whole of liquid
phase is solidified to produce solid solution d whose composition is the same
as that of starting liquid solution (i.e. point a). Further cooling from d to e,
merely decreases the temperature of solid solution.
Conclusion From the above analysis, the following conclusions can be drawn.
A point within the area AbBdA represents a solid solution in equilibrium
with a liquid solution. Their compositions are given by the intersection points
of the tie line (horizontal line) drawn from the given point with those of solidus
(AdB) and liquidus (AbB) curves, respectively. The relative amounts of the two
are given by the lever rule. On gradually cooling, the composition of liquid
solution moves along BbA and that of solid solution along the curve BdA.
Labelling of the Table 6.8.1 describes, in brief, the phase diagram shown in Fig. 6.8.1.
Phase Diagram

Table 6.8.1 Description of the Phase Diagram shown in Fig. 6.8.1

Location of the Status of the system

system

A Freezing point of A
B Freezing point of B
Curve AbB Freezing point curve of solid solution
Curve AdB Fusion point curve of solid solution
Area above AbB Liquid
Area below AdB Solid solution
Area AbBdA A point within this area represents a solid solution (whose
composition lies on the curve AdB) in equilibrium with a
liquid solution (whose composition lies on the curve AbB).

Fractional Since the present system has phase diagram very similar to that of liquid-vapour
Crystallization system exhibiting ideality or little deviations from ideality, the two components
can be separated from each other following the method of fractional
crystallization—a method very similar to the fractional distillation employed in
the liquid-vapour system. This method involves alternative cooling and heating
repeatedly which results in the preferential separation of the two constituents—
the solid carries more of the component of higher freezing point and the liquid
carries lesser of this constituent (or larger of the other constituent of lesser freezing
 Phase Diagrams of Two-Component Systems 291

point). Finally, we can collect the pure component of larger freezing point in the
solid form and the component of lesser freezing point in the liquid form.
The technique of zone refining is based on the principle of fractional
crystallization. It is employed to remove impurities from a given substance. The
end products obtained in fractional crystallization have been described above.
The principle of fractional crystallization may be outlined again in order to
facilitate the description of the technique of zone refining.
Principle Consider a solid solution of composition e as shown in Fig. 6.8.1.
Let it be heated to the point c. At this point, the system consists of two phases,
liquid solution c and solid solution c in equilibrium with each other. Let the
two phases be separated and the solid solution c be heated separately to the
point b . Again we get two phases, a liquid solution b and a solid solution b .
Again let the two phases be separated and the solid phase be heated separately
and so on. Ultimately, we will get the solid phase consisting of pure B. The
liquid solutions at different stages may be mixed together, solidified and
subjected to the same sequence of steps as discussed above. At each stage, the
preferential separation of the two constituents takes place, solid carries more of
the constituent of higher freezing point and the liquid carries lesser of this
constituent (or more of the other constituent of lesser freezing point). Carrying
the above process repeatedly will result into the separation of the two
constituents—the constituent of higher freezing point in the solid phase and
that of lesser freezing point in the liquid phase.
Process Now the process of zone refining may be described. The substance to
be purified is taken in the form of a narrow cylinder and is heated in a narrow,
disc-like zone which is swept from one end of the sample to the other (Fig. 6.8.2).
Heater
Furnace wall

A B

Purified
solid

Impure
Molten zone solid material

Fig. 6.8.2 Schematic

representation of a zone Movable heater
refining apparatus

Immediately in front of the heater, the solid melts forming a liquid zone
which carries more of impurity provided it has a lower melting point. As the
heater moves forward this liquid zone also moves forward and immediately at
the back of the heater, we get a solid which carries lesser of impurity. The liquid
292 A Textbook of Physical Chemistry

zone as it moves forward becomes more and more enriched in the impurity
as it is preferentially partitioned into the liquid phase. One pass of the heater
from one end of the substance to the other may have the effect of reducing the
impurity content only slightly. In order to get rid of more and more of impurity,
the heater is passed repeatedly from one end to the other.
Examples Substances of similar constitution or closely related elements usually form solid
solutions of the the type discussed above. A few examples are: Co-Ni, Au-Ag,
Au-Pt, AgCl-NaCl, PbCl2-PbBr2, and naphthalene- -naphthol.

Example 6.8.1 The following data were observed for Si-Ge system:
% Si (by mass) 0 10 25 40 45 62 75 80 90 100
(θc/°C) at which 940 1062 1160 1235 1252 1310 1350 1370 1395 1412
first solid appears
(θc/°C) at which 940 697 1010 1070 1090 1170 1245 1275 1340 1412
complete solidi-
fication occurs
(a) Plot the phase diagram and indicate the phases present in each region.
(b) What is composition of the phases present when the solid mixture containing 50
mass % Si is heated at 1200 °C.
(c) Explain, how you would attain a pure Si from a solid mixture containing 70 mass %
Si.

Solution (a) The phase diagram plotted from the given data is shown in Fig. 6.8.3. The present
system of Si-Ge will form a complete series of solid solutions.
(b) The phases present in equilibrium with each other when the solid mixture containing
50 mass % Si is heated to 1200 °C are:
Liquid solution containing 32.5 mass % Si
Solid solution containing 70 mass % Si.
(c) Pure Si can be obtained by the method of fractional crystallization. The residue will
finally consist of pure Si.

Fig. 6.8.3 Required

phase diagram
 Phase Diagrams of Two-Component Systems 293

MINIMUM TYPE SOLID SOLUTION

Depiction of the Systems with these characteristics have phase diagram as shown in Fig. 6.8.4.
Phase Diagram

Liquid B

A
b
b¢
Temperature

s
1+
Liquidus +
1

us
s

lid
So
c¢ c

Fig. 6.8.4 Phase

M
diagram of a system
exhibiting continuous Solid solution
series of solid solutions
with a minimum freezing Pure Composition Pure
point A B

Labelling of the The labelling of Fig. 6.8.4 is shown in Table 6.8.2.

Phase Diagram

Table 6.8.2 Description of the Phase Diagram shown in Fig. 6.8.4

Location of the system Status of the system

A Freezing point of A
B Freezing point of B
M Minimum freezing point of the liquid solution. Here, the
composition of liquid and solid solutions are identical.
The system here is nonvariant. Thus freezing or fusion
takes place at constant temperature. This is exhibited by
the arrest of temperature in the cooling curve
Area above Liquid
Ab MbB
Area below Solid solution
Ac McB
Area Solid solution (composition lies on Ac M) in equili-
Ab Mc A brium with liquid solution (composition lies on Ab M)
Area Solid solution (composition lies on BcM) in equili-
BbMcB brium with liquid solution (composition lies on BbM)
294 A Textbook of Physical Chemistry

Comment on the Phase diagram of this system is similar to that of the liquid-vapour system
Phase Diagram exhibiting positive deviation from ideality (Fig. 4.16.1) and thus has characteristics
resembling those of the liquid-vapour system. Depending on the composition, the
fractional crystallization of this system will yield either pure A or pure B as a solid
phase (to the left to point M, pure A and to the right of M, pure B) and a liquid of
composition corresponding to the minimum freezing point M.
Examples Table 6.8.3 includes a few examples of a system exhibiting minimum type solid
solution.
Table 6.8.3 Systems Exhibiting Continuous Series of Solid Solutions with
a Minimum Freezing Point

System Minimum point M

m.pt. m.pt. Temperature

A ºC B ºC ºC Composition
Cu Mn
Mn Ni
Co Mn
HgBr2 HgI2
KC1 781 AgCl 748 716 60 mol % B
p-dichloro- 52.8 p-chloro- 53 41 50 mol % B
benzene iodobenzene
Chloro- – 44 iodobenzene –29 –51.3 39.02 mass
benzene % B
Stilbene 123.5 Hydrazo- 130.5 93 52.26 mass
benzene % B
Dibenzyl 52.5 Hydrazo- 130.5 45.9 13.8 mass
benzene %B

In most cases, the two members of a system are found to have the same
crystal structure (isostructural or isomorphic). Thus, in each of the solid solution-
liquid fields shown in Fig. 6.8.4, it is the same solid phase that coexists with
liquid. Besides, as indicated above, both the solidus and liquids curves are
continuous, which meet each other only at a single point.

MAXIMUM TYPE SOLID SOLUTION

Depiction of the In this case, the addition of one component into another elevates the freezing point
Phase Diagram of the latter and thus the phase diagram has an appearance as shown in Fig. 6.8.5.
Description of the diagram is straightforward and is not given here.
Comment on the The phase diagram shown in Fig. 6.8.5 resembles that of a liquid-vapour system
Phase Diagram exhibiting negative deviation from ideality (Fig. 4.16.2) and thus has characteristics
similar to those of a liquid-vapour system. Depending on the initial composition,
the fractional crystallization will yield either pure A or pure B in the liquid phase
(to the left of point M, pure A and to the right of point M pure B) and a solid phase
of composition corresponding to the maximum freezing point M.
 Phase Diagrams of Two-Component Systems 295

Fig. 6.8.5 Phase

diagram for a system
exhibiting continuous
series of solid solutions
with a maximum

Examples Very few examples of systems yielding a continuous solid solutions and having
a freezing-point curve with a maximum are known. A few examples are d- and
l-monobornyl esters of malonic acid.
The two constituents are the d- and l-forms of the same optically active
compound. Since both of them have the same melting point, the phase diagrams
are symmetrical with the maximum at a midway point. It has been suggested
that the maximum may represent a racemic compound.

Slope of T versus x For a binary mixture, Gibbs-Duhem equation is

Curve at Azeotropic
S dT - V dp + nA dm A + nB dm B = 0 (6.8.19)
Temperature
For a unit amount of mixture, we have
Sm dT - Vm dp + xA dm A + xB dm B = 0 (6.8.20)
Using the expression μ = μ* + RT ln a (where a is activity), Eq. (6.8.20) may
be written as
Sm dT - Vm dp + RT [xA d ln aA + xB d ln aB ] = 0 (6.8.21)
For a system of two binary solutions in equilibrium, Eq. (6.8.21) holds good
separately for both the solutions. Hence, we write
Sm(a ) dT - Vm(a ) dp + RT [xA(a ) d ln aA + xB(a ) d ln aB ] = 0 (6.8.22)

Sm(b ) dT - Vm(b ) dp + RT [xA(b ) d ln aA + xB(b ) d ln aB ] = 0 (6.8.23)

Note that the chemical potential and thus activity of A (as well as those of B)
in both the solutions will have the same value as the component A is in
equilibrium between the two solutions.
296 A Textbook of Physical Chemistry

Subtraction of Eq. (6.8.23) from Eq. (6.8.22) gives

D trs Sm dT - D trsVm dT + RT [xA(a ) - xA(b ) ] d ln aA
+ RT [xB(a ) - xB(b ) ] d ln aB = 0 (6.8.24)
where D trs Sm = Sm(a ) - Sm(b ) and D trsVm = Vm(a ) - Vm(b )
Since the solutions are at equilibrium at temperature T, we will have
D H
D trs Sm = trs m
T
With this, Eq. (6.8.24) may be written as
D trs H m D trsVm
2
dT - dp + [xA(a ) - xA(b ) ] d ln aA
RT RT
+ [xB(a ) - xB(b ) ] d ln aB = 0 (6.8.25)
At azeotropic temperature
xA(a ) = xA(b ) and xB(a ) = xB(b )
With these, Eq. (6.8.25) become
D trs H m D trsVm
2
dT - dp = 0 (6.8.26)
RT RT
From Eq. (6.8.26) is follows that
Ê ∂T ˆ Ê ∂p ˆ
ÁË ∂x ˜¯ = 0 and ÁË ∂x ˜¯ = 0
B p B T

Thus, the slope of T versus xB curves in Figs (6.8.4) and (6.8.5) will have zero
slope at the point M.

6.9 FORMATION OF PARTIAL MISCIBLITY IN THE SOLID STATE LEADING TO STABLE

SOLID SOLUTIONS
Depiction of the In some cases, solids are miscible with each other in limited range of concentrations.
Phase Diagram Outside this range, they form two solid solutions in equilibrium with each other.
These are saturated solutions of A in B and B in A. This phenomenon is quite
analogous to that of the partially miscible liquids and thus the phase diagram
of the present system has an appearance similar to that of Fig. 4.18.8. This
diagram can be relabelled by writing liquid and solid in places of vapour and
liquid, respectively (Fig. 6.9.1).
This type of diagram is observed only when KB in A < 1 and KA in B < 1,
i.e. the freezing point of A (or B) is lowered when B (or A) is added to it.
Construction of the From the cooling curves of pure components, the points A and B
Phase Diagram representing respectively the freezing temperatures of A and B are obtained.
From the cooling curves I and II of two systems of B in A, the points a
and b indicating respectively the start of freezing of solid solution of B in A
(hereafter referred to as S1) and a and b indicating respectively the end of
solidification of S1 are obtained.
From the cooling curve III, the point c representing the start of freezing of
solid solution S1 is obtained.
 Phase Diagrams of Two-Component Systems 297

Fig. 6.9.1 Phase diagram exhibiting partial miscibility in the solid state with the eutectic point

If a line passing through A, a, b and c is drawn, we get the freezing point

curve Aabc of solid solution S1. Similarly, if a line passing through A, a
and b is drawn, we get the fusion point curve of solid solution S1.
From the cooling curves IV and V of two systems of A in B, the points d
and e indicating respectively the start of freezing of solid solution of A in
B (hereafter referred to as S2) and d and e indicating respectively the end
of solidification of S2 are obtained.
From the cooling curve VI, the point f representing the start of freezing of
solid solution S2 is obtained.
If a line passing through B, d, e and f is drawn, we get the freezing point
curve Bdef of solid solution S2. Similarly, if a line passing through B, d
and e is drawn, we get the fusion point curve Bd e of solid solution S2.
Along the line Aabc, liquid solution is in equilibrium with solid solution S1
whose composition lies on the line Aa b . For a given point on Aabc, the
composition of solid solution in equilibrium is represented by the intersection
point of the tie line (horizontal line) drawn from the given point with the
line Aa b . Similarly, the lines Bdef and Bd e , respectively, describe the
compositions of liquid solution and solid solution S2 in equilibrium with
each other.
If the lines Aabc and Bdef are extended they meet at the point O. Here both
solid solutions S1 and S2 will be in equilibrium with liquid phase O. The
compositions of S1 and S2 can be obtained by extending the lines Aa b and
Bd e up to the points where they meet the tie line (horizontal line) drawn
from the point O. Thus, the points C and D shown in Fig. 6.9.1 represent
the two solid solutions S1 and S2 in equilibrium with liquid O.
298 A Textbook of Physical Chemistry

A system on the line COD contains three phases in equilibrium and, according
to the phase rule, is an invariant system. Hence, the temperature corresponding
to the line COD will have a fixed value. Moreover, solidification of solid
solutions S1 and S2 from the liquid O occurs isothermally. Consequently,
the cooling curves III and VI exhibit arrest of temperature at points c and
f , respectively. The overall composition of solid phase (i.e. total amount of
S1 and S2) separated on the line COD is the same as that of liquid phase,
vis-à-vis, the composition of liquid phase remains unchanged.
When the solidification of liquid O is complete, the system contains two
solid solutions C and D in equilibrium with each other. According to the
phase rule, the system becomes univariant (F = C + 1 – P = 2 + 1 – 2 = 1).
Consequently, the system will exhibit cooling during which the compositions
of solid solutions S1 and S2 change along the lines CE and DF, respectively.
Effect produced on The labelling of the phase diagram can be done easily with the help of the
Cooling a System above discussions. However, to make it more understandable, it is worth
considering the sequence of effects that is produced during the cooling of the
system III.
Up to the point c, the system remains in the liquid phase.
At c, the solid solution corresponding to the point c1 starts precipitating.
Since the solid solution c1 is rich in A as compared to the liquid phase c,
the composition of the latter moves towards B axis. If the crystallization of
S1 is to be continued, the temperature of the liquid phase has to be lowered
so that its composition moves on the line cO. Thus, on cooling the system
from c to c , the composition of liquid phase moves along cO whereas that
of solid phase along c1C. The relative amounts of solid and liquid solutions
at any stage of cooling can be determined with the help of the lever rule.
For example, if the system is cooled up to the point g, then we have
Amount of solid solution g ¢ gg ≤
=
Amount of liquid solution g ≤ gg ¢
When the system is cooled up to the point c , the solid solution C is in equili
-brium with liquid O. The relative amounts of the two solutions are given by

Amount of solid solution C Oc ¢

=
Amount of liquid solution O c ¢C
If the cooling is continued, both S1 and S2 are separated isothermally from the
liquid O. Since now solid contains both S1 and S2, the point representing solid
phases moves from C towards c as more and more solid solutions are solidified.
When this point is reached at c , whole of liquid solution is solidified.
From c to c , only cooling of solid solutions S1 and S2 takes place. The
composition of the former moves along CE whereas that of the latter moves
along DF.
Labelling of the Table 6.9.1 describes the labelling of Fig. 6.9.1
Phase Diagram
 Phase Diagrams of Two-Component Systems 299

Table 6.9.1 Labelling of the Diagram shown in the Fig. 6.9.1

Location of Status of the system

the system
A Freezing point of A
B Freezing point of B
AO Freezing point curve of solid solution S1
AC Fusion point curve of solid solution S1
BO Freezing point curve of solid solution S2
BD Fusion point curve of solid solution S2
O Eutectic point where solid solutions S1 and S2 represented by C
and D, respectively, are in equilibrium with the liquid O.
CE and DF Compositions of the two conjugate solid solutions S1 and S2
Area to the
left of ACE Solid solution S1
right of BDF Solid solution S2
Area AOCA A point in this area represents a solid solution S1 in equilibrium
with a liquid phase; composition of the former lies on the line AC,
whereas that of the latter on the line AO. These compositions can
be determined by drawing a tie line from the given point.
Area BODB A point in this area represents a solid solution S2 in equilibrium
with a liquid phase; composition of the former lies on the line BD
whereas that of the latter on the line BO.
Area within the A point within this area respresents two conjugate solutions
lines CE and DF S1 and S2 in equilibrium with each other. The compositions of
these two solutions are given by the two intersection points of
the tie line drawn from the given point with the lines CE and DF,
respectively.
Area above AOB Liquid

Cooling Patterns The nature of the cooling curve will depend on the composition of the system.
The following are a few typical patterns.
(i) Composition anywhere between AC (or BD):
Rapid cooling of Break at the appearance Slower cooling; solidifica-
liquid of solid solution tion continues

Cooling of solid Break; solidification

solution completes
(ii) Composition anywhere between CO (or DO):
Rapid cooling of Break at the appearance Slower cooling; solidifica-
liquid of solid solution tion continues

Cooling of the two Horizontal portion at

conjugate solutions eutectic point
(iii) Eutectic composition:
Rapid cooling of Horizontal portion at Cooling of the two
liquid eutectic point conjugate solid solutions
These cooling patterns are shown in Fig. 6.9.1
300 A Textbook of Physical Chemistry

Fractional Results of fractional crystallization are also very similar to those of fractional
Crystallization distillation of the liquid-vapour system showing partial miscibility in the liquid
phase. We give below the end products that are obtained in fractional crystallization
of the present system.
(i) When the original composition of the system lies to the left of the
eutectic point O:
Solid phase—pure A,
and liquid phase—a liquid of eutectic composition.
(ii) When the original composition of the system lies to the right of the
eutectic point O:
Solid phase—pure B,
and liquid phase—a liquid of eutectic composition.
(iii) When the original composition of the system is the eutectic composition:
In this case, no fractional crystallization is possible as the melt has the same
composition as that of the solid phase.
Examples A few examples of system exhibiting the phase diagram of Fig. 6.9.1 are given
below: Au–Ni, Bi–Pb, Cd–Sn, Fe–Cr, naphthalene-monochloroacetic acid,
azobenzene-azoxybenzene, and dibenzyl and benzylphenate.
Theoretical Aspects Phase diagram of Fig. 6.9.1, in fact, lies between those for components which are
of Fig. 6.9.1 completely miscible in the solid state with the minimum freezing point and those
which form completely immiscible mixture in the solid phase. If the solids in
Fig. 6.9.1 are assumed to become more and more miscible, points C and D will
eventually coincide and the phase diagram will resemble Fig. 6.8.4—a phase
diagram in which solid solution with a minimum freezing point is formed. On
the other hand, if the two solids become less miscible, points C and D will
recede from each other and eventually lie on the axes of pure A and pure B,
respectively, and the phase diagram will resemble Fig. 6.4.1, which respresents
the separation of solid mixture.
Limited solid-phase solubility may result because of the contamination of
each of the two members of a binary system by the other. If we assume that the
two members A and B have different crystal structures, then if B contaminates
A, the atoms of B in A conform to the crystal structure of A. Conversely, if A
contaminates B, the atoms of A in B conform to the crystal structure of B. As
mentioned above, if the contaminations are vanishingly small, phase diagram
of the system will have the major characteristics of a simple eutectic system. If
the two substances exhibit considerable solid solubility in each other, then the
liquidus and solidus of A and B regions acquire the appearances of descending
solid solutions of A in B, and B in A, respectively. Since the crystal structures
of the two members are identical in the solid solution region, it is expected that
the contaminated phase in this region is present in the metastable form whose
crystal structure is identical with that of the primary phase. Thus, the entire
phase diagram of Fig. 6.9.1 may be visualized to be formed as a result of two
intersecting descending diagram as shown in Fig. 6.9.2.
 Phase Diagrams of Two-Component Systems 301

Fig. 6.9.2 Metastable

extensions of the liquids
and solidus curves of a
system exhibiting limited
solubility with eutectic
temperature

To be specific, let the crystal structures of A and B be and , respectively.

The solid solution in the regions ACE and ACO of Fig. 6.9.1 has -structure
of primary phase A. The component B in this solid solution has the metastable
-structure whose metastable melting point is represented by the point F in
Fig. 6.9.2. Thus the region CAO may be considered to be a portion of complete
descending solid solution diagram AOFCA. Similarly, the regions BOD and BDF
of Fig. 6.9.1 have a solid solution of -structure and is formed as a result of
stable -structure of B and metastable -structure of A. The metastable melting
point of the latter is shown by the point E in Fig. 6.9.2. Hence the region
OBD may be considered to be a portion of complete descending solid solution
diagram BOEDB. From Fig. 6.9.2, it is obvious that a system will exhibit the
phase diagram of Fig. 6.9.1 only when the metastable melting points E and F
lie below the stable melting points A and B, respectively.

6.10 FORMATION OF PARTIAL MISCIBLITY IN THE SOLID PHASE LEADING TO SOLID

SOLUTIONS STABLE UP TO A TRANSITION TEMPERATURE
Instead of exhibiting an eutectic, two solid solutions may undergo a peritectic
reaction of the type
S1 S2 + Liquid solution
The above reaction takes place at a constant temperature since the system
with three phases in equilibrium is an invariant system.
The phase diagram exhibiting the above peritectic reaction has an appearance
as shown in Fig. 6.10.1. This type of diagram is observed only when KB in A > 1
302 A Textbook of Physical Chemistry

Fig. 6.10.1 Phase diagram exhibiting partial miscibility in the solid state with a peritectic transition

and KA in B < 1, i.e., the freezing point A is elevated when B is added to it and
that of B is lowered when A is added to it (or vice versa).
Construction of the From the cooling curves of pure components, the points A and B representing
Phase Diagram respectively the freezing temperatures of components A and B are obtained.
From the cooling curves I and II of two systems of B in A, the points a and
b representing respectively the start of freezing of solid solution S1 and the
points a and b representing respectively the end of freezing of solid solution
S1 are obtained.
If a line passing through the points A, a and b is drawn, we get the
freezing point curve Aab of solid solution S1. Similarly, if a line passing
through the points A, a and b is drawn, we get the fusion point curve Aa b
of solid solution S1.
From the cooling curves III and IV of two liquid systems of A and B, the
points c and d representing respectively the start of freezing of solid solution
S2 and the points c and d representing respectively the end of freezing of
solid solution S2 are obtained.
From the cooling curves V and VI of two systems of A and B, the points
e and f representing respectively the start of freezing of solid solution S2 are
obtained.
If a line passing through the point B, c, d, e and f is drawn, we get the
freezing point curve Bcdef of solid solution S2. Similarly, if a line passing
through the points B, c and d is drawn, we get the fusion point curve
Bc d of solid solution S2.
 Phase Diagrams of Two-Component Systems 303

Since the equilibrium

Solid solution S1 (on Aa b ) liquid solution (on Aab)
exists at lower temperatures whereas the equilibrium
Solid solution S2 (on Bc d ) liquid solution (on Bcd)
exists at higher temperatures, the peritectic reaction
S1 + solution S2 + solution
will take place at a temperature (peritectic) which will lie in between the
freezing temperatures of pure components A and B. The composition of the
associated liquid phase will have a fixed value since the peritectic reaction
involves three phases in equilibrium (F = C + 1 – P = 2 + 1 – 3 = 0).
Since the curves Aab and Bcdef describe respectively the start of freezing
of solid solutions S1 and S2, these two curves on extending will meet at
point O which describes the composition of the liquid phase in equilibrium
with solid solutions S1 and S2. The compositions of two solid solutions will
be given by the intersection points C and D of the tie line drawn from the
point O with the extensions of the fusion point curves Aa b and Bc d ,
respectively. Thus, a point on the line OCD represents a system where solid
solution S1 of composition C, solid solutions S2 of composition D and liquid
solution of composition O exist together in equilibrium with one another.
Since a system on the line OCD has three phases in equilibrium, it will be
invariant. Thus, so long three phases remain in equilibrium, the temperature
of the system will remain constant. Thus, the cooling curves V and VI will
exhibit a complete arrest of temperature at the points e and f , respectively.
The point C on the line OCD represents solid solution S1 in equilibrium
with liquid O. If this system is heated gradually, more and more of this solid
solution is converted isothermally into solid solution S2 and liquid solution
O. Thus, at a temperature greater than the peritectic temperature the system
will consist of a solid solution S2 in equilibrium with a liquid solution. In
fact, a system anywhere on the line OCD on heating will yield a system of
solid solution S2 (whose composition lies on the curve BD) in equilibrium
with a liquid solution (whose composition lies on the curve BO).
The state of the system at a temperature below the peritectic temperature
depends upon the overall composition of the system. We will have either
solid solutions S1 in equilibrium with solid solution S2 or solid solution S1
in equilibrium with a liquid solution. This can be explained on the basis of
the peritectic reaction:

t < tp
S2 + liquid O �
����
��� � S1
�
t >t p

The reaction between S2 and liquid O proceeds isothermally to form the

solid solution S1 until either all the solid solution S2 or all the liquid O has
been consumed. We have
304 A Textbook of Physical Chemistry

(i) If solid solution S2 is present in excess amount than the requisite quantity
that is required for the formation of the solid solution S1 with whole of liquid
O, then solid solution S2 will remain in excess and hence the system will
possess this excess quantity of S2 and the solid solution S1. This happens
when the point representing S2 solution lies in between the points C
and D. Thus, a system below the line CD represents solid solution S1 in
equilibrium with solid solution S2.
(ii) If solid solution S2 is present in deficient amount than the requisite quantity
that is required for the formation of S1 with whole of the liquid O; then
whole of solid solution S2 will disappear and the system will possess the
excess quantity of liquid phase and the solid solution S1. This happens
when the point representing S2 solution lies in between the points O
and C. Thus, the system below the line OC represents solid solution S1
(whose composition lies on the line CA) in equilibrium with liquid phase
(whose composition lies on the line OA).

Labelling of the With the help of above analysis, the labelling of the phase diagram can be easily
Phase Diagram done and is described in Table 6.10.1.

Table 6.10.1 Labelling of the Phase Diagram shown in Fig. 6.10.1

Location of Status of system

the system
A Freezing point of A
B Freezing point of B
AO Freezing point curve of solid solution S1
AC Fusion point curve of solid solution S1
BO Freezing point curve of solid solution S2
BD Fusion point curve of solid solution S2
O Composition of liquid phase at the peritectic temperature
OCD A system on this line represents a solid solution S1 of
composition C, a solid solution S2 of composition D, and
a liquid solution O in equilibrium with one another
CE and DF Compositions of two conjugate solutions S1 and S2
Area AOCA A point in this area represents a solid solution S1 (whose
composition lies on the line AC) in equilibrium with a
liquid phase (whose composition lies on the line AO)
Area BODB A point in this area represents a solid solution S2 (whose
composition lies on the line BD) in equilibrium with a
liquid phase (whose composition lies on the line BO)
Area within the A point in this area represents a solid solution S1 (whose
lines EC, CD and composition lies on the line EC) in equilibrium with a solid
DF solution S2 (whose composition lies on the line DF)
Area within the Solid solution S1
lines AC and CE
Area to the right of BDF Solid solution S2
Area above the curve AOB Liquid
 Phase Diagrams of Two-Component Systems 305

Cooling Patterns The nature of cooling curve will depend upon the composition of the system.
A few typical cases shown in Fig. 6.10.1 are described below.
(i) Composition anywhere between A and O
Rapid cooling of Break; appearance of Slower cooling;
liquid solid solution S1 solidification continues

Cooling of solid Break; solidification

solution S1 completes
(ii) Composition anywhere between O and C
Rapid cooling of Break; appearance of Slower cooling; solidi-
liquid solid solution S2 fication continues

Break Slower cooling; Horizontal portion;

solidification solidification transformation of solid
completes of S1 continues solution S2 to solid
solution S1
Smooth cooling; Break if Slower cooling
cooling of solid second solid of two solid
solution S1 solution appears solutions
(iii) Composition anywhere between C and D
Rapid cooling of Break appearance Slower cooling;
liquid of solid solution S2 solidification continues

Slower cooling of two Horizontal portion; appea-

solid solutions rance of two solid
solutions
(iv) Composition anywhere between D and B
Rapid cooling Break; appearance Slower cooling;
of liquid of solid solution S2 solidification continues

Break; if second Slower cooling Break; solidification

solid solution of solid solution S2 completes
appears

Cooling of two
solid solutions

Examples A few examples of system exhibiting partial miscibility in the solid state with
a peritectic transition are given below.
AgCl–LiCl, AgNO 3–NaNO 3, Co–Fe and p-iodochlorobenzene-p-di-
iodobenzene.

Theoretical Aspects Limited solid-phase solubility with a peritectic temperature is observed when
of Fig. 6.10.1 the metastable melting point of one of the components (e.g., Bm) lies above the
melting point of other stable component (e.g., A) so that the two ascending solid
solution diagrams ascend in the same direction (Fig. 6.10.2)
306 A Textbook of Physical Chemistry

Bm

O C

Temperature
D

A
F
E

Fig. 6.10.2 Metastable

extensions of the liquidus
Am
and solidus curves of a
system exhibiting limited Pure Composition Pure
solubility with peritectic A B
temperature

Example 6.10.1 Metals A and B melt at 1 200 °C and 1 600 °C, respectively. Thermal analysis shows
presence of the following three-phase equilibria at 1 600 °C, melt containing 10 mol %
B and two solid solutions containing 20 mol % B and 30 mol % B, respectively, at
1 250 °C, solid solution containing 65 mol % B, melt containing 75 mol % B and solid
solution containing 95 mol % B. There is one compound A2B3 which melts at 1 700 °C
(congruently). Construct the phase diagram and label the phase regions.

Solution Analysis of data

(i) Since there is a formation of a congruently melting compound A2B3, we may

draw the phase diagrams of systems A-A2B3 and A2B3-B separately (Fig. 6.10.1).
(ii) At 1 600 °C, the melt contains lesser of B as compared to those present in the
two solid solutions. This implies the formation of two solid solutions with a
peritectic temperature. Therefore, the nature of the phase diagram of A-A2B3
system will be similar to that shown in Fig. 6.10.1.
(iii) At 1 250 °C, composition of B in the melt is between those present in the two
solid solutions. This implies the formation of stable solid solutions with an eutectic
point and hence the nature of the phase diagram will be similar to that shown in
Fig. 6.9.1.

Keeping in mind the above information, we obtain the phase diagram as shown in
Fig. 6.10.3. The labelling of areas is also shown in the figure.
 Phase Diagrams of Two-Component Systems 307

Fig. 6.10.3 Required

phase diagram

6.11 FORMATION OF PARTIAL MISCIBILITY IN THE LIQUID PHASE AND

CRYSTALLIZATION OF PURE COMPONENTS
The phase diagram of the present system has an appearance as shown in
Fig. 6.11.1.

Fig. 6.11.1 Phase diagram exhibiting partial miscibility in the liquid phase

Construction of the If the two components are partially miscible in the liquid phase, they will
Phase Diagram form two conjugate liquid solutions within certain range of concentrations.
In the phase diagram, compositions of these two conjugate solutions will be
represented by a dome-shaped curve such as CMD in Fig. 6.11.1. The curve
CM represents compositions of saturated solutions of B in A whereas DM
represents compositions of corresponding conjugate saturated solutions of
A in B. The point M is the upper critical solution temperature.
308 A Textbook of Physical Chemistry

From the cooling curves of pure components, the points A and B representing
respectively the freezing temperatures of A and B are obtained.
From the cooling curves I and II of two systems of B in A, the points a
and b representing respectively the start of freezing of A are obtained. If a
line passing through A, a and b is drawn, we get the freezing point curve
Aab of the component A.
From the cooling curves III and IV of two systems of A in B, the points c
and d representing respectively the start of solidification of B are obtained.
If a line passing through B, c and d is drawn, we get the freezing point
curve Bcd of the component B.
If the line Aab is extended, it meets the saturation solubility curve CM of
B in A at the point C. At this point, a single solution in equilibrium with
solid A just splits into two conjugate solutions C and D, respectively. Thus,
at the temperature corresponding to the point C, three phases, viz., solid A
and two solutions C and D are in equilibrium with the one another. Since,
the three phases in equilibrium constitutes an invariant system (F = C + 1
– P = 2 + 1 – 3 = 0), the temperature corresponding to the the point C will
have a fixed value. Thus, the cooling curves I and II will exhibit an arrest
of temperature at points a and b , respectively.
The tie line drawn at the point a or b starts from the point E (representing
solid A) and after passing through the point C (representing one conjugate
solution) ends at the point D (representing another conjugate solution). Thus,
a point on the line ECD will represent solid A and two liquid solutions C
and D in equilibrium with one another. The relative amounts of solid A and
the two solutions taken together may be determined with the help of the
lever rule. For example, at point a , we have
Amount of solid A a ¢C
=
Amount of solutions C and D Ea ¢
Further cooling of the system at a (or b ) causes more and more solidification
of A without any change in temperature. The removal of A from the liquid
phases moves the composition point C towards D along the line CD. As the
point C moves towards D, the relative length of the segment of the tie line
lying right to the point a increases indicating that more of A is precipitated.
Besides this, the relative amounts of conjugate solutions change in favour of
solution D. These facts are in agreement with the lever rule. For example, if
the overall composition of solutions is moved to the point g, we will have
Amount of solid A a ¢g
=
Amount of solutions C and D Ea ¢
Amount of solution C Dg
=
Amount of solutions D Cg
From the above expressions, the individual amounts of solid A, solution C
and solution D can be determined for the given amount of the total system.
When the overall composition of the solution is moved to the point D,
virtually whole of solution C disappears and the system contains solid A and
the solution D in equilibrium with each other. At this stage, the system a
 Phase Diagrams of Two-Component Systems 309

becomes univariant (F = C + 1 – P = 2 + l – 2 = l) and thus it is expected

to exhibit cooling along a a .
If the cooling curves V and VI of two systems situated slightly right to the
point D are studied, they will exhibit a break at the points e and f, respectively,
where the solidification of A will just start. Thus, if a line passing through
D, f and e is drawn, we get the freezing point curve Dfe of A from liquid
whose compositions lie to the right of the point D. Hence, cooling of the
system from a to a , merely causes more and more solidification of A
from a solution whose composition moves along the line Dfe. This fact is
in agreement with the lever rule as the relative length of the segment of tie
line right to the cooling line a a increases as temperature is lowered.
When the system a has been cooled up to the point a , the solution (on the
extension of line Dfe) becomes saturated with respect to B and hence both
solids A and B start solidifying together. This occurs at the eutectic point
O where solid A and solid B are in equilibrium with the solution O. The
system at this stage is invariant (F = C + 1 – P = 2 + 1 – 3 = 0). Thus, the
temperature corresponding to the point O will have a fixed value. The
cooling curves I, II, V and VI will exhibit an arrest of temperature at points
a , b , e and f , respectively.
If the freezing point curve Bcd is extended, it will meet the freezing point
curve Dfe at the eutectic point O. Thus, the cooling curves III and IV will
exhibit an arrest of temperature at the points c and d , respectively.
Labelling of the With the help of the above analysis, the phase diagram shown in Fig. 6.11.1 can
Phase Diagram be easily labelled. Table 6.11.1 describes the labelling of Fig. 6.11.1.

Table 6.11.1 Labelling of the Phase Diagram shown in Fig. 6.11.1

Location of the system Status of the system
A Freezing point of A
B Freezing point of B
Curve CMD Composition of two conjugate solutions
M Critical solution point
AabCDfe Freezing point curve of A
BcD Freezing point curve of B
O Eutectic point involving solid A, solid B and liquid solution
O
ECD A system on this line represents solid A in equilibrium with
the two conjugate solutions C and D
GOF A system on this line represents solid A and solid B in
equilibrium with solution O
Area ACDOFA Solid A in equilibrium with liquid solution whose composition
lies on the line ACDO
Area BGOB Solid B in equilibrium with liquid solution whose composition
lies on the line OB
Area below GOF Solid mixtures of A and B
Area above ACMDOB Liquid
Area CMDC Two conjugate solutions (compositions lie on the curves CM
and DM) in equilibrium with each other.
310 A Textbook of Physical Chemistry

Cooling Patterns The nature of cooling curve will depend upon the composition of the system.
A few typical cases shown in Fig. 6.11.1 are now described:
(i) Composition anywhere between AC
Rapid cooling of Break; appearance Slower cooling; solidification
liquid of solid A of A continues and the compo-
sition of melt moves along AC

Horizontal portion Slower cooling; solidi- Horizontal portion; formation

at the eutectic fication of A continues, of two liquid solutions. Solidi-
point O; solidifi- composition of the fication of A continues till the
cation of solid mixture melt moves along DO melt has composition D

Cooling of solid mixture

(ii) Composition corresponding to the point C
Rapid cooling of Horizontal portion; for- Slower cooling; solidification
liquid mation of two liquid of A continues and the com-
solutions; solidification position of the melt moves
of A continues till the along DO
melt has composition D
Cooling of solid Horizontal portion
mixture at the eutectic point O
(iii) Composition anywhere between C and D
Rapid cooling Break; formation of Cooling of two liquid
of liquid two liquid solutions solutions continues

Horizontal Slower cooling; Horizontal portion; solid

portion at the solidification of A A starts forming and
eutectic point O continues, com- continues till the com-
position of the position of the melt is D
melt moves along DO
Cooling of
solid mixture
(iv) Composition anywhere between B and O (or D and O)
Cooling of Break; solidification Slower cooling; solidi-
liquid of B (or A) starts fication of B (or A)
continues and the com-
position of the melt
moves along BO (or DO)

Cooling of Horizontal portion

solid mixture at the eutectic point

Examples A few examples which form two liquid layers are; benzoic acid-water, phenol-
water, succinic nitrile-water, resorcinol-benzene and Zn-Bi.
 Phase Diagrams of Two-Component Systems 311

6.12 PHASE DIAGRAMS OF AQUEOUS SOLUTIONS OF SALTS

An aqueous solution of a salt is an example of a two-component system where
we may have
(1) Formation of a simple eutectic or cryohydrate.
(2) Formation of compounds (hydrates) with congruent melting points.
(3) Formation of compounds (hydrates) with incongruent or meritectic points.
At atmospheric pressure, the solubilities of most of salts in water are
limited and, therefore, such systems are usually studied at high pressures. In
this section, we shall discuss phase diagrams listed above by taking a typical
example of each.

FORMATION OF A SIMPLE EUTECTIC OR CRYOHYDRATE

An aqueous solution of KI constitutes a simple eutectic system the phase
diagram of which is shown in Fig. 6.12.1. It has an appearance similar to that
of Fig. 6.4.1. The description of the phase diagram is included in the figure
itself. Along AO, ice separates and thus this curve represents the freezing point
curve of water; along BO, solid KI separates and thus it represents the solubility
curve of KI. Point O is the eutectic point where both ice and KI separate, the
corresponding eutectic temperature is – 23 °C. Thus, this is the lowest temperature
at which the system can exist in the liquid form.

Fig. 6.12.1 Required

phase diagram

Eutectic systems involving a salt and water were the first to be studied and
were named as cryohydrates (Greek: frost water). Earlier, it was thought that at the
cryohydric point (eutectic point) formation of a definite compound occurs. However,
this view-point was rejected on the basis of following experimental facts:
Composition of the eutectic varies with the external pressure and it seldom
corresponds to a simple molecular proportion
The heterogeneous structure of the solution can be seen under a microscope.
312 A Textbook of Physical Chemistry

Alcohol or acetone may dissolve the ice and leave behind a network of KI.
X-ray analysis reveals the existence of two solid phases.
The enthalpy of solution and density are the mean of the values for the two
components.
Besides these facts, the phase rule also predicts that the formation of two
solid phases at the cryohydric point is an invariant point.
Production of When a salt is added to ice and a little water at 0 °C, a freezing mixture is
Freezing Mixture produced. The principle of the freezing mixture can be explained on the basis of
with a Salt and Ice the phase diagram shown in Fig. 6.12.1. Initially, we have three phases, namely,
ice, solution and the salt; such a system can be stable only at the eutectic point
which lies far below 0 °C. Thus at 0 °C, the system is not stable and it tries
to attain the eutectic point by melting ice and dissolving more and more salt in
the produced water. Since the melting of ice and in most cases the dissolution
of the salt are endothermic processes, a fall in temperature of the system is
observed. This is continued till either one of the phases is completely used up
or the eutectic point is reached. The temperature of the system when this point
is attained remains constant till sufficient heat from the surroundings is absorbed
to cause all the ice to melt or all the salt to dissolve. The resultant system has
two phases in equilibrium and, therefore, becomes univariant. Further absorption
of heat from the surroundings will result in an increase in temperature of the
system.

FORMATION OF COMPOUNDS WITH CONGRUENT MELTING POINTS

The best known example in which more than one congruent melting compound
Water System is formed is that of ferric chloride-water system. This salt forms four stable
hydrates. These are
Fe2Cl6 12H2O; Fe2Cl6 7H2O; Fe2Cl6 5H2O and Fe2Cl6 4H2O
where double formula are used for ferric chloride in order to avoid a fractional
number of molecules of water of crystallization. The phase diagram of this system
has an appearance as shown in Fig. 6.12.2. The description of the diagram is
given in Table 6.12.1.
Isothermal The cooling curve of a solution for a given composition can be drawn following
Evaporation of the principles outlined earlier. For the present system it is of interest to consider
Solution isothermal evaporation of the solution. One such case is described below.
Let the solution be isothermally evaporated from the point a to m
(Fig. 6.12.1). The sequence of events that takes place is as follows.
Point a to b: Unsaturated solution of ferric chloride.
At b: Solid Fe2Cl6 12H2O commences.
From b to c: More and more of dodecahydrate separates, composition of the
liquid remains unchanged and has a value corresponding to the point b. The
volume of the solution decreases.
Point c: The solution completely disappears and the system consists of only
solid Fe2Cl6 12H2O.
 Phase Diagrams of Two-Component Systems 313

K
Soln I

G J¢ J J²
C
H¢ H H²
E g h j
b c d e k
a m
f
F¢ F²
F
Temperature D¢ D D²

Fe2Cl6×12H2O
A

Fe2Cl6×7H2O

Fe2Cl6×5H2O

Fe2Cl3×4H2O
Ice
+ soln.
B²
B¢ B

Ice +
Fig. 6.12.2 Phase
Fe2Cl6×12H2O
diagram of FeCl3-H2O C¢ E¢ G¢ I¢
system Water Amount per cent FeCl3

Table 6.12.1 Description of the Phase Diagram shown in Fig. 6.12.2

Location of the system Status of the system

A Freezing point of water
C Composition point of dodecahydrate
C Congruent melting point of dodecahydrate (37 °C)
CC Solid dodecahydrate
E Composition point of heptahydrate
E Congruent melting point of heptahydrate (32.5 °C)
EE Solid heptahydrate
G Composition point of pentahydrate
G Congruent melting point of pentahydrate (56 °C)
GG Solid pentahydrate
I Composition point of tetrahydrate
I Congruent melting point of tetrahydrate (78.5 °C)
II Solid tetrahydrate
B Eutectic point involving ice, dodecahydrate and solution
B(–55 °C)
B BB Tie line at the point B. It starts from B (ice) and after passing
through the point B (solution) ends at B (dodecahydrate)
D Eutectic point involving dodecahydrate, heptahydrate and
solution D (27.4 °C)
D DD Tie line at the point D. It starts from D (dodecahydrate)
and after passing through the point D (solution) ends at D
(heptahydrate)
F Eutectic point involving heptahydrate, pentahydrate and solution
F (30 °C)
(Contd.)
314 A Textbook of Physical Chemistry

Table 6.12.1 (Contd.)

Location of the system Status of the system

F FF Tie line at the point F. It starts from F (heptahydrate) and after

passing through the point F (solution) ends at F (pentahydrate)
H Eutectic point involving pentahydrate, tetrahydrate and solution
H (55 °C)
H HH Tie line at the point H. It starts from H (pentahydrate) and after
passing through the point H (solution) ends at H (tetrahydrate)
J Eutectic point involving tetrahydrate, anhydrous salt and solution
J (66 °C)
J JJ Tie line at the point J. It starts from J (tetrahydrate) and after
passing through the point J (solution) will end at J (anhydrous
salt)
AB Freezing point curve of ice
BCD Solubility curve of dodecahydrate
DEF Solubility curve of heptahydrate
FGH Solubility curve of pentahydrate
HIJ Solubility curve of tetrahydrate
JK Solubility curve of anhydrous salt
Areas
ABB A Ice solution (AB)
BCB B Dodecahydrate solution whose composition lies on BC
DCD D Dodecahydrate solution whose composition lies on DC
DED D Heptahydrate solution whose composition lies on DE
FEF F Heptahydrate solution whose composition lies on FE
FGF F Pentahydrate solution whose composition lies on FG
HGH H Pentahydrate solution whose composition lies on HG
HIH H Tetrahydrate solution whose composition lies on HI
JIJ J Tetrahydrate solution whose composition lies on IJ
J JKJ Anhydrous salt solution whose composition lies on JK
Area below B BB Solid mixtures of ice and dodecahydrate
D DD Solid mixtures of dodecahydrate and heptahydrate
F FF Solid mixtures of heptahydrate and pentahydrate
H HH Solid mixtures of pentahydrate and tetrahydrate
J JJ Solid mixtures of tetrahydrate and anhydrous salt
Area above the curve
ABCDEFGHIJK Aqueous solution

Between c and d: There exists an equilibrium between dodecahydrate and the

solution, but now composition of the latter corresponds to the point d. From c to
d, more and more of the solution is produced and less and less of the solid is left.
Point d: Solid dodecahydrate disappeares and the system is completely a solution.
Between d and e: Once again the solution becomes unsaturated.
At e: Solid Fe2Cl6 7H2O starts separating.
Between e and f: More and more of heptahydrate separates from the solution
of e, volume of the solution decreases gradually.
Point f: Complete solidification of Fe2Cl6 7H2O occurs at this point.
Point f to g: Again solution g appears, volume of the solution increases, and
the amount of solid heptahydrate decreases.
 Phase Diagrams of Two-Component Systems 315

Point g: Solid heptahydrate disappears and the system is completely a solution.

Between g and h: Again the solution becomes unsaturated.
Point h: Fe2Cl6 5H2O starts appearing.
Point h to j: More and more of pentahydrate appears, volume of the solution h
decreases.
Point j: Complete solidification to give Fe2Cl6 5H2O.
Point j to k: Transformation of more and more of the solid Fe2Cl6 5H2O to
Fe2Cl6 4H2O.
At k: Transformation of Fe2Cl3 5H2O to Fe2Cl3 4H2O is completed and we
have only Fe2Cl6 4H2O.
From k to m: Transformation of solid Fe2Cl6 4H2O to anhydrous salt.
If the evaporation is continued, then ultimately one would get the pure anhydrous
salt.
Other Examples of Hydrates of congruent melting points have also been discovered in which one of
Hydrates the components is not a salt. A few examples are
N2O5 H2O system: Compounds are N2O5 7H2O
N2O5 3H2O and N2O5 H2O
and SO3 H2O system: Compounds are SO3 5H2O, SO3 3H2O
SO3 2H2O, SO3 H2O and 2SO3 H2O

Example 6.12.1 Sulphuric acid forms three hydrates. All have congruent melting points. There are no
solid solutions.

Compound Melting point / °C

H2SO4 (anhydrous) 10.5
H2SO4 H2O 8.6
H2SO4 2H2O –39.9
H2SO4 4H2O –24.5
Eutectic (ice + H2SO4 4H2O) – 74
Eutectic (H2SO4 4H2O + H2SO4 2H2O) – 51
Eutectic (H2SO4 2H2O + H2SO4 H2O) – 44
Eutectic (H2SO4 H2O + H2SO4) – 38

(i) Sketch the temperature-amount fraction phase diagram. Label each area to
indicate the phases present.
(ii) Describe all the changes that occur when sulphuric acid is added in small
increment to a sample of ice being maintained at –30 °C.
Solution (i) The temperature-amount fraction phase diagram from the given data is shown in
Fig. 6.12.3. Labelling of the phase diagram is shown in Table 6.12.2.
(ii) The changes that occur when sulphuric acid is added in small increment to a sample
of ice maintained at – 30 °C can be described by drawing a horizontal line at –30 °C
such as shown in Fig. 6.12.3. The effects produced will be as follows.
From a to b, the system consists of solid ice and solution of composition corresponding to
the point b. The only things that variy from a to b are the relative amounts of the two; the amount
of ice decreases whereas that of solution increases. At b, the last crystal of H2O disappears
and from b to c, the system is in liquid state. At c, crystals of H2SO4 4H2O start
316 A Textbook of Physical Chemistry

Fig. 6.12.3 Required

phase diagram of H2SO4
– H2O system

Table 6.12.2 Labelling of the Phase Diagram

Area System
1 solution
2 ice + solution
3 solid H2SO4 4H2O + solution (OC)
4 ice + solid H2SO4 4H2O
5 solid H2SO4 4H2O + solution (CO )
6 solid H2SO4 2H2O + solution (O D)
7 solid H2SO4 4H2O + solid H2SO4 2H2O
8 solid H2SO4 2H2O + solution (O D)
9 solid H2SO4 H2O + solution (O E)
10 solid H2SO4 2H2O + solid H2SO4 H2O
11 solid H2SO4 H2O + solution (EO )
12 solid H2SO4 + solution (BO )
13 solid H2SO4 H2O + solid H2SO4

appearing and continue to appear till the point d is reached keeping all the while the solution
composition at c. At d the system consists of only solid H2SO4 4H2O. From d to e, again we
have solid H2SO4 4H2O and solution, but now the solution composition is represented by the
point e. The only thing that varies from d to e is that the amount of solid H2SO4 4H2O
decreases whereas the amount of solution increases. At e, the last crystal of solid H2SO4
4H2O disappears and from e to f, the system is present in the solution form. From f to g, solid
H2SO4 H2O is in equilibrium with the solution of composition corresponding to the point f.
At g, the system consists of only solid H2SO4 H2O. From g to h, the system contains solid
 Phase Diagrams of Two-Component Systems 317

H2SO4 H2O in equilibrium with solution of composition corresponding to the point h.

From h to i, it is present in the solution form and from i to j, the system consists of anhydrous
H2SO4 and solution of composition corresponding to the point i. At j, the system consists of
only solid anhydrous H2SO4.

FORMATION OF COMPOUNDS WITH INCONGRUENT MELTING POINTS

Formation of compounds (hydrates) with incongruent or meritectic melting points
Water System are more common, one of the well-known examples is the sodium sulphate and
water system. The phase diagram of this system is shown in Fig. 6.12.4 and is
described in Table 6.12.3.

Fig. 6.12.4 Phase

diagram of Na2SO4 – H2O
system

Table 6.12.3 Description of The Phase Diagram shown in Fig. 6.12.4

Location of Status of system

the system
A Freezing point of water
C Incongruent point where solid Na2SO4 10H2O undergoes the
following peritectic reaction
Na2SO4 10H2O Na2SO4(rhombic) + Solution C
C Composition of solution which is produced at point C
CC C Tie line at the point C. It starts from C (solution) and after passing
through C (Na2SO4 10H2O) ends at C (rhombic Na2SO4)
B Eutectic point where ice and Na2SO4 10H2O are in equilibrium
with solution B
(Contd.)
318 A Textbook of Physical Chemistry

Table 6.12.3 (Contd.)

B BB Tie-line at the point B. If starts from B (ice) and after passing through
the point B (solution) ends at B (Na2SO4 10H2O)
AB Freezing point curve of ice
BC Solubility curve of Na2SO4 10H2O.
CD Solubility curve of rhombic Na2SO4. This curve is slightly curved at
left up to about 125 °C since solubility of rhombic Na2SO4 decreases
with increase in temperature. Beyond this temperature, the solubility
increases with increase in temperature
D At temperature corresponding to the point D, polymorphic modification
of rhombic Na2SO4 into monoclinic Na2SO4 takes place
DE Solubility curve of monoclinic Na2SO4 (solubility of monoclinic Na2SO4
decreases with increase in temperature)
E This point gives the maximum limit of the temperature up to which
the system can be studied and represents critical temperature of water
in solution. Above this temperature, liquid water does not exist. This
temperature is very close to the critical temperature of pure water
since the solubility of Na2SO4 at this temperature is very small
Areas
ABB A ice solution (AB)
BCC B B Na2SO4 10H2O(s) solution (BC)
Below the line
B BB Solid mixtures of ice and Na2SO4 10H2O
CDD C C Rhombic Na2SO4(s) solution (CD)
Below the line
CC Solid mixtures of Na2SO4 (rhombic) and Na2SO4 10H2O
DEE D D Monoclinic Na2SO4(s) solution (DE)
Line CF Extension of the curve DC where metastable equilibrium between
rhombic Na2SO4 and solution exists. This curve is continued up to the
point F where metastable heptahydrate (Na2SO4 7H2O) is deposited
Line BG Extension of the curve AB where metastable equilibrium between ice
and solution exists. This curve is extended up to the point G where
both ice and Na2SO4 7H2O solidify together
GF Metastable solubility curve of heptahydrate
G Metastable eutectic point where ice and heptahydrate are in equilibrium
with the solution G
F The temperature corresponding to this point represents an incongruent
melting point where the following equilibrium exists
Na2SO4 7H2O(s) Na2SO4 (rhombic) + Solution F

Solubilities of Stable The fact that the metastable curve GF lies to the right of the stable curve BC
and Metastable indicates that at a given temperature, the metastable form is more soluble than
Forms the stable form. This is a universal rule and can be derived thermodynamically.
Since, the reaction
Metastable solid form Stable solid from
(ms) (ss)
is a spontaneous process (and the reverse of this reaction can never occur), we
must have
μss < μms
 Phase Diagrams of Two-Component Systems 319

Since both these salts exist in equilibrium with the corresponding saturated
solutions, we also have
mss = mss(soln)
mms = mms(soln)
With these, the previous expression modifies to
mss(soln) < mms(soln)
that is, the chemical potential of the stable solute Na2SO4 10H2O in the
saturated solution (represented by the curve BC) is less than that of the unstable
solute Na2SO4 7H2O in the corresponding saturated solution (represented by
the curve GF). If it is assumed that both the solutions behave ideally (or depart
from ideality to the same extent), then it is obvious that
xss(soln) < xms(soln)
More Examples A few other examples in which compounds of incongruent melting points are
formed are now described.
Sodium Chloride-Water System In this system, we have
(i) Stable eutectic temperature at – 21.2 °C, where ice, NaCl 2H2O and the
solution are in equilibrium.
(ii) Meritectic temperature at 0.15 °C where the following transformation takes
place:
Solid NaCl 2H2O NaCl + solution
Calcium Chloride-Water System In CaCl2-H2O system, we have more than
one compound formation. There are four stable hydrates and one metastable
hydrate. These are
CaCl 2 ◊ 6H 2 O ¸
CaCl 2 ◊ 4H 2 O (a )ÔÔ
˝ Stable hydrate
CaCl 2 ◊ 2H 2 O Ô
CaCl2 ◊ H 2 O Ô˛
CaCl2 ◊ 4H 2 O(b) Unstable hydrate
Four stable transition points will be present in the phase diagram
corresponding to the following transformations.
29.8 ∞ C
CaCl 2 ◊ 6H 2 O �
�����
���� � CaCl 2 ◊ 4H 2 O(a ) + solution
�
45.3 ∞ C
CaCl 2 ◊ 4H 2 O(a ) �
�����
���� � CaCl2 ◊ 2H 2 O + solution
�
175.5 ∞ C
CaCl 2 ◊ 2H 2 O �
������
����� � CaCl 2 ◊ H 2 O + solution
�

CaCl 2 ◊ H 2 O �
��
��� CaCl 2 + solution
Besides these four points, two more points will exist corresponding to the
following two unstable transformations.
29.2 ∞ C
CaCl 2 ◊ 6H 2 O �
�����
���� � CaCl 2 ◊ 4H 2 O(b) + solution
�
38.4 ∞ C
and CaCl 2 ◊ 4H 2 O(b) �
�����
���� � CaCl2 ◊ 2H 2 O + solution
�
320 A Textbook of Physical Chemistry

Sodium Iodide-Water System We have

-31.5 ∞ C
Ice + NaI ◊ 5H2 O �
������
����� � solution (39 mass % NaI)
�

-13.5 ∞ C
NaI ◊ 5H 2 O � � NaI ◊ 2H 2 O + solution (60.2 mass % NaI)
������
�
�����
65 ∞ C
NaI ◊ 2H 2 O �
����� NaI + solution (74.4 mass % NaI)
����

Cupric Nitrate-Water System We have

-24 ∞ C
Ice + Cu(NO3 )2 ◊ 9H2 O �
�����
�
����� solution (35.9 mass % Cu(NO3 )2 )
-20 ∞ C
Cu(NO3 )2 ◊ 9H 2 O �
�����
�
����� Cu(NO3 )2 ◊ 6H2 O + solution
(39.9 mass % Cu(NO3 )2 )
24.5 ∞ C
Cu(NO3 )2 ◊ 6H 2 O �
�����
���� � Cu(NO3 )2 ◊ 3H2 O + solution
�
(61.4 mass % Cu(NO3 )2 )

Example 6.12.2 Given below are the data of the binary system ferrous sulphate-water. Construct the phase
diagram and label it.

Composition of Saturated Solution at Various Temperatures

Temperature m(FeSO4)/g Solid phase

°C per 100 g solution

–0.7 5.18 Ice

–1.3 9.47 ”
–1.8 12.99 Ice + FeSO4 7H2O
0 13.53 FeSO4 7H2O
+ 10 17.02 ”
20 21.0 ”
30 24.78 ”
40 28.67 ”
50 32.7 ”
52 33.42 ”
54 34.25 ”
56.17 35.32 FeSO4 7H2O + FeSO4 4H2O
60 35.46 FeSO4 4H2O
64 35.65 FeSO4 4H2O + FeSO4 H2O
68 34.35 FeSO4 H2O
77 31.46 ”
80.4 30.35 ”
85 28.8 ”
90 27.15 ”
FeSO4 7H2O = 54.6 mass % FeSO4
FeSO4 4H2O = 67.8 mass % FeSO4
FeSO4 H2O = 89.4 mass % FeSO4
 Phase Diagrams of Two-Component Systems 321

Solution First of all, the points corresponding to the given data on temperature versus composition
were located in a two-dimension phase diagram. After this, the points corresponding to the
given three compounds, viz., FeSO4 7H2O, FeSO4 4H2O and FeSO4 H2O, were located
on the composition axis and the vertical lines were drawn from these points as shown in
Fig. 6.12.5.

Fig. 6.12.5 Required phase diagram of FeSO4-H2O system

From the given data, we find that the temperature at which ice separates out from
the solution decreases as more and more of FeSO4 is dissolved in it. This decrease of
temperature is continued up to the temperature of –1.8 °C where the solution composition
is 12.99 mass per cent of FeSO4. At this temperature, the two solids, viz., ice and
FeSO4 7H2O separate out. On increasing the mass per cent of FeSO4 from 12.99 to 13.53,
we find that there is a separation of only FeSO4 7H2O and the freezing point of the
solution increases from –1.8 to 0 °C. Obviously, the temperature –1.8 °C is the lowest
temperature at which the two solids separate out and thus must represent eutectic
temperature. So, we draw a horizontal line at this temperature starting from the pure ice line
to the vertical line of FeSO4 7H2O. At temperature 56.17 °C, the two solids FeSO4 7H2O
and FeSO4 4H2O are present in equilibrium with the solution which contains 35.32 mass
per cent of FeSO4. Since this composition is different from the mass per cent of FeSO4 in
the compound FeSO4 7H2O, it is obvious that the compound FeSO4 7H2O has decomposed
at a temperature lower than its actual melting point, i.e. the compound FeSO4 7H2O has
an incongruent melting point of 56.17 °C. Thus, the vertical line representing this compound
322 A Textbook of Physical Chemistry

must end at this temperature. Since FeSO4 4H2O is separated out at temperature
immediately higher than 56.17 °C, we draw a horizontal line from the peritectic point (56.17
°C and 35.32 mass per cent of FeSO4) up to the vertical line representing the compound
FeSO4 4H2O (Fig. 6.12.5). Similar arguements at temperature 64 °C, where again two
phases FeSO4 4H2O and FeSO4 H2O are separated out, indicates that the compound
FeSO4 4H2O also has an incongruent melting point. So the vertical line representing
this compound must end at the temperature 64 °C. Since FeSO4 H2O separates out at
temperature immediately above 64 °C, we draw a horizontal line from the peritectic point
(64 °C and 35.65 mass percent of FeSO4) up to the vertical line representing the compound
FeSO4 H2O. At higher temperatures, we have only the solubility curve of FeSO4 H2O.
Finally a smooth curve passing through the points of temperature versus composition
is drawn. This gives us the phase diagram of the present system. Labelling of different
areas is straightforward and is described in Fig. 6.12.5 itself.

Example 6.12.3 Given below are the data of the binary system sodium hydroxide-water. Construct the
phase diagram and label it.

Composition of Saturated Solutions at Various Temperatures

Temperature m(NaOH)/g per Solid phase

°C 100 g solution
– 5.27 5.78 Ice
– 10.29 10.03 ”
– 17.20 14.11 ”
– 25.2 18.17 ”
–28.0 19.0 Ice + NaOH 7H2O
–26.0 19.98 NaOH 7H2O
–25.2 21.1 ”
–24.0 22.1 NaOH 7H2O + NaOH 5H2O
–21.7 23.31 NaOH 5H2O
–19.95 23.97 ”
–18.0 24.7 NaOH 5H2O + NaOH 4H2O
–12.60 25.47 NaOH 4H2O
–8.45 26.91 ”
+ 1.62 30.38 ”
5.40 32.3 NaOH 4H2O + NaOH 3.5H2O
7.00 32.97 NaOH 3.5H2O
13.2 35.51 ”
15.55 38.83 ”
13.95 42.28 ”
10.75 44.22 ”
5.00 45.5 NaOH 3.5H2O + NaOH 2H2O
7.80 47.3 NaOH 2H2O
10.30 49.11 ”
12.30 50.8 NaOH 2H2O + NaOH H2O
18.00 51.7 NaOH H2O
40.25 56.44 NaOH H2O
57.85 62.85 ”
63.23 66.45 ”
(Contd.)
 Phase Diagrams of Two-Component Systems 323

(Contd.)
Temperature m(NaOH)/g per Solid phase
°C 100 g solution
64.3 68.49 ”
63.0 71.17 ”
62.0 74.2 NaOH H2O + NaOH
80.0 75.83 NaOH
110.0 78.15 NaOH
NaOH 7H2O = 24.1 mass % NaOH
NaOH 5H2O = 30.7 mass % NaOH
NaOH 4H2O = 35.7 mass % NaOH
NaOH 3.5 H2O = 38.9 mass % NaOH
NaOH 2H2O = 52.7 mass % NaOH
NaOH H2O = 69.0 mass % NaOH

Solution Analysis of data

(i) The temperature –28.0 °C must be an eutectic temperature as the temperatures
of data above and below this are higher than –28.0 °C.
(ii) The temperature –24.0 °C, where the two solids NaOH 7H2O and NaOH 5H2O
appear must be a peritectic temperature as solution composition of 22.1 mass per
cent of NaOH is different from the corresponding composition in the compound
NaOH 7H2O (24.1 mass per cent). Thus, the compound NaOH 7H2O
decomposes earlier than its actual melting point. The vertical line representing
NaOH 7H2O must end at the temperature –24 °C, and the horizontal line
representing the range of peritectic reaction at –24.0 °C will end at the vertical
line of NaOH 5H2O.
(iii) The temperature –18.0 °C, where the two solids NaOH 5H2O and NaOH 4H2O
appear, is also a peritectic temperature as solution composition of 24.7 mass per
cent of NaOH is different from the corresponding composition in the compound
NaOH 5H2O (30.7 mass per cent). The vertical line representing NaOH
5H2O will end at the temperature –18.0 °C and the horizontal line representing
peritectic reaction at – 18.0 °C will end at the vertical line of NaOH 4H2O.
(iv) The temperature 5.4 °C, where the two solids NaOH 4H2O and NaOH 3.5H2O
appear, is also a peritectic temperature as solution composition of 32.3 mass per
cent of NaOH is less than that in the compound NaOH 4H2O (35.7 mass per
cent). Thus, the compound NaOH 4H2O decomposes earlier than its actual
melting point. The vertical line representing NaOH 4H2O will end at the
temperature 5.4 °C, and the horizontal line representing peritectic reaction at 5.4 °C
will end at the vertical line of NaOH 3.5H2O.
(v) The compound NaOH 3.5H2O is a congruently melting compound as its
solubility curve passes through a maximum around 15.55 °C.
(vi) The temperature 5.0 °C, where the two solids NaOH 3.5H2O and NaOH 2H2O
appear, must be an eutectic temperature as it has a minimum value in the
composition range under study (44.22–47.3 mass per cent of NaOH).
(vii) The temperature 12.30 °C, where the two solids NaOH 2H2O and NaOH H2O
appear, is a peritectic temperature as the solution composition of 50.8 mass
per cent of NaOH is less than that in the compound NaOH 2H2O. Thus, the
compound NaOH 2H2O decomposes earlier than its actual melting point. The
324 A Textbook of Physical Chemistry

vertical line representing NaOH 2H2O will end at the temperature 12.30 °C
and the horizontal line representing peritectic reaction at 12.30°C will end at the
vertical line of NaOH H2O.
(viii) The compound NaOH H2O is a congruently melting compound as its solubility
curve passes through a maximum around 64.3 °C.
(ix) The temperature 62.0 °C where the two solids NaOH H2O and NaOH appear
must be an eutectic temperature as it has a minimum value in the composition
range under study (71.17–75.83 mass per cent NaOH).
Keeping in mind the above analysis, the phase diagram of the present system can
be drawn as shown in Fig. 6.12.6. The labelling of various areas is also shown in
Fig. 6.12.6

Fig. 6.12.6 Required phase diagram of NaOH – H2O system

 Phase Diagrams of Two-Component Systems 325

REVISIONARY PROBLEMS
6.1 (a) Determine the variance of a two-component system having number of phases
equal to one, two and three, respectively.
(b) Show that in a system where the external pressure remains constant, the degrees
of freedom can be calculated by employing the reduced phase rule F = C – P + 1.
6.2 (a) What do you understand by condensed systems? Classify various solid-liquid
equilibria based on the nature of the liquid phase and the solid phase in two-component
systems.
(b) Explain why we should exclude a case of forming a series of solid solutions
when the two components are partially miscible in the liquid state?
6.3 Explain, how does thermal analysis help in drawing the phase-diagram of one and two-
component systems? Support your answer by drawing a few typical cooling curves.
6.4 (a) Draw the phase diagram of a two-component system exhibiting simple eutectic
behaviour.
Explain, why the melting point of a pure component and the eutectic point are
invariant points. How will you establish that the solid which separates out at the
eutectic point is a solid mixture and not a compound?
(b) Derive thermodynamically the relation governing the solubility curve of an ideal
binary system.
(c) Explain, how the eutectic temperature and composition be determined by making
use of the relation derived in part (b)?
(d) Derive the lever rule as applicable to the solid-liquid region of a simple eutectic
phase diagram.
6.5 Explain, what modifications in the phase diagram of a simple eutectic system take
place when one of the components exists in two allotropic forms. Show that the
transition point is an invariant point.
6.6 (a) What do you understand by the congruent and incongruent melting points? What
are the number of components and the variance at the congruent melting point of a
system consisting of two constituents?
(b) Explain, why the curve passing through the congruent melting point shows a
rounded maximum instead of a sharp intersecting point.
(c) Draw a typical phase diagram with complete labelling of a two-component system
exhibiting a single congruent melting point. Draw also a few typical cooling curves.
6.7 (a) What do you understand by the peritectic reaction or incongruent fusion? Show
with the help of phase rule that the above reaction takes place at a definite temperature,
i.e. the system at the peritectic point is invariant.
(b) Draw a typical phase diagram of a system exhibiting incongruent compound
formation. Explain in what respect it differs from that of a system exhibiting allotropic
modification by one of its components.
6.8 What is meant by a binary solid solution? How does it differ from a solid mixture?
Show that the minimum number of degrees of freedom when a solid solution is in
equilibrium with a liquid solution is one. What do you conclude from this regarding
the general nature of phase diagram of such a system?
6.9 (a) Show that the shift in the freezing point of solvent when a binary solid solution
separates on cooling is given by
– DTf = Kf m2(1) (1 – K )
where m2(1) is the molality of the solute in the liquid phase and K is the distribution
constant defined as
Amount fraction of solute in the solid phase
K=
Amount fracction of solute in the solution
326 A Textbook of Physical Chemistry

What approximations are involved in deriving the above expression?

(b) Under what conditions, (i) an increase in the freezing point of the solvent, and
(ii) a decrease in the freezing point of the solvent is observed when a solute is added
to the solvent?
From the derived conditions, deduce the statements of Konowaloff’s rule as applicable
to the solid-liquid equilibria.
6.10 Derive the following relations as applicable to the ascending type solid solution.
exp( - A) {exp( - B ) - 1}
x1(1) =
exp( - B ) - exp( - A)
exp( - B ) - 1
x1(s) =
exp( - B ) - exp( - A)

D fus H1,∞ m Ê 1 1 ˆ D fus H 2,∞ m Ê 1 1 ˆ

where A= - and B = -
R ÁË T T * ˜¯ R ÁË T T2* ˜¯
1

Derive the following conclusions from the above relations:

(1) None of the relationships is linear.
(2) The liquidus and solidus curves do not coincide except at T1* and T2*.
(3) For any composition between 0 and 1, temperature of the liquid and solid curves
lies between the melting points of the two components.
6.11 Classify phase diagrams involving solid solutions of nonideal binary systems on the
basis of the distribution constants KA in B (i.e. xA(s)/xA(1), A is acting as a solute and
B as a solvent) and KB in A (i.e. xB(s)/xB(1), B acting as a solute and A as a solvent).
Draw their phase diagrams and label each area and line. Discuss the sequence of
events that takes place on cooling a system in the above cases.
6.12 (a) What are the end products of fractional crystallization of a system exhibiting (i)
ascending type solid solution, (ii) minimum type solid solution, and (iii) maximum
type solid solution? (b) Describe the principle underlying the technique of zone
refining.
6.13 Draw a typical phase diagram of a two-component system in which the two
constituents are partially miscible in the solid state and form stable solid solutions.
Is it possible to separate completely the two components in such a system by the
method of fractional crystallization?
6.14 Draw a typical phase diagram of a two-component system in which the two constituents
are partially miscible in the solid state and form solid solutions which are stable only
up to a transition point. Is it possible to separate completely the two constituents in
such a system through fractional crystallization?
6.15 Draw a typical phase diagram of a two-component system in which the two
constituents are partially miscible in the liquid state and the solid phases consist of
pure components.
6.16 (a) Draw a simple eutectic phase diagram as shown by KI-H2O system. Explain,
why the name cryohydrate is given to this type of system. Explain, with the help of
the phase diagram, the formation of a cooling mixture when a salt is added to ice
containing a small amount of water.
(b) Ferric chloride forms four stable hydrates. These are Fe 2 Cl 6 12H 2 O,
Fe2Cl6 7H2O, Fe2Cl6 5H2O and Fe2Cl6 4H2O. Draw the phase diagram of
FeCl3-H2O system with complete labelling. Explain, what do you understand by the
isothermal evaporation of the solution. Selecting any point in the unsaturated solution
region, describe the sequence of steps that takes place during the isothermal evaporation
of water.
 Phase Diagrams of Two-Component Systems 327

(c) Draw the phase diagram of Na2SO4-water system and describe its complete
labelling. Show thermodynamically that at a given temperature the metastable form
is more soluble in water than the stable form.

TRY YOURSELF PROBLEMS

6.1 Derive the lever rule for the point c given in Fig. 6.4.1.
6.2 What types of cooling curves are expected for a one-component system?
6.3 Solid ammonium nitrate can exist in five crystalline forms with the following transition
temperatures:

Explain the type of phase-diagram which you would expect for the NH4NO3–H2O
system.
6.4 Explain, why the congruent and incongruent melting points are invariant points.
6.5 Explain, why we observe a region over which binary solid solution is in equilibrium
with the melt. How are the relative amounts of the two solutions, namely, solid and
liquid, in equilibrium with each other determined?
6.6 Figure 6.9.1 shows an eutectic phase diagram of a system exhibiting limited solubility
in the solid state. Besides this, if a system also exhibits a compound formation, then
the phase diagram has an appearance as shown in Fig. 1. Label the diagram with
adequate explanation.
Temperature

Pure AxBy Pure

Fig. 1 A Composition B

6.7 Figure 6.10.1 is a peritectic phase diagram of a system exhibiting limited solubility
in the solid state. Besides this, if a system also exhibits an incongruent compound
formation, then the phase diagram has an appearance as shown in Fig. 2. Label the
diagram with adequate explanation
328 A Textbook of Physical Chemistry

Fig. 2

6.8 Figure 3 depicts the phase diagram of a system where (i) the two components are
partially miscible in the liquid phase over a certain range of compositions and (ii) the
two components also form two solid solutions. Label the diagram and sketch the
cooling curves for the system shown therein.
Temperature

Pure Composition Pure

Fig. 3 A B
6.9 (a) Given are the following equilibria:
(i) CuSO4 5H2O(s) CuSO4 3H2O(s) + 2H2O(g)
(ii) CuSO4 3H2O(s) CuSO4 H2O(s) + 2H2O(g)
(iii) CuSO4 H2O(s) CuSO4(s) + H2O(g)
 Phase Diagrams of Two-Component Systems 329

With the help of the phase rule, show that each of the above equilibria is univariant.
(b) Let the various equilibria given in part (a) be studied at a constant temperature.
Since each equilibrium is univariant, it implies that the pressure of water vapour in
equilibrium with two solid salts will have a definite value. Show that this conclusion
is in agreement with that derived from a consideration of the equilibrium constant.
(c) At 25 °C, the pressures of water vapour of various equilibria given in part (a) are found
to be pi = 7.8 mmHg, pii = 5.6 mmHg and piii = 0.8 mmHg, respectively. The dehydration of
CuSO4 5H2O is studied by enclosing it in a closed container (attached to a vacuum pump
and manometer) followed by evacuation. The pressure of the system is determined from
time to time and the results obtained are shown in Fig. 4. Explain the results shown therein.

Fig. 4
6.10 What type of cooling curve do you expect for a pure substance?
6.11 The phase diagram of a binary system exhibiting partial miscibility both in liquid
and solid phases has an appearance as shown in Fig. 5. Label the diagram and draw
the cooling curves for the points shown therein.
(Ans. (1) L1, (2) L2, (3) L1 + L2, (4) solid solution , (5) and L1,
(6) and L2, (7) solid solution ,
(8) and L2, and , (9) and )
6.12 The elements Ag and Sr form four stable congruent compounds. Construct the phase
diagram of Ag-Sr system from the following data:
m.pt. of Ag 960.5 °C ¸
˝ Eu1 750 ºC
m.pt. of Ag4Sr 781 °C ˛ ¸
˝ Eu2 693 ºC
m.pt of Ag5Sr3 760 ºC ¸ ˛
˝ Eu3 638 ºC
m.pt. of AgSr 680°C ˛ ¸
˝ Eu4 645 ºC
m.pt. of Ag2Sr3 665 °C ¸ ˛
˝ Eu5 436 ºC
m.pt. of Sr 757 °C ˛
Label the entire phase diagram.
6.13 (a) The phase diagram of the Ca-Al system has the following data:
m.pt. of Ca 840 °C
m.pt. of Al 660 °C
Congruent m.pt. of CaAl2 1 063 °C
Incongruent m.pt. of CaAl3 700 °C
330 A Textbook of Physical Chemistry

1
3
5

Temperature
6

8
4

9 7

Pure Composition Pure

A B
Fig. 5
Composition of the melt at 700 °C is 14 mass % Ca.
Eutectic point involving Ca and CaAl2 is at 540 °C and has 75 mass % of Ca.
Eutectic point involving Al and CaAl3 is at 600 °C and has 8 mass % Ca.
(b) Draw the phase diagram and from it predict the nature of the system for the
following data:
(i) 80 mass % Ca at 700 °C. (vi) 25 mass % of Ca at 650 °C.
(ii) 60 mass % Ca at 800 °C. (vii) 25 mass % of Ca at 500 °C.
(iii) 37 mass % of Ca at 800 °C. (viii) 10 mass % of Ca at 650 °C.
(iv) 37 mass % of Ca at 600 °C. (ix) 5 mass % of Ca at 640 °C.
(v) 25 mass % of Ca at 750 °C. (x) 5 mass % of Ca at 500 °C.
Also calculate wherever possible the relative amounts of the two phases.
6.14 Figure 6 depicts the phase diagram of CuSO4-H2O system. Label the various

Fig. 6
 Phase Diagrams of Two-Component Systems 331

points, lines and areas of the diagram. Describe the sequence of phase changes if a
dilute solution of copper sulphate is dehydrated at 5 °C ending up with anhydrous
copper sulphate.
6.15 Cooling curves for the binary alloy system, gold-antimony, give the following data:

Mass % Sb Start of freezing Completion of freezing

ºC ºC
0 1 063 1 063
10 830 360
20 470 360
30 400 360
40 445 360
45 455 360
55 460 460
60 495 460
70 545 460
80 580 460
90 610 460
100 631 631
(a) Plot the phase diagram for the system and identify all areas and phases.
(b) Describe the sequence of events when liquid melts of 20, 50 and 80 amount per
cent antimony are cooled from 800 °C to 300 °C.
(c) If a sample of overall composition 40% by mass Sb were examined at 200 °C.
what components would be present and in roughly what proportions?
6.16 The following information is known about the two-component A-B system: m.pt.
of pure A 660 °C, m.pt. of pure B 1 500 °C. Compound C having 24 mol % B
decomposes at 950 °C to give D (50 mol % of B) and liquid containing 20 mol % of
B. Compound D melts congruently at 1 650 °C. (Eutectic)1 at 600 °C. corresponding
composition is 10 mol % B. (Eutectic)2 at 1 380 °C, corresponding composition is
80 mol % B. Draw the phase diagram. Give the form of compounds involved. A
melt containing 40 mol % of B is cooled from 1 650 °C. Indicate the various phase
changes which take place.
6.17 The following information is known about the two-component A-B system:
Molar mass of A = 24.3 g mol–1, m.pt. of A = 651 °C
Molar mass of B = 59.7 g mol–1, m.pt. of B = 450 °C
Two compounds C and D are formed.
C contains 54.7% by mass of B and melts incongruently at 770 °C yielding D and
a liquid containing 38% by mass of B.
D melts sharply at 1 180 °C yielding a liquid containing 83% by mass of B.
Two eutectics at 510 °C with 28% by mass of B and at 1 080 °C with 88% by mass
of B.
Solids are immiscible in the solid state and completely miscible in the liquid phase.
Construct the phase diagram, and label it. Draw cooling curves for 45% and 60%
by mass of B. Deduce the forms of C and D.
6.18 The system CaF2(m.pt., 1 360 °C) and CaCl2 (m. pt. 772 °C) shows an incongruent
behaviour, forming a compound at 1 : 1 ratio. The compound melts at 737 °C giving a
liquid containing 60 mol % of CaCl2. The eutectic point is at 625 °C with the eutectic
composition of 80 mol % of CaCl2. Draw the phase diagram and label it. Draw cooling
curves for 50% and 60% by mol of CaCl2.
332 A Textbook of Physical Chemistry

6.19 Given here are the data of the binary system copper nitrate-water. Construct the
phase diagram and label it.
Composition of Saturated Solution at Various Temperatures

Temperature Cu(NO3)2
ºC g per 100 g Solid phase
solution
– 2.35 8.0 Ice
– 9.3 21.3 ”
– 20.0 34.3 ”
– 24.0 35.9 Ice + Cu(NO3)2 9H2O
– 21.0 37.4 Cu(NO3)2 9H2O
– 20.0 39.8 Cu(NO3)2 9H2O + Cu(NO3)2 6H2O
0 45.0 Cu(NO3)2 6H2O
+ 20.0 55.6 ”
24.5 61.4 Cu(NO3)2 6H2O + Cu(NO3)2 3H2O
40.0 61.5 Cu(NO3)2 3H2O
60.0 64.2 ”
80.0 67.5 ”
114.5 77.6
Cu(NO3)2 9H2O = 53.7 mass % of Cu(NO3)2
Cu(NO3)2 6H2O = 63.5 mass % of Cu(NO3)2
Cu(NO3)2 3H2O = 77.7 mass % of Cu(NO3)2
6.20 Give below are the data of the binary system sodium iodide-water. Construct phase
diagram and lable it.
Composition of Saturated Solution at Various Temperatures

Temperature NaI
ºC g per 100 g Solid phase
solution
– 4.25 14.6 Ice
– 9.75 26.5 ”
– 31.4 3900 lce + NaI 5H2O
– 15.2 57.2 NaI 5H2O
– 13.5 60.2 NaI 5H2O + Nal 2H2O
0 61.3 NaI 2H2O
10 62.8 ”
20 64.2 ”
30 65.5 ”
40 67.2 ”
50 69.5 ”
60 72.0 ”
65 74.4 NaI 2H2O + Nal
80 74.7 Nal
100 75.1 ”
120 76.3 ”
140 77.2 ”
Nal 5H2O = 62.5 mass % Nal
Nal 2H2O = 80.6 mass % Nal
 Phase Diagrams of Two-Component Systems 333

6.21 A system of A (1 100 °C) and B (600 °C) shows incongruent behaviour. It has a
peritectic temperature at 700 °C where a solid containing 25 mol % of B melts giving
a liquid of 48 mol % of B. The eutectic temperature is 400 °C and the corresponding
composition is 85 mol % of B. Plot a phase diagram and label it. Draw cooling
curves for solutions containing 25 mol % B, 48 mol % B and 56 mol % of B.
6.22 The following data were obtained for Mg-Ni system:
m.pt. of Mg = 651 °C
m.pt. of Ni = 1 450 °C
Compound MgNi2 melts congruently at 1 180 °C.
Compound Mg2Ni melts incongruently at 770 °C giving a melt of 38 mass % of Ni.
First eutectic at 510 °C with eutectic composition of 28 mass % of Ni
Second eutectic at 1 080 °C with eutectic composition of 88 mass % of Ni
No solid solution formation
Construct phase diagram and label it.
6.23 Describe the sequence of effects that is produced when a 10% solution of ferrous
sulphate of Fig. 6.12.5 is subjected to the isothermal dehydration at 10 °C.
6.24 The following data were obtained for the copper-lanthanum system:
Melting point of Cu = 1 083 °C
Melting point of La = 812 °C
The compound LaCu6 melts congruently at 913 °C
The compound LaCu4 melts incongruently at 735 °C
The compound LaCu2 melts congruently at 834 °C
The compound LaCu melts incongruently at 551 °C
Three eutectic temperatures were observed:
840 °C (Cu + LaCu6)
725 °C (LaCu2 + LaCu4)
468 °C (LaCu + La)
Sketch the phase diagram and label each area.
6.25 The melting points and enthalpies of fusion of Pb and Sb are
Pb 327.4 °C 5.10 kJ mol–1
Sb 630.5 °C 20.08 kJ mol–1
Calculate the solid-liquid equilibrium lines. Estimate the eutectic composition
graphically and then calculate the eutectic temperature.
(Ans. xPb = 0.855, 520 K)
6.26 Metals A and B form compounds AB3 and A2B3. Solids A, B, AB3 and A2B3 are
immiscible in each other as solids but are completely miscible as liquids. Melting
points of A and B are 600 °C and 1 100 °C, respectively. Compound A2B3 melts
congruently at 900 °C and gives a simple eutectic with A at 450 °C. Compound AB3
decomposes at 800 °C to give another compound and the melt. This gives another
eutectic with B at 650 °C. Draw the simplest phase diagram with these facts and
label it. Draw cooling curves for melts of 90 mol% A and 30 mol% A.
6.27 The following phase transitions are observed for iron:
Body-centred 910 ∞C Face-centred 1 401 ∞C
Body-centred 1 535 ∞C
����� �
� cubic structure �
�����
����� �����
����� � liquid
cubic structure ����� � cubic structure �
(a -iron) (g -iron) (d -iron)

The iron-rich portion of the phase diagram of iron-carbon system is of interest and
is shown in Fig. 7
334 A Textbook of Physical Chemistry

Fig. 7

The description of the phase diagram is as follows.

Location of the Status of the system

system
Areas
1 Liquid phase
2 Solid solution of Fe and C known as austenite
3 Austenite Liquid
4 -Fe containing some C
5 Austenite + -Fe (with some C)
6 Austenite + Fe3C (called cementite)
7 -Fe + cementite
Lines
at 700 °C A eutectic-type three phase line at 700 °C
Phases are -Fe with some C, austenite and cementite
at 1 125 °C A eutectic-type three phase line. Phases are austenite, liquid
and cementite.
Answer the following:
(a) Iron with about 2 per cent carbon forms a fairly crude steel known as cast iron.
It has valuable corrosion-resistant properties. One such system in liquid phase is
shown by the point a1 in Fig. 7. Describe the sequence of events that takes place
when this system is cooled along the isopleth a1a2 a3a4a5.
(Note: The system of composition of cast iron does not become a single phase until
its melting point is reached. If the composition is close to the eutectic, its melting
point is low enough to allow a fairly easy casting procedure.)
 Phase Diagrams of Two-Component Systems 335

(b) When more of carbon is eliminated, a higher grade of steel is obtained. One such
system in the austenite form is shown by the point b1 in Fig. 7
Describe the sequence of events that takes place when this system is cooled along
the isopleth b1b2b3b4.
(Note: Steel when present in austenite form can be rolled very easily. At temperature
below 700 ºC, it contains -Fe (with some C) and cementite. The rigidity of steel
is due to extreme hardness of cementite.)
6.28 In Mg-Zn system, there are four temperatures at which three phases exist with mass
percentage of Zn as follows:
340 °C solid solution (8%) + liquid (53%) + MgZn
354 °C liquid (55%) + MgZn + MgZn2
380 °C liquid (96%) + MgZn2 + MgZn5
364 °C liquid (97%) + MgZn5 + Zn
Melting points of Mg, Zn and MgZn2 are 923 K, 693 K, and 863 K, respectively.
Sketch the phase diagram and label it.
 7 Phase Diagrams of Three-Component
Systems

7.1 APPLICATION OF THE PHASE RULE

The expression of the degrees of freedom of a three-component system as given
by the phase rule is
F =C -P +2=3-P +2=5-P
As in the case of a two-component system, various equilibria studied in this chapter
do not involve any gaseous phase. Hence, the degrees of freedom of a system are
reduced by one. Thus for a condensed three component system, we have
F =C -P +l=3-P +l=4-P
System of One In this case, F = 4 – 1 = 3, and therefore, the values of three variables have to
Phase only be stated in order to define the system completely. These are temperature and
the amount fractions of any of the two components.
System of Two Here F = 4 – 2 = 2, and thus the values of two variables have to be specified
Phases in order to define the system completely. These are temperature and the amount
fraction of any one component in either of the two phases. These two phases
will be in equilibrium with each other and thus the amount fraction of the stated
component in the second phase will have a definite value.
System of Three In this case, F = 4 – 3 = 1, and this degree of freedom is the temperature of the
Phases system. All the three phases will have definite compositions at a given temperature.

7.2 SCHEME OF TRIANGULAR PLOT

The most commonly used scheme for plotting the two-dimensional equilibrium
diagram for three-component systems is the scheme of triangular plot as suggested
by Stokes and Roozeboom. In this scheme, various equilibria are studied at
a constant temperature and are plotted in an equilateral triangle as shown in
Fig. 7.2.1. The sides of this triangle are divided into 10 (or sometimes more,
say 100) equal parts and within the triangle, various lines parallel to the three
sides are drawn. The concentrations of various species are represented according
to the following scheme.
System Involving Each apex of the triangle represents a single component system and is designated
One Component by the symbol used for the component. For example, point A represents 100%
of the component A, or at this point the composition of the ternary system is
xA = 1, xB = 0 and xC = 0. In terms of mass per cent, we have 100 mass % of
A, 0 of mass % of B and 0 mass % of C.
 Phase Diagrams of Three-Component Systems 337

System Involving A point on the sides of the triangle represents a two-component system consisting
Two Components of the constituents written on either ends of the line. For example, a point any-
where on the line BC in Fig. 7.2.1 represents a two-component system of B and
C. The component A is completely absent here and thus has xA = 0. Since the
line BC is divided into 10 equal parts, the compositions of systems at the points
shown on this line can be determined easily and are described in Table 7.2.1.
A

g a

h b

i c

j D d

m² n² p²
k e

l m¢ n¢ o¢ p¢ q¢
f

Fig. 7.2.1 The triangle

plot B m n o t p q r C

Table 7.2.1 Compositions of Ternary System on the Line BC

Amount fractions
Point xA xB xC
B 0.0 1.0 0.0
m 0.0 0.9 0.1
n 0.0 0.8 0.2
— — — —
— — — —
— — — —
q 0.0 0.2 0.8
r 0.0 0.1 0.9
C 0.0 0.0 1.0

Alternatively, the composition at any point on the line BC (or on the other
two lines) can be determined with the help of the lever rule. For example, at
the point n, we have
338 A Textbook of Physical Chemistry

Amount of B in the system nC 8 units

= =
Amount of C in the system Bn 2 units

If concentrations are expressed in amount fractions, it is obvious that at the

point n, the amount fraction of B is equal to 0.8 whereas that of C is 0.2.
System Involving The perpendicular distance from A to BC is also divided into ten equal parts
Three Components with lines drawn parallel to the line BC, and thus these parallel lines represent
systems with different proportions of the component A; xA being one at A and
zero on the line BC. Points anywhere on one of the parallel lines represent
systems with a constant amount fraction of the component A. For example, the
line lf represents the systems with xA = 0.1. It can be verified that the length
of this line is 9/10 of the line BC and thus it represents a total amount fraction
of 0.9 of both the components B and C. At the point 1, composition of the
system is xA = 0.1, xB = 0.9 and xC = 0.0 and that at the point f is xA = 0.1,
xB = 0.0 and xC = 0.9. The line lf is divided into nine equal parts. The compositions
of systems at the points shown on this line are described in Table 7.2.2.

Table 7.2.2 Compositions of Ternary Systems on the Line lf

Amount fractions
Point xA xB xC
1 0.1 0.9 0.0
m 0.1 0.8 0.1
n 0.1 0.7 0.2
— — — —
— — — —
— — — —
p 0.1 0.2 0.7
q 0.1 0.1 0.8
f 0.1 0.0 0.9

On the line ke, compositions of systems represented by the points as

shown in Fig. 7.2.1 are given in Table 7.2.3.

Table 7.2.3 Compositions of Ternary Systems on the Line ke

Point Amount fractions

xA xB xC
k 0.2 0.8 0.0
m 0.2 0.7 0.1
n 0.2 0.6 0.2
— — — —
— — — —
— — — —
p 0.2 0.1 0.7
e 0.2 0.0 0.8
 Phase Diagrams of Three-Component Systems 339

The compositions of ternary systems on the other parallel lines can be

similarly written down.
Thus the composition of a ternary system with non-zero amount fractions
of components is represented by a point within the triangle. The composition
corresponding to any given point (or the location of the point corresponding to
any given composition) can be readily determined by the above method. Take,
for example, the point D shown in Fig. 7.2.1, the composition corresponding
to this point can be determined as follows:
(i) This point lies on the third parallel line from the bottom of BC and
thus has xA = 0.3.
(ii) This point also lies on the second parallel line from the line AC and
thus has xB = 0.2.
(iii) This point lies on the fifth parallel line from the line AB and thus has
xC = 0.5.
Hence, the composition of the system is
xA = 0.3, xB = 0.2 and xC = 0.5

METHODS OF COMPUTING COMPOSITION OF A TERNARY SYSTEM

The following general methods may be employed for computing the composition
of a ternary system.
Method of Parallel From the given point (say, D in Fig. 7.2.1) draw three lines parallel to the three
Lines sides of the triangle. It can be proved that the sum of the lengths of these
three such lines is always constant and is equal to the side of the triangle.†
Moreover, distance of the line from the point D to any side is proportional to
the amount fraction of the component occupied by the opposite corner. Thus,
we have
Length of the line Dd (or Ds) amount fraction of B
Length of the line Dt (or Dq) amount fraction of A
Length of the line Dh (or Dj) amount fraction of C
The ratio of the lengths of these lines are
Dd : Dh : Dt : : 2 : 5 : 3
and thus the composition of the system is

xB = 0.2, xC = 0.5 and xA = 0.3

†
The parallel lines drawn from the point D are Dh, Dt and Dd. We have the following
equalities:
Dt = Dq, Dd = qC = eC, hq = Ae
Now the sum of the lengths of the three sides is
Dh + Dt + Dd = Dh + Dq + eC = hq + eC = Ae + eC = AC
340 A Textbook of Physical Chemistry

Method of From the given point, draw three perpendiculars De, Df and Dg on the three sides
Perpendicular Lines of the triangle as shown in Fig. 7.2.2.

g f

Fig 7.2.2 Computation

of composition of a
ternary system B e C

The distances De, Df and Dg will be proportional to the amounts of A, B and

C, respectively. Thus
Length of line De
= xA
Sum of the lengths of lines De, Df and Dg
Length of line Df
= xB
Sum of the lengths of lines De, Df and Dg
Length of line Dg
= xC
Sum of the lengths of lines De, Df and Dg

It can be shown that the sum of the three perpendiculars De, Df and Dg is
equal to 0.867 × edge-length of the triangle. Thus, if edge-length is 100 mm,
the above relations of amount fractions are modified as follows:
Length of line De
= xA
86.7 mm
Length of line Df
= xB
86.7 mm
Length of line Dg
= xC
86.7 mm
 Phase Diagrams of Three-Component Systems 341

A Direct Method If the edge-length of the triangle is 100 mm, a direct method for computing
composition for a given point D (or vice versa) may be employed. At point D,
a scale parallel to the side BC is placed and the distances in mm between the
point D and the sides AB and AC are measured. These distance yield directly the
per cent of C and B, respectively.† The per cent of A at the point D will be
100 – (% B + % C).
For locating a point corresponding to the given composition, we adopt the
following procedure. The distance of perpendicular from apex A to the side BC
is
0.867 (edge-length) = 0.867 × 100 mm = 86.7 mm
This length represents 100 per cent of A. The per cent composition of
A in the given ternary system is multiplied by 0.867 and let it be x. A scale
at a distance of x (in mm) parallel to the side BC is placed and a point at a
distance (in mm) equal to the per cent of C from the side AB is located. This
point represents the required composition of the given ternary system.
Alternatively, a point at a distance (in mm) equal to the given per cent
of A along the side BA or CA (i.e. from B or C towards A) is located. A scale
at this point parallel to the side BC is placed and a point at a distance (in
mm) equal to the given per cent of C from the side AB as located. This point
represents the required composition of the given ternary system.
By Using the Lever The composition corresponding to a given point can be determined by making
Rule use of the lever rule twice. For example, for the point a shown in Fig. 7.2.3,
we can determine its composition as follows.
A line Aa joining the apex A and the given point a is drawn and is extended
up to the side BC. Applying the lever rule at a along the line Ab, we get

Total mass of B and C Aa

= (7.2.1)
Mass of A ab
Adding one on both sides and taking its inverse, we have

Mass of A ab
=
Total mass of A, B and C Ab

Ê ab ˆ
Mass of A = Á
Ë Ab ˜¯
or (Total mass of A, B and C) (7.2.2)

Now applying the lever rule at b along the line BC, we get

Mass of C Bb
= (7.2.3)
Mass of B bC

†
If the edge-length is not equal to 100 mm (say, x) the lengths may be multiplied by a
factor of 100 mm/x to yield directly the per cent compositions C and B, respectively.
342 A Textbook of Physical Chemistry

5.7 cm

3.1 cm

Fig. 7.2.3 Use of the

lever rule within a
triangle B 6.6 cm b 3.4 cm C

Adding one on both sides and taking its inverse, we get

Mass of B bC
=
Mass of B and C BC

Ê bC ˆ
Mass of B = Á
Ë BC ˜¯
or (Mass of B and C) (7.2.4)

Finally, we will have

Mass of C = (Total mass of A, B and C) – (Mass of A and B) (7.2.5)
For calculating per cent composition, total mass of A, B and C will be equal
to 100 g. Thus, Eqs (7.2.2), (7.2.4) and (7.2.5) will be reduced to

Ê ab ˆ
Mass of A = Á
Ë Ab ˜¯
(100 g)

Ê bC ˆ
Mass of B = Á (100 g - mass of A)
Ë BC ˜¯
Mass of C = 100 g - (mass of A and B)
Hence, for the point a, shown in Fig. 7.2.3, we have

Ê 3.1 cm ˆ
Mass of A = Á
Ë 8.8 cm ˜¯
(100 g) = 35.23 g
 Phase Diagrams of Three-Component Systems 343

Ê 3.4 cm ˆ
Mass of B = Á (100 g - 35.23 g) = 22.02 g
Ë 10 cm ˜¯
Mass of C = 100 g - (35.23 g + 22.02 g) = 42.75 g
Method Based on The following two features of an equilateral triangle can also be used to locate
the Two Features of the point corresponding to a given ternary system or vice versa.
an Equilateral (1) Various systems with a constant ratio of two components and the varying
Triangle amount of the third component will lie on a line drawn from the apex representing
the third component to the opposite side of the triangle. Take, for example, the
perpendicular line AX from the corner A to the opposite side BC in Fig. 7.2.4.
A
B²¢
B² b
B¢ c

B²¢1 C²¢
e X²¢

f
B²1 C²
g X²

h
Fig. 7.2.4 Triangular
i
plot showing various B¢1
systems of constant ratio C¢
j X¢
of B and C and varying B C
amount of A. X X1

This line intersects just in the middle of various lines drawn parallel to
BC and hence a point anywhere on this line represents a system in which the
ratio of the components B and C is always one (i.e. equal amount fractions of
B and C). The compositions of systems represented by the points on this line
as shown in Fig. 7.2.4 are given in Table 7.2.4.
Table 7.2.4 Compositions of the Ternary System on the Line AX.

Amount fractions
Point A B C
A 1.0 0 0
b 0.9 0.05 0.05
c 0.8 0.1 0.1
— — — —
— — — —
— — — —
i 0.2 0.4 0.4
j 0.1 0.45 0.45
X 0.0 0.5 0.5
344 A Textbook of Physical Chemistry

The fact that a point on the line AX represents a constant ratio of B and
C is also true for any line drawn from A to BC. For example, on the line AX1
of Fig. 7.2.4, the constant ratio of B and C is
Amount fraction of B CX1 C¢X ¢
= =
Amount fraction of C BX1 B1¢ X ¢ (or B¢ X ¢)
C≤ X ≤ C≤¢ X ≤¢
= =
B1≤ X ≤ (or B≤ X ≤ ) B1≤¢ X ≤¢ (or B≤¢ X ≤¢ )
The above feature can also be used to locate the point corresponding to the
composition of a given ternary system (say, for example, x mass % A, y mass %
B and z mass % C). First of all, a binary system (say B-C) having the given ratio of B
and C in the ternary system is imagined. In the present case, the binary system B-C
will contain y/(y + z) × 100 mass per cent of B). A point on the line BC corresponding
to this composition (say, b in Fig. 7.2.3) is chosen and it is joint with the apex A.
The distance bA represents 100 mass % A. The length corresponding to the given
mass per cent A is determined. In the present case, it is
Ê bA ˆ
ÁË ˜ (mass % A)
100 mass % A ¯
A point at the above distance on the line bA from the side BC is located.
This point represents the required composition of the ternary system.
(2) The fact that the binary systems A-B, B-C and A-C are represented by points
on the lines AB, BC and AC, respectively, and the ternary system A-B-C by a
point within the triangle ABC can be extended to any line or smaller triangle
within bigger triangle ABC. For example, a point on the line DE in Fig. 7.2.5
represents a system that is composed of two systems D and E with their relative
amounts as given by the lever rule. Take, for example, the point G on the line
DE. The system corresponding to this point can be prepared from the two
systems D and E by mixing them in the following ratio.
Amount of D in the system GE
=
Amount of E in the system DG
In other words, we can say that all systems that can be prepared from
D and E will lie on the line DE. The same is also true on the lines EF and
FD. Thus, all those systems which can be prepared by mixing E and F will
lie on the line EF whereas those prepared from F and D will lie on FD. In a
similar manner, all possible combinations that can be prepared from D, E and
F will lie within the triangle DEF. Their relative amounts may be determined
by employing the lever rule twice.
Many categories of three-component systems are possible depending on the
Three-Component characteristics of the components. For example, the given component may exist
Systems either in the liquid form or in the solid form and may be miscible or partially
miscible or completely immiscible with other components. In the present chapter,
we will consider only two important categories of these systems. These are:
(i) Systems composed of three liquid components which exhibit partial miscibility.
(ii) Systems composed of two solid components and a liquid.
 Phase Diagrams of Three-Component Systems 345

E
G

Fig. 7.2.5 Triangular F

plot showing the
application of the lever
rule on any line drawn
within the triangle B C

In the next two sections, we shall consider the triangular plots of systems
belonging to the above two categories.

7.3 SYSTEMS OF THREE LIQUID COMPONENTS EXHIBITING PARTIAL MISCIBILITY

In this section, we consider the following three possibilities based on the mutual
solubilities of the three components.

Formation of one pair of partially miscible liquids.

Formation of two pairs of partially miscible liquids.
Formation of three pairs of partially miscible liquids.
The general appearance of triangular plots of these three possibilities are
discussed below one after the other.†

FORMATION OF ONE PAIR OF PARTIALLY MISCIBLE LIQUIDS

System of Two We assume that out of the three components A, B and C, the components B and
Partially Miscible C show partial mutual solubility with each other and the third component A
Liquids exhibits complete miscibility with both the components B and C. Let us start with
only two components B and C. The state of such a system can be represented

†
Throughout this Chapter, a system is represented by an alphabet, printed in roman type,
and its composition is represented by the same alphabet printed in italics.
346 A Textbook of Physical Chemistry

by a point on the line BC. The two components will be completely miscible in
each other only in the limited range of concentrations and will exhibit partial
miscibilities beyond these ranges with the formation of two conjugate saturated
solutions, one composed of a solution of C in B and the other of B in C. These
two solutions will have definite compositions at a given temperature and will be
independent of individual amounts of the two liquids. Let these compositions
be represented by the points b and c on the line BC as shown in Fig. 7.3.1.
Thus, the two liquids B and C will be completely miscible in each other from
the range B to b and from c to C and form two conjugate solutions b and c in
the range b to c. The relative amounts of these two solutions can be determined
with the help of the lever rule. For example, at the point X, we have

Amount of the solution of C in B Xc

=
Amount of the solution of B in C Xb

Fig. 7.3.1 Triangular

plot showing the
formation of one pair of
partially miscible liquids

Effect of Adding If now the component A is added to a system represented by a point on the line
Third Component BC, the state of the system will move along a line obtained by joining the given
point with the apex A. Let us add this component to a system represented by
the point X. Since A is miscible in both the conjugate solutions, the addition
of A will cause an increase in the mutual solubilities of the two components
B and C. Consequently, compositions of the two conjugate solutions will now
become more close to each other.
Nature of the As usual the compositions of the two conjugate solutions will be given by the
Tie Line two ends of a tie line. In general, the various tie lines are neither parallel to
the line BC nor parallel to each other, if the added component A is not equally
 Phase Diagrams of Three-Component Systems 347

soluble in both the solutions. If the component A is relatively more soluble in

the layer rich in C than it is in the layer rich in B, then obviously the state
point of the layer rich in C will lie nearer to the apex A than that of the layer
rich in B. The tie line becomes shorter and shorter as more of A is added to the
system indicating that the compositions of the two solutions become closer and
closer to each other. This is consistent with the fact that the mutual solubilities
of the two components increase as more and more of A is added to the system.
Plait Point At point P, compositions of the two solutions become identical and thus two
solutions merge into each other and form a single solution. This is an invariant
point (at constant T and p, F = C – r – P + 0 = 3 – 1 – 2 = 0) and is known
as plait point.
Binodal Curve When a smooth curve passing through various points representing the
compositions of the conjugate solutions is drawn, one gets a binodal curve bPc,
with a maximum at M. In general, the plait point P lies either to the left or to the
right of this maximum point M since various tie lines are not horizontal. The plait
point will coincide with the maximum only in one particular case when the added
constituent distributes equally in both the layers. In this particular case, various
tie lines are horizontal and thus at the maximum point M, the two solutions have
identical compositions and thus merge into each other to form a single solution.
General The general characteristics of the phase diagram of a system exhibiting one pair
Characteristics of of partially miscible liquids can now be summarized as follows:
the Phase Diagram Point outside the binodal curve A point outside the binodal curve bPMc
represents one liquid layer only. According to the phase rule, such a system
can be completely defined if the values of two degrees of freedom, apart from
temperature and pressure, are stated (F = C – P + 2 = 3 – l + 2 = 4, minus
2 of temperature and pressure, and thus F = 4 – 2 = 2). These two degrees
of freedom are the two composition terms corresponding to any of the two
components of the liquid phase.
Point within the binodal curve A point inside the binodal curve represents
a system in which the two partially miscible liquid solutions are formed. The
compositions of these two solutions are the intersection points of the tie line
drawn from the point under study with the binodal curve. The relative amounts
of the two solutions are given by the lever rule. For example, at the point X , we
have
Composition of the solution of B in C (i.e. richer in C) = c
Composition of the solution of C in B (i.e. richer in B) = b

Amount of the solution of B in C (i.e. richer in C) b ¢X ¢

and =
Amount of the solution of C in B (i.e. richer in B) c ¢X ¢

Applying the phase rule to a system within the binodal curve (where P = 2),
we have

F =C -P +2=3-2+2=3
348 A Textbook of Physical Chemistry

Leaving two degrees of freedom corresponding to the constant temperature and

pressure, we have
F=1
and thus one concentration term, which allows the position of one layer to be
fixed on the binodal curve, is sufficient to define the system completely.

Effects Produced When the Component A is Added to a Binary System of B and C

As indicated earlier the state of the overall system will move along a line
obtained by joining the state point, say X in Fig. 7.3.1, of the binary system
with the apex A of the triangle. In general, the following two types of behaviour
are observed depending on the original composition of the binary system.
When the line AX does not pass through the plait point P Suppose the line AX
lies to the right of the plait point P. Then as we move from X to A, we observe
that the relative lengths of tie lines right to the line AX decrease steadily till the
point Y is reached. The net effect that is produced is that the relative amounts
of the two solutions change as more and more of A is added to the system; the
amount of the solution of C in B decreases steadily whereas that of B in C steadily
increases.† At the point Y, practically whole of the solution of C in B disappears
and the system mainly consists of the solution of B in C. Above the point Y, the
system remains that of one liquid only. Thus, the conversion of two liquid layers
into one takes place through the vanishing of liquid layer of C in B. The same is
also true if the line AX lies left to the point P. Here, it is the solution of B in C
that gradually decreases and ultimately disappears completely.
When the line AX passes through the plait point P The above behaviour of
conversion of two liquid layers into one layer through the vanishing of one of
the layers, however, is not observed when the line AX passes through the plait
point P. In this case, both the solutions remain intact right up to the point P
but their compositions approach each other and become identical at the point
P. Consequently, the two liquid layers merge into each other at the point P to
give a single liquid layer. Thus, the production of a single layer is not through
the disappearance of one of the liquid layers but through the merger of the two
solutions into each other at the point P. Similarly, the effects produced when
component B (or C) is added to a mixture of A and C (or A and B) can be analysed.

Effects Produced When the Proportion of A is Kept Constant and the Amounts of Other
Two Components are Varied
The state of the system in which the proportion of A is kept constant and the

†
Strictly speaking, after adding A, we get a ternary system of A. B and C. However, for
the sake of discussion, we retain the original terminology of binary system. Thus for a
ternary system, a solution of B in C means a solution of A and B in C or a solution
that is richer in C.
 Phase Diagrams of Three-Component Systems 349

amounts of the other two are varied will be represented by the points on a line
drawn parallel to the side BC of the type xy shown in Fig. 7.3.1. The sequence
of effects that is produced as one moves from x to y can be readily interpreted
with the help of Fig. 7.3.1. The system continues to be a single layer till the
binodal curve is reached where the single liquid splits into two layers x and y ;
the former being the solution of C in B whereas the latter is of B in C. Now
as one moves from x to y , one finds that the line xy cuts various tie lines in
different ratios as can be seen from the lengths of tie-lines below the line x y
and those lying above this line; the former increases gradually whereas the
latter decreases. Consequently, the relative amounts of the two solutions vary
as one moves from x to y ; the amount of the solution of B in C gradually
increases whereas that of C in B gradually decreases. Besides this, composition
of the solution of C in B moves along x b whereas that of B in C moves along
y y . At the point y , the solution of C in B completely disappears and thus
the system mainly consists of the solution of B in C. From y to y, the system
continues to be a single liquid. The above sequence of conversion from one
layer to two, and then back to one layer will be observed only for those liquids
which contain lesser amount of component A as compared to that present in a
solution corresponding to the maximum point M of the binodal curve.
If the original composition of the system happens to lie between P and
M, it is obvious that the single solution that splits into two is of the one of B
in C. The two solutions again merge on the other side of the binodal curve to
the given back the solution of B in C. This behaviour is observed whenever the
amount of A in the original system lies between plait point P and maximum
point M. Such solutions are said to show retrograde solubility.

Effect of Area within the binodal curve of a triangular plot represents the region of partial
Temperature miscibility where two conjugate solutions are formed. If it be assumed that the
mutual solubilities of these two solutions increase with increasing temperature,
the compositions of the two solutions will come more close to each other when
the temperature is increased. Consequently, the area enclosed by the binodal curve
will become smaller and smaller. In order to express these effects adequately,
we will have to construct triangular plots at different temperatures and then
correlate them with each other or, alternatively, a 3-dimensional plot can be
constructed with an equilateral triangle as a base and the vertical axis representing
temperature of the system. This model, in fact, will be a triangular prism. Any
horizontal section of such a three-dimensional diagram gives a triangular plot
at a constant temperature. However, in the present case, the general behaviour
can be understood by plotting a number of isothermal binodal curves in the
same triangle as shown in Fig. 7.3.2. The binodal curve enclosing larger area
corresponds to a lower temperature as the mutual solubilities of the two conjugate
solutions are lesser at lower temperatures. At a sufficiently low temperature, the
area covered may become so large that the binodal curve may cut the side AB
as shown in Fig. 7.3.2 indicating that the two components A and B like B and
C also become partially miscible with each other.
350 A Textbook of Physical Chemistry

Fig. 7.3.2 Effect of B C

temperature on the Tc T4 T3 T2 T1
binodal curve, T1 < T2 <
T3 < T4 < ... < Tc

Critical Solution When the temperature is raised, the area enclosed by the binodal curve becomes
Temperature smaller and smaller and is ultimately reduced to a point at a sufficiently high
temperature (say, at Tc). Thus, the three liquids will become completely miscible
in all proportions at temperatures greater than Tc. The temperature Tc for this
reason is known as the critical solution temperature for the ternary system. This,
however, is not true as on the line BC, where this point lies, we have a system
of two components of B and C, and thus more precisely, temperature Tc should
be known as the binary critical solution temperature.
The true critical solution temperature for the ternary system is observed
only when the various binodal curves have the general appearance as shown
in Fig. 7.3.3. In this particular case, the binodal curves at high temperatures
consists of closed curves and thus have two plaits points. The area of the closed
curve decreases as the temperature is raised and ultimately reduces to a point K
at some higher temperature. It is obvious that at temperatures higher than this,
the three liquids will be completely miscible and thus the system consists of
a single liquid layer only. The temperature corresponding to the point K is, in
fact, the true critical solution temperature for the ternary system.
Examples Examples of system yielding one pair of partial miscible liquids
are
Acetic acid-chloroform-water (Fig. 7.3.1)
Aniline-phenol-water at 50 °C (Fig. 7.3.2)
Acetone-phenol-water (Fig. 7.3.3)
 Phase Diagrams of Three-Component Systems 351

P¢

Fig. 7.3.3 Triangular K

plot showing the critical
solution temperature for B C
P
the ternary system

Example 7.3.1 For the ternary system benzene-isobutanol-water at 25 °C and 1 atm, the following
compositions have been obtained for the two phases in equilibrium.

Water-rich phase Benzene-rich phase

isobutanol water isobulanol benzene
mass % mass % mass % mass %
2.33 97.39 3.61 96.20
4.30 95.44 19.87 79.07
5.23 94.59 39.57 57.09
6.04 93.83 59.48 33.98
7.32 92.64 76.51 11.39

Plot these data on a triangular graph, indicating the tie lines.

(a) Estimate the compositions of phases that will be produced from a mixture of 20 mass
% isobutanol, 55 mass % water and 25 mass % benzene and also calculate their relative
amounts.
(b) What will be the composition of the principal phase if the first drop of the second
phase separates when water is added to a solution of 80 mass % isobutanol in benzene?
Solution The triangular plot obtained is shown in Fig. 7.3.4.
(a) The compositions of the two conjugate solutions produced at the given composition
point a (20 mass % isobutanol + 55 mass % water and 25 mass % benzene) are
(i) Water-rich layer: 5.23 mass % isobutanol, 94.5 mass % water
(ii) Benzene-rich layer: 39.57 mass % isobutanol, 57.09 mass % benzene
352 A Textbook of Physical Chemistry

Fig. 7.3.4

The relative masses of the two solutions can be determined from the lever rule. Thus,
we have

Mass of water-rich layer 4.6 cm

m 1.3
= =
Mass of benzene-rich layer 3.5 cm 1

(b) Point g represents a solution of 80 mass % isobutyl alcohol in benzene. If water is

added to this system, the state of the overall system will move along gh—a line obtained
by joining g to the apex C. At the point h, the solution will just split into two. The
composition of the system at h is
mass % benzene = hh /mm = 18
mass % water = hh /mm = 10
and mass % isobutanol = 100 – 18 – 10 = 72

FORMATION OF TWO PAIRS OF PARTIALLY MISCIBLE LIQUIDS

Expected Phase Let us assume that out of the three components A, B and C, two pairs of liquids
Diagram which show partial miscibilities be A and B, and B and C, and let the third pair
of liquids A and C be completely miscible with each other. In such a case, the
triangular plot will contain two binodal curves with their own plait points and
various tie lines corresponding to each of these two pairs of partially miscible
liquids as shown in Fig. 7.3.5. The binodal curve aQb is for the mixtures of two
liquids A and B containing C and the curve bPc is for B and C containing A.
Points Q and P are the respective plait points. The area enclosed within the curve
aQb represents the region of compositions where two conjugate solutions of A
 Phase Diagrams of Three-Component Systems 353

b¢
Q
P

Fig. 7.3.5 Triangular

plot depicting the
formation of two pairs of
partially miscible liquids B b c C

in B (containing C) and B in A (containing C) are formed; composition of the

former lies on Qb and that of the latter on the line Qa. Compositions of the two
conjugate solutions are joined with each other through various tie lines. At the
point Q, the two solutions have identical compositions and thus merge into each
other to give a single liquid layer. In a similar manner, the area enclosed within
the curve bPc represents the region of compositions where two conjugate solutions
of C in B (containing A) and B in C (containing A) are formed; composition of
the former lies on bP and that of the latter on the line cP. Again compositions of
the two conjugate solutions are joined with each other through various tie-lines
drawn within this area. At point P, the two solutions have identical compositions
and thus merge into each other to give a single liquid layer.
The area outside of these two binodal curves gives the region where the
three components are completely miscible and thus form a single liquid layer.
Example The system ethyl alcohol-water-succinic nitrile shows this type of behaviour
between 18.5 °C to 31 °C and thus has a triangular plot similar to Fig. 7.3.5
Effect of If it be assumed that the mutual solubilities decrease as temperature is lowered,
Temperature the area covered by the two binodal curves will become larger and larger on
decreasing the temperature. Ultimately a stage would be reached where the two
curves may overlap with each other and thus form a band type diagram, such
as shown in Fig. 7.3.6.
This diagram is very similar to the binodal curve of a system exhibiting
one pair of partially miscible liquids at some low temperature (e.g. the binodal
curve at T1 of Fig. 7.3.2). It is thus obvious that if the binodal curve forms a
band, it is not possible to predict the behaviour of the system when the temperature
354 A Textbook of Physical Chemistry

Fig. 7.3.6 Overlapping

of the two binodal curves B C

is raised, that is, whether it will form a system containing only one pair or two
pairs of partially miscible liquids.
Examples of systems exhibiting binodal bands are
Water-phenol-aniline
Water-ethyl acetate-n-butyl alcohol
Water-ethyl acetate-isobutyl alcohol
Water-ethyl acetate-sec-butyl alcohol

Example 7.3.2 Following are the compositions of the phases in equilibrium with each other in the system
methylcyclohexane-aniline-n-heptane at 1 atm and 25 °C.

Hydrocarbon layer Aniline layer

Methylcyclohexane n-Heptane Methylcyclohexane n-Heptane
mass % mass % mass % mass %
0.0 92.0 0.0 6.2
9.2 83.0 0.8 6.0
18.6 73.4 2.7 5.3
33.8 57.6 4.6 4.5
46.0 45.0 7.4 3.6
59.7 30.7 9.2 2.8
73.6 16.0 13.1 1.4
83.3 4.4 15.6 0.6
88.1 0.0 16.9 0.0

(a) Draw the triangular plot including tie lines.

(b) Characterize the system to which this triangle plot represents.
(c) Calculate the composition of the solution which just splits into two
 Phase Diagrams of Three-Component Systems 355

obtained by adding sufficient amount of aniline to a solution of 40 mass % of

methylcyclohexane in n-heptane.
(d) 100 g of a solution having composition 30 mass % methylcyclohexane
+ 28 mass % n-heptane was prepared. What is the nature of the system, whether it
forms a single solution or two solutions? If two solutions are formed what will be their
compositions and the respective amounts?
(e) If the system as given in part (d) represents two solutions, calculate the mass of
methylcyclohexane which should be added so that the system becomes one of a single
solution. What would be the composition of the resultant solution?
Solution (a) The triangular plot obtained is shown in Fig. 7.3.7. The edge length of the triangle
is 100 mm.

Fig. 7.3.7 Required

ternary plot

(b) The present system represents a case where two pairs of partially miscible liquids are
formed with an overlapping of the two binodal curves. The two pairs are
n-Heptane-Aniline
Methylcyclohexane-Aniline
The two liquids in the third pair, namely, methylcyclohexane and n-heptane, are completely
miscible with each other.
(c) Point a on the line AB represents a binary system of 40 mass % methylcyclohexane
in n-heptane. If aniline is added to this system, the state of the overall system
will move along abC. At point b, the single solution will just split into two
356 A Textbook of Physical Chemistry

solutions. The composition of the system corresponding to the point b can be calculated
as follows.

length ab 7.5 mm
Mass % of aniline, Wa = ¥ 100 = ¥ 100 = 8.662 = 9
length aC 86.6 mm

Since the edge length of the triangle plot is 100 mm, the length bb in mm on the line
b bb will also represent the mass % of aniline. This length is 9 mm as may be verified
from Fig. 7.3.7. Similarly, mass % of n-heptane will be equal to the length bb , which
is equal to 55 mm. Thus
Mass % n-heptane, Wh = length bb /mm = 55
and mass % methylcyclohexane, Wm = 100 – Wa – Wh = 100 – 9 – 55 = 36
(d) The point d represents the system of 30 mass % methylcyclohexane and
28 mass % n-heptane. The system will consist of two conjugate solution of compositions
given below.
(i) Hydrocarbon layer: Its composition is given by the point d at which we have
Mass % aniline = d1d /mm = 4
Mass % n-heptane = d2d /mm = 45
(ii) Aniline layer: Its composition is given by the point d at which, we have
Mass % aniline = d3d /mm = 89
Mass % n-heptane = d4d /mm = 4
The relative amounts of the two solutions may be calculated by employing the lever rule
as follows.

Mass of hydrocarbon layer dd ¢¢ 4.1 mm

= =
Mass of aniline layer dd ¢ 2.8 mm

Adding one to both sides, we get

Mass of hydrocarbon layer + Mass of aniline layer 4.1 + 2.8

=
Mass of anniline layer 2.8

Mass of aniline layer 2.8

or =
Total mass in the system 6.9

2.8
or Mass % of aniline layer = ¥ 100 = 40.59
6.9

Thus mass % of hydrocarbon layer = 100 – 40.59 = 59.41

(e) When methylcyclohexane is added to a system represented by the point d, the state
of the overall system will move along dA. At the point e, the two solutions will just
merge into one. The composition of the solutions at e is
Mass % n-heptane = ee /mm = 8
Mass % n-aniline = ee /mm = 12
Mass % methylcyclohexane = 100 – 12 – 8 = 80
The relative ratio of n-heptane and aniline at the point e will be the same as that of the
point d. Thus 8 mass % of n-heptane at e represents 28 g of n-heptane (same as that
 Phase Diagrams of Three-Component Systems 357

at point d) and 12 mass % of aniline at e represents 42 g of aniline. Thus the mass of

methylcyclohexane at the point d (80 mass %) is given as

28 g
Mass of methylcyclohexane = ¥ 80% = 280 g
8%

Thus, the amount of methylcyclohexane that need to be added to get one solution
= 280 g – Mass of methylcyclohexane at the point d
= 280 g – 30 g = 250 g

FORMATION OF THREE PAIRS OF PARTIALLY MISCIBLE LIQUIDS

Expected Phase Here all the three pairs A and B, B and C, and A and C show partial mutual
Diagram solubilities with each other and thus the triangle plot will contain three binodal
curves corresponding to each of these three pairs of partially miscible liquids
(Fig. 7.3.8). Each binodal curve will have its own plait point and the various lies
lines indicating the compositions of the two conjugate solutions that are formed.
A

Fig. 7.3.8 Triangular

plot for the formation of
three pairs of partially
miscible liquids B C

Interpretation of the phase diagram of Fig. 7.3.8 is straightforward. A

point anywhere within the three binodal curves represents a system of the two
conjugate solutions and that outside of these curves represents a single solution.
At lower temperatures, the partial mutual solubilities of the two components
become smaller, and thus the area enclosed by each of these binodal curved
becomes larger as temperature of the system is lowered. Eventually a stage may
be reached where the three binodal curves overlap each other and the triangular
plot takes the form as given in Fig. 7.3.9. A point anywhere in the area (marked
as 1) near each of the three corners of the triangle represents one liquid phase,
358 A Textbook of Physical Chemistry

2 2

E F
Fig. 7.3.9 Overlapping
of the three binodal 2 1
1
curves B C

whereas any point within the areas (marked as 2) traversed by tie lines implies
two conjugate liquids whose compositions are given by the two ends of the
tie line passing through the given point. Area within the smaller triangle DEF
(marked as 3) represents the region where three liquid layers in equilibrium are
formed, their compositions are given by the points D, E and F, respectively.
The compositions of these three liquids are definite at a given temperature
and pressure; this fact is in agreement with the phase rule since for P = 3,
F = C – P + 0 = 3 – 3 + 0 = 0.
An example of a system yielding three liquid phases in equilibrium is
succinic nitrile-ether-water.

7.4 TRIANGULAR PLOTS OF A TERNARY SYSTEM DEPICTING CRYSTALLIZATION OF

ITS COMPONENTS AT VARIOUS TEMPERATURES
It was stated in Section 7.3 that the triangular plots of a ternary system at various
temperatures can be represented in a 3-dimensional model of a triangular prism.
In this model, we have a base of an equilateral triangle and a vertical axis
which represents temperature of the system. Thus, any horizontal section of this
3-dimensional model gives the triangular plot at that particular temperature.
The understanding of the planar model involving the crystallization of the solid
components becomes much simplified if the qualitative nature of the above
3-dimensional model is studied at a glance. In this model, we have the following
characteristics.
 Phase Diagrams of Three-Component Systems 359

Depiction of Pure Each vertical axis represents the pure component at different temperatures. Thus,
Components the axis AA in Fig. 7.4.1 represents the component A only, while BB and
CC represent the components B and C, respectively. On each of these axes,
the melting point of the corresponding component can be shown. The points a,
b and c in Fig. 7.4.1 represent the melting points of the components A, B and
C, respectively. Thus, the component above its melting point is present in the
liquid form and that below this point is present in the solid form.
Depiction of Two- Each vertical face of the triangular prism represents a two-component system
Component System involving components occupied by the two corners of the triangle. Thus, the
vertical faces AA B BA, BB C CB and AA C CA represent the two-component
systems of A-B, B-C and A-C, respectively. On each of these faces, one can
draw the binary equilibrium phase diagram of the respective two-component
system. If, at present, it is assumed that the three two-component systems
show simple phase diagrams involving only the formation of eutectics with no
compound formation and solid solution, then the general appearance of the three
two-component phase diagrams will be as shown in Fig. 7.4.1. The curve adb is
the equilibrium phase diagram of A and B; along the line ad, solid A separates
out and along bd solid B separates out. At point d, both A and B separate out
simultaneously. It is thus the eutectic point of the system A-B. Similarly, the
curves bec and afc are the equilibrium diagrams of the systems B-C and A-C,
respectively, and the points e and f are the respective eutectic points.
Depiction of Three- If the third component, say A, is added to a system B-C, the resultant system
Component System will be represented by a point that lies within the triangular prism. Addition of
the third component will also affect the equilibrium curves depicting the start
of crystallization of the two components. In fact, the addition of A to B-C will
shift the eutectic point e to g along the line eg while the addition of B to A-C
will shift the eutectic point f to g along the line fg and that of C into A-B will
shift the eutectic point d to g along the line dg.
Crystallization of The three lines dg, eg and fg divide the total surface area of the prism into three
One component distinct surfaces begdb, cegfc and adgfa. Previously, along the lines be and bd,
from Ternary System we have the separation of solid B from the binary liquid mixtures of B-C and
A-B, respectively, and now the separation of B in the ternary system is represented
by the surface area begdb. Similarly, the separation of A and C is represented
by the points on the surface areas adgfa and cegfc, respectively. Thus, these
three surfaces describe the conditions of equilibrium of the melt and one of the
solids; melt solid A on the surface adgfa, melt solid B on the surface
begdb and melt solid C on the surface cegfc.
The fact that the separation of the solid in a ternary system is represented
by the surface is consistent with the requirements of the phase rule since P = 2
and thus F = C – P + l = 3 – 2 + l = 2. Thus, two degrees of freedom must
be stated in order to define the system completely. These are temperature and
the amount fraction of one of the components.
At temperature above any one surface, the system consists of only melt and
the moment the surface is reached on cooling the system, the pure component
360 A Textbook of Physical Chemistry

Fig. 7.4.1 Triangular

plots at various
temperatures on a
3-dimensional triangular
prism
 Phase Diagrams of Three-Component Systems 361

starts crystallizing. Thus, on cooling, the first crystal that separates out will
consist of pure A if the original composition of the system lies above the surface
of adgfa, it is pure B if the composition lies above the surface of begdb and is
pure C if the composition lies above the surface cegfc.
Crystallization of The surfaces begdb and cegfc intersect each other along the line eg. Thus, the
Two Components line eg represents various equilibria involving solid B, solid C and the melt. The
from a Ternary line eg, in fact, is the ternary eutectic curve. In a similar manner the lines dg
System and gf are other eutectic curves where solids A and B, and solids A and C are
in equilibrium with the melt, respectively. Thus, these three lines eg, dg and gf
indicate the conditions for separation of the two solid phases from the liquid of
different compositions. Systems along these lines are univariant as P = 3 and
thus F = C – 1 + l = 3 – 3 + l = l.
Crystallization of The three ternary eutectic eg, dg and fg curves meet one another at the common
all the Three point g which now represents a system when three solids A, B and C are in
Components equilibrium with the melt of composition g. According to the phase rule, the
point g is an invariant point since P = 4 and thus F = C – P + l = 3 – 4 + l
= 0. Thus, temperature and composition of the melt corresponding to the point
g are quite definite and are independent of the relative amounts of the three
components. At all temperatures below the temperature corresponding to the
point g, the system simply consists of a mixture of three solids A, B and C.
Depiction of In order to show the process of initial crystallization from ternary melts of
Crystallization on an various compositions on a two-dimensional model of an equilateral triangle, we
Equilateral Triangle project out the boundaries eg, dg and fg separating the three surfaces on the
base of the triangular prism as shown in Fig. 7.4.1. These projections are e g ,
d g and f g and they divide this phase triangle into three areas.
Crystals of pure component A freeze out first of all from systems whose
compositions lie within the area Ad g f A and components B and C freeze out
respectively from systems whose compositions lie within the other two areas.
If the composition of the system corresponds to any of the three lines, then on
cooling two components will appear simultaneously; along d g , the components
are A and B, along f g , the components are A and C and along e g , we have B
and C. If composition of the system corresponds to the point g, then on cooling
all the three components will crystallize simultaneously the moment point g is
reached.
Description of the System at Different Temperatures
In order to exhibit the behaviour of a ternary system at any particular temperature,
we draw a horizontal plane passing through the three-dimensional triangular prism
corresponding to the given temperature. This plane may or may not intersect
the three surface areas adgfa, bdgeb and cfgec depending upon the temperature
of the system. In Fig. 7.4.1, we have also drawn planes corresponding to the
temperatures T0, T1, T2, T3, T4, T5, T6 and T7. We will now consider the behaviour
of the system at these temperatures one by one.
At Temperature T0 The temperature T0 is greater than the respective melting points of the three
components with the result that the horizontal plane at this temperature does
362 A Textbook of Physical Chemistry

not intersect any of the three surfaces. Therefore, no crystallization takes place
and the ternary system consists of one liquid layer.
At Temperature T1 The temperature T1 is greater than the melting points of A and C and is smaller
than that of B. Consequently, the plane drawn at this temperature intersects only
the surface bdgeb along the curve b1b1 as shown in Fig. 7.4.1. The equilateral
triangle along with this intersection curve is also shown separately in Fig. 7.4.2.
The curve b1b1 gives the compositions of various systems at which initial
solidification of B will start at the given temperature of T1. Since the plane
under study does not intersect the other two surfaces (i.e. adgfa and cegfc),
crystallization of A and C will not take place. The portion Ab1b1CA of the
triangle (Fig. 7.4.2) lies above the surface areas adgfa and cegfc and, therefore,
represents the region where the system can exist only in the molten state consisting
of only one liquid layer. The portion b1B1b1b1 of the triangle lies below the
surface area begdb but above the points e and d. Thus at a point anywhere in
this region, we have solid B in equilibrium with the melt. The composition of
the latter lies on the curve b1b1. Take, for example, the point n in the region
b1Bb1b1. This point represents a system in which solid B is in equilibrium with
the melt of composition m. The latter can be obtained by joining the apex B
with the point n and then extending the line Bn to m where it meets the curve
b1b1. The relative amounts of the two phases, viz., solid B and the melt, can be
determined as usual with the help of the lever rule. For example, at n, we have

Amount of solid phase B mn

=
Amount of melt nB
It may be pointed out here that for an ideal ternary system, the line b1b1
b1
A B
n
m

b¢1

Liquid Solid B +
liquid

Fig. 7.4.2 Triangular

plot at the temperature
T1 just below the melting
point of B but above the
melting points of A and C C
 Phase Diagrams of Three-Component Systems 363

of Fig. 7.4.2 would be a straight line parallel to the side AC of the equilateral
triangle. The implication of this parallel line is that the precipitation of the solid
B from the melt depends solely on the amount fraction of B in the solution and
is independent of the nature of the components A and C. In other words, it is
the total concentration of A and C that determines the melting point depression
of B rather than the nature of A and C. Thus, if the amount fraction of B in
the liquid phase of a binary solid-liquid equilibrium has the value of xB(liquid),
its melting point will be lowered by an amount given by the simple van’t Hoff
equation. In a ternary system where the amount fraction of B is again xB(liquid),
the melting point of B will be lowered by precisely the same amount as in the
binary case, the sum of total of the amount fractions of A and C acting as if
only a single additional component were present. In real cases, this situation is
perturbed and thus the line b1b1 may be curved as shown in Fig. 7.4.2.
At Temperature T2 The temperature T2 is greater than the melting point of the component C and is
smaller than those of A and B. Consequently, the plane drawn at this temperature
intersects two surfaces begdb and adgfa along the curves b2b 2 and a2a 2,
respectively, and does not intersect with the third surface cegfc. The curve b2b2
gives compositions of various systems at which initial solidification of B will start
at the given temperature of T2 while the curve a2a2 gives compositions at which
the initial solidification of A will start. Since the plane at temperature T2 lies above
the melting point of the third component C. vis-à-vis, does not intersect the curve
cegfc, crystallization of the component C will not take place at temperature T2.
The equilibrium curve obtained at this temperature is also shown in
Fig. 7.4.3. The interpretation of the diagram is described below
Solid A + liquid

A a2 b2
B
Solid B +
liquid
a¢2

b¢2
Liquid

Fig. 7.4.3 Triangular

plot at temperature T2
which lies below TA* and
TB* but above TC* C
364 A Textbook of Physical Chemistry

Apex A: Solid component A.

Apex B: Solid component B.
Apex C: Liquid component C.
Side a2b2: Binary liquid mixtures of A and B.
Side b2C: Binary liquid mixtures of B and C.
Side a2C: Binary liquid mixtures of A and C.
Area Aa2a2A: A point in this region represents solid A in equilibrium
with the melt whose composition lies on the line a2a 2.
Area Bb2b2B: A point in this region represents solid B in equilibrium
with the melt whose composition lies on the line b2b2.
Area Ca2a2b2b2C: A point in this region represents a liquid system
consisting of a single layer only.
At Temperature T3 The temperature T3 is smaller than all the three melting points of the three
components, vis-à-vis, the plane drawn at this temperature intersects all the three
surfaces adgfa, begdb and cegfc along the curves a3a3, b3b3 and c3c3, respectively.
The equilibrium curve obtained is also shown in Fig. 7.4.4. The interpretation of
the diagram can be done as usual, only the main features are described below.

Fig. 7.4.4 Triangular

plot at the temperature
T3 which lies below TA*,
TB* and TC*

Curve a3a3: A point on this line represents a system where the crystallization
of solid A has just started from the melt of composition corresponding to the
given point.
Area within the curve Aa3a3A: A point (say, n) in this region represents a
system where again solid A is in equilibrium with the melt. The composition of
the latter will lie on the line a3a3 and can be obtained by extending the line An
 Phase Diagrams of Three-Component Systems 365

up to the curve a3a3. The relative amounts of the two phases can be determined
with the help of the lever rule.
In a similar manner, along the curves b3b3 and c3c 3 the precipitation of
solids B and C, respectively, has just started. A point within the curve Bb3b3B
(or Cc3c 3C) represents a system where solid B (or solid C) is in equilibrium with
the melt whose composition lies on the curve b3b3 (or c3c 3). The latter can be
obtained by joining the apex B (or C) with the given point and extending it to
the curve b3b3 (or c3c3). The intersecting point gives the required composition
of the melt.
Area within the curve a3a3c3c3b3b3a3: A point inside this region represents
a system of a single liquid layer.
At Temperature T4 This temperature corresponds to the eutectic temperature of the A-B system. The
equilateral triangle at this temperature intersects the two surfaces adgfa and bdgeb
along a4d and b4d, respectively. The two intersection curves a4d and b 4d meet
each other at the eutectic point d which lies on the side AB of the triangle, the
equilibrium curve at this temperature is also shown in Fig. 7.4.5. The interpretation
of the diagram can be done as usual, though the main features are described below.
A d
B

Solid A + liquid
Solid B + liquid

a¢4
Liquid b¢4

c4 c¢4
Solid C +
Fig. 7.4.5 Triangular liquid
plot at the temperature
T4 which corresponds to
the eutectic temperature
of binary system A and B C

Along the line a4d, solid A is in equilibrium with the melt and along b4d,
solid B is in equilibrium with the melt. Both these curves meet at d. Thus at
this point, we have an equilibrium involving both the solids A and B and the
melt of composition d. The relative amounts of the two solids can be calculated
by using the lever rule as follows:

Amount of solid A Bd
=
Amount of solid B Ad
366 A Textbook of Physical Chemistry

At Temperature T5 This temperature lies below the eutectic temperature of the system A-B and
also corresponds to the eutectic temperature of the system A-C. The equilateral
triangle at this temperature intersects the two surfaces adgfa and begdb along
fx and b5x, respectively. These two intersection curves meet each other at the
point x which lies on the line dg. The triangle intersects the surface cegfc along
the curve fc5. The intersection curves fx and fc5 meet each other at the eutectic
point f. These three intersection curves are shown separately in Fig. 7.4.6. The
interpretation of the diagram can be done as usual, however, the main features
are now described.

Fig. 7.4.6 Triangular

plot at the temperature
T5 which lies at the
eutectic point of A and C
system as well as below
that of A and B

(i) Along the curve fx, the initial solidification of A starts and within the area
AxfA, we have solid A in equilibrium with the melt. The composition of
the latter lies on the line fx and can be obtained by joining the apex A with
the point under study and then extending it to the curve fx. The relative
amounts of solid and melt, as usual, can be obtained with the help of the
lever rule.
(ii) A point on the curve b5x. represents a system in which solidification of B
has just started from the melt whose composition corresponds to the point
under study. Within the area Bb5xB, we have solid B in equilibrium with
the melt. The composition of the latter lies on the curve b5x and can be
obtained by joining apex B with the point under study and then extending
it to the curve b5x.
(iii) The curve c5f represents systems where solidification of C has just started
from the melt whose composition lies on the curve c5f. A point anywhere
within the area fc5Cf represents an equilibrium of solid C with the melt
whose composition again lies on the curve c5f.
 Phase Diagrams of Three-Component Systems 367

(iv) The point f is the eutectic point of the system A and C. Thus at f both
solids A and C are in equilibrium with the melt of composition f. The
relative amounts of the two solids will be given by the lever rule.
(v) The point x lies on the line dg and thus represents a system where both
solids A and B are in equilibrium with the melt of composition x. At this
point, solidification of mixture of A and B have just started.
(vi) A point inside the region ABxA corresponds to a system where two solids
A and B are in equilibrium with the melt of composition x. The amounts
of the melt and the solid components in equilibrium can be determined
with the help of the lever rule. Take, for example, the point n within this
triangle (Fig. 7.4.6). This point will represent an equilibrium involving
solid A, solid B and the melt of composition x. The relative amounts of
the total solid present and the melt can be determined from the lever rule
by drawing a line xn and then extending it to the side AB. If the line xn
intersects AB at point w, then we have

Total amount of solid separated nx

=
Amount of melt nw
Knowing the total amount of crystals separated, we can determine the
amount of each of the crystalline components by applying again the lever
rule at w on the line AB. Thus
Amount of A wB
=
Amount of B wA
(vii) A point in the middle portion b5xfc5b5 of the triangle (Fig. 7.4.6) represents
a system of a single liquid layer.
At Temperature T6 This temperature lies below the eutectic temperatures of systems A–B and A–C
and also corresponds to the eutectic temperature of system B–C. The equilateral
triangle at this temperature intersects the three surfaces adgfa, begdb and cegfc
along x y, ex and ey, respectively. The curves ex and ey meet each other at point
e which lies on the side BC. Since the temperature T6 lies below the eutectic
temperatures of A–B and A–C systems, the intersection curve x y does not cut
the sides AB and AC but lies within the triangle. This curve meets the solubility
curves of B and C (i.e. ex and ey) at points x and y, respectively. The three
intersection curves are shown separately in Fig. 7.4.7. The interpretation of the
diagram can be done as usual, however, the main features are described below.
Line ex Solubility curve of B.
Line ey Solubility curve of C.
Line x y Solubility curve of A.
Area Bex B Solid B is in equilibrium with the melt whose composition
lies on the line, ex
Area CeyC Solid C is in equilibrium with the melt whose composition
lies on the line ey.
Area Ax yA Solid A is in equilibrium with the melt whose composition
lies on the line x y.
368 A Textbook of Physical Chemistry

A B

Solids A + B
and liquid

Solid A x¢
+ liquid
Solid B
+ liquid

Solids A + C
and liquid Liquid
y
e

Solid C + liquid
Fig. 7.4.7 Triangular
plot at temperature T6
which lies at the eutectic
point of B–C system as
well as below those of
A–B and A–C systems C

Area Ax BA: Solids A and B are in equilibrium with the melt of composition
corresponding to the point x .
Area AyCA: Solids A and C are in equilibrium with the melt of composition
corresponding to the point y.
Area x yex : Single liquid phase.
At Temperature T7 This temperature lies below all the three eutectic temperatures. Thus, the
equilateral triangle at this temperature intersects the three surfaces adgfa, begdb
and cegfc of Fig. 7.4.1 within the triangle along x1yl, x1z1 and y1z1, respectively.
In Fig. 7.4.8 these three lines are shown by x y , x z and y z respectively. The
main features of the diagram are described below.
Area Ax y A: Solid A is in equilibrium with melt whose composition lies
on the curve x y .
Area Bx zB: Solid B is in equilibrium with the melt whose composition
lies on the curve x z.
Area Cy zC: Solid C is in equilibrium with the melt whose composition
lies on the curve y z.
Area Ax BA: Solids A and B are in equilibrium with the melt of composition
corresponding to the point x .
Area Ay CA: Solids A and C are in equilibrium with the melt of composition
corresponding to the point y .
Area BzCB: Solids B and C are in equilibrium with the melt of composition
corresponding to the point z.
Area x y zx : Single liquid phase.
Crystallization Figures 7.4.2 to 7.4.8 have been shown together in Fig. 7.4.9 along with the
Scheme At a Glance projections of binary eutectic points d, e and f, ternary eutectic point g, and the
 Phase Diagrams of Three-Component Systems 369

three ternary eutectic curves dg, fg and eg. A few comments about the behaviour
of the system at a particular temperature may be made here.
(i) If the temperature of the system is above the melting point of any one
component, then the crystallization of that component will not take place at
the given temperature, i.e. the triangular plot will not include the solubility
curve for that component.
A B

Solid A + B
and liquid
Solid B
+ liquid

Solid A + liquid
x¢
Solids B + C
and liquid
Solids A + C Liquid
y¢ z
and liquid
Solid C + liquid

Fig. 7.4.8 Triangular

plot at temperature T7
which lies below the
eutectic temperatures of
A–B, A–C and B–C systems C

Fig. 7.4.9 Triangular

plots at different
temperatures on a single
triangle
370 A Textbook of Physical Chemistry

(ii) The triangular plot will contain as many solubility curves as the number of
components having their freezing points above the temperature at which the
system is being studied. These solubility curves will not meet each other
if the temperature of the system is greater than the three binary eutectic
temperatures and thus the triangular plot will have separate regions of
crystallizations.
(iii) The solubility curves will meet each other on a side of the triangle if the
temperature of the system is the same as that of the binary eutectic point
for a system involving the two components which lie on either ends of the
involved side. If the temperature of the system is lesser than the binary
eutectic temperature but greater than the ternary eutectic temperature, the
two solubility curves of components of the binary system will meet each
other on the ternary eutectic curve which lies within the triangle. In such
a case, the triangular plot will also include a region where the two solids
can exist in equilibrium with a solution of constant composition.
(iv) If the temperature of the system lies below the eutectic temperatures of
A–B, A–C and B–C systems but above the ternary eutectic temperature, the
solubility curves of A, B and C will intersect each other on the respective
ternary eutectic curves and thus lie within the triangle. In this case, the
triangle plot will include the regions where (a) pure components are in
equilibrium with the respective solubility curves, and (b) two components,
viz., A and B, A and C, and B and C, are in equilibrium with the respective
solution of fixed composition.
(v) If the temperature of the system is less than the ternary eutectic temperature,
the system merely consists of a mixture of the three solids.
Effects Produced on Suppose we have a ternary system represented by the point h of Fig. 7.4.10. Let
Cooling a Ternary the temperature of the system at the point h be T0. Since the point h lies above
System the solid A-liquid surface afgda, the system is in the liquid state.
On lowering the temperature, the system moves along the line hi and it
remains in the liquid state till the temperature T1 is reached. At this temperature
the system has reached to solid A-liquid surface afgda. Thus solid A starts
precipitating.
On lowering the temperature further, the system moves below the surface
afgda and thus represents solid A in equilibrium with the liquid. Since only solid
A precipitates, the amounts of the components B and C in the liquid phase will
remain unaffected. That is, so long as only solid A is in equilibrium with liquid,
the ratio B : C in the liquid would remain constant. Thus during cooling of the
system, the composition of the liquid phase is shifted on the surface afgda along
the line ijkl which represents the constant ratio of B/C in the liquid phase. If the
projections of the points i, j, k and 1 are made on the equilateral triangle, the
projected points i, j, k and l would make a straight line which on extending will
pass through the point A. This is shown at the bottom of Fig. 7.4.10. Each system
on the line Aijkl represents the liquid composition with constant ratio of B/C and
different amounts of A. Since the line ijkl passes through the apex A, it is the
solid A which is in equilibrium with the liquid. At the point i, the temperature of
the system is T1, and at this point, solid A just starts precipitating. At the point j,
 Phase Diagrams of Three-Component Systems 371

Fig. 7.4.10 The

sequence of effects
produced on cooling a
ternary system.
The tie-lines are as follows.
Ai at T1, Aij at T2,
Aik at T3, Ail at T4,
oim at T5, pin at T6, and
qig at T7.
The arrows 1 and 2 indicate
the directions of change in
compositions of liquid and
solid phases, respectively.
372 A Textbook of Physical Chemistry

temperature of the system is T2 and the relative amounts of solid A and liquid
as given by the lever rule are:
Amount of solid A ij
=
Amount of liquid Ai
At temperature T3, the composition of liquid phase is given by the point k and
the relative amounts of solid A and liquid are
Amount of solid A ik
=
Amount of liquid Ai

Obviously, the amount of solid A at T3 is more than that at T2.

Solid A continues to appear till the system has been cooled to temperature
T4, where the liquid composition lies on the intersection line fg of A and C
liquidus surfaces. Thus, at temperature T4, solid C also starts crystallizing along
with solid A. As the solid C is also being removed from the liquid, the amount
of C in the latter decreases, consequently, the C/B ratio in the liquid is decreased,
and hence its composition will shift away from the apex C and towards the apex
B, i.e. along the line lg shown at the bottom triangle of Fig. 7.4.10. Since the
solid is no longer pure A but is a mixture of A and C, it is obvious that the line
passing through the liquid composition and the point i does not pass through the
apex A but will intersect the line AC. Thus on lowering the temperature further,
the composition of liquid is shifted along lg and that of the solid along the line
AC. For example, at temperature T5, the liquid composition is represented by
the point m and that of solid by the point o. At T6, the liquid composition is
represented by the point n and that of the solid by p. It may be seen that the
length of the tie-line from the point i to the liquid composition increases while
that from the point i to the solid composition decreases as a result of lowering
the temperature of the system. This, according to the lever rule, implies that
the amount of solid relative to that of liquid is increasing with the decrease
in temperature. The composition of the solid mixture at any instant can be
determined again with the help of the lever rule. For example, at temperature
T6, the relative amounts of A and C in the solid mixture is

Amount of solid A pC
=
Amount of solid C Ap
Finally, when the temperature of the system is lowered to T 7, the
composition of liquid has reached the point g which represents the ternary eutectic
point. Thus, at this temperature solid B also starts crystallizing along with A
and C in such a manner that the composition of liquid remains unaltered. The
process of crystallization at this point is isothermal in nature. The composition
of solid must now reflect a composition increasing in B from its zero value
on the line AC up to the original amount of B in the starting mixture at point
i. Thus, the solid composition moves from point q to i keeping all the while
temperature and composition of liquid to constant values. When the solid
acquires the composition of point i, the entire liquid is solidified and further
cooling results only in the cooling of the three-phase solid mixture.
 Phase Diagrams of Three-Component Systems 373

7.5 TERNARY SYSTEMS OF TWO SOLID COMPONENTS AND A LIQUID

In this section, we shall describe phase diagrams of systems involving
crystallization of solid phases from an aqueous solution containing two
components. We consider these diagrams with reference to an important type
of systems in which the two solid components are salts with an ion common
between them. The condition of a common ion is essential to keep the system
to a three-component one, since otherwise the number of components will
become four. In the present treatment, it will be assumed that temperature at
which the system is being studied lies above 0 °C, as otherwise one would also
have to include an equilibrium curve corresponding to the separation of ice in
the triangular plot.
The description of various equilibria diagrams can be conveniently discussed
according to the following classification depending upon the nature of solids
that crystallize at a given temperature.
(1) Crystallization of pure components only.
(2) Formation of binary compounds such as hydrates.
(3) Formation of a double salt.
(4) Formation of a ternary compound.
(5) Formation of a complete series of solid solutions.
(6) Formation of solid solutions with partial miscibility.
We discuss below phase diagrams of the above categories one after the other.

7.6 CRYSTALLIZATION OF PURE COMPONENTS ONLY

Expected Triangular Figure 7.6.1 shows the triangular plot of a ternary system in which only pure
Plot components crystallize from the aqueous solution.

Fig. 7.6.1 Triangular

plot for a system where
only pure components
crystallize from the
solution
374 A Textbook of Physical Chemistry

Description of the Point D: This point represents the saturation solubility of component B in water.
Diagram Thus from D to A(H2O), we have unsaturated solution of B in water and from
D to B, we have saturated solution of B of composition D in equilibrium with
the solid B; their relative amounts are given by the lever rule. For example, at
the point X, this ratio is given as
Amount of solid B XD
=
Amount of saturated solution of B XB
Line DF: This line represents the saturation solubility of B in water in the
presence of the component C.
Point E: This point represents the saturation solubility of the component C in
water.
Line EF: This line represents the saturation solubility of C in water in the
presence of the component B.
Point F: At the point F, the two lines DF and EF meet each other and thus
represents a system where both solids B and C are in equilibrium with the
solution F. According to the phase rule, the point F is an invariant point since
P = 3 and F = C – P + 0 = 3 – 3 + 0 = 0.
Area ADFEA: A point within this area represents an unsaturated solution of B
and C.
Area BDFB: A point within this area represents a system where solid B is in
equilibrium with the solution. The composition of the solution lies on the line
DF and can be obtained by joining the apex B with the point under study and
then extending it to the line DF. For example, at the point G, we have solid B
in equilibrium with the solution of composition corresponding to the point H.
Their relative amounts as given by the lever rule are
Amount of solid B GH
=
Amount of solution H BG
The line BGH is, in fact, the tie line.
Area CEFC: A point in this region represents a system where solid C is in
equilibrium with the solution whose composition lies on the line EF. The
composition of the solution can be obtained by joining the apex C with the
given point under study and then extending it to the line EF.
Area BFCB: A point in this area represents a system of two solids B and C in
equilibrium with the melt of composition corresponding to the point F. In this
area, each system is invariant as P = 3 and F = C – P + 0 = 3 – 3 + 0 = 0.
The relative amounts of the two solids and those of total solid and the solution
F can be obtained by making use of the lever rule twice as indicated below for
the point I (Fig. 7.6.1).
The composition of the solid mixture at the point I can be obtained by joining
the point F to the point I and then extending the line FI up to the side BC where it
meets at the point J. The composition of the solid mixture is given by the point J.
The ratio of the amounts of the two solids as given by the lever rule is
Amount of solid B CJ
=
Amount of solid C BJ
 Phase Diagrams of Three-Component Systems 375

The ratio of amounts of the total solid and the solution as given by the lever
rule is
Amount of total solid FI
=
Amount of solution F IJ
In fact, a point on the line JIF represents a system where the solid mixture of
composition J is in equilibrium with the solution F. The only thing that varies from
point to point is the relative amounts of the total solid and the solution.
Process of The sequence of events that takes place when an unsaturated solution is subjected
Isothermal to isothermal evaporation (i.e. when more and more of water is gradually
Evaporation removed) can be easily predicted from Fig. 7.6.1. Let the unsaturated solution x
be subjected to isothermal evaporation. The state of the overall system will move
along the line xs during the isothermal evaporation. The line xs can be obtained
by joining the apex representing water with the point x and then extending it to
side BC where it meets at the point s. From the point x to m, the solution remains
unsaturated. At m the solution becomes saturated with respect to the component
B and thus the pure component B starts precipitating. The removal of B from the
solution shifts the composition of the solution away from the apex B, i.e. along
the line mF. As more of water is removed, the state of the system moves along mp
with the removal of more and more of B. This may be verified from the increasing
length of the portion of various tie lines lying right to the line mp relative to those
lying left to this line. At the point m, the relative ratio of solid B and the solution
is zero while at the point o, this ratio is
Amount of solid B on
=
Amount of the solution n Bo
and that at p is
Amount of solid B pF
=
Amount of the solution F Bp
At the point p, the removal of a very small amount of water further brings
the state of the system within the area BFCB. Thus, now the system consists
of two solids B and C in equilibrium with the solution F. The following effects
are produced when the state of the system moves along the line ps as a result
of the removal of more and more water from the system.
(i) The composition of the solid mixture steadily shifts from the point B
to s and thus the proportion of C steadily increases.
(ii) The relative amounts of the total solid mixture and the solution are
shifted more and more in favour of the solid mixture as may be seen from the
increasing length of the portion of various tie lines lying right above the line
ps relative to those lying below it.
At the point s, complete evaporation of water has taken place and the
system merely consists of the mixture of solids B and C in the ratio given below.
Amount of solid B Cs
=
Amount of solid C Bs
376 A Textbook of Physical Chemistry

This ratio will also be equal to the original ratio of B and C present in
the unsaturated solution x.
If the composition of the original unsaturated solution lies at the point
x , then on gradual evaporation, it is the solid C that separates first as the line
joining A to x passes through the saturation curve EF. If the original composition
of the solution lies on the line obtained by joining the invariant point F to the
apex representing H2O, then both solids B and C will appear simultaneously.
Moreover, the proportion of the two solids present in the mixture will be the
same as that present in the solution F, since the composition of the latter remains
unchanged during the process of evaporation.
Process of Isothermal In a similar manner the effects produced during the isothermal addition of water
Addition of Water to a mixture of salts can be predicted. In fact, the sequence of steps that is
produced is exactly reverse of those seen during the isothermal evaporation.
Take, for example, the system represented by the point s. The addition of water
to this system will cause the system to move initially along the line sp and then
along pm and finally along mx. From s to p, the addition of water will result in
the formation of a saturated solution of constant composition corresponding to
the point F keeping all the while both solids B and C in equilibrium with the
solution; the relative amounts of the two solids increase in favour of solid B, i.e.
the composition of the mixture will move along the line sB. At the point p, solid
C has completely dissolved and we get a system of solid B in equilibrium with
the saturated solution of composition corresponding to the point F. The addition
of more water now causes the dissolution of more and more of solid B, and thus
composition of the solution is shifted to the left along the line Fm. The relative
amount of the remaining solid B decreases as may be seen from the decreasing
portion of various tie lines lying above the line pm relative to those present below
it. Finally from m to x, the solution becomes more and more unsaturated.
Maximum Amount of The equilibrium diagram as given in Fig. 7.6.1 can also be utilized for determining
B or C Recoverable the maximum amount of solid B (or C) that can be separated from a mixture of
B and C of the given composition. Pure solid B will be obtained if the original
composition of the solid mixture lies to the left of the point K, but pure solid C
will be obtained if the composition lies to the right of this point. The maximum
amount of solid B (or solid C) is obtained when enough water has been added
so that the composition of the resultant system lies on the line BF (or CF). This
amount can be calculated as follows.
Let the composition of the original solid mixture of B and C be represented
by the point s. Let enough water be added so that the point p is reached. Applying
the lever rule at the point p on the line BF, we have
Amount of solution F pB
=
Amount of solid B pF
Adding one to both sides, we have
Amount of solution F + Amount of solid B pB + pF BF
= =
Amount of solid B pF pF
 Phase Diagrams of Three-Component Systems 377

Ê pF ˆ
or Amount of solid B = Ë (Total amount of the system) (7.6.1)
BF ¯
Total amount of the system at the point p may be determined again through
the application of the lever rule at the point p on the line sA(H2O). Thus, we have

Amount of water to be added to reach the point p ps

=
Amount of solid mixture is pA
Adding one on either sides, we have
Amount of water + Amount of solid mixutre ps + pA
=
Amount of solid miixture pA

Total amount of the system sA

i.e. =
Amount of solid mixture pA

Thus, Eq. (7.6.1)

Ê pF ˆ Ê sA ˆ
Amount of solid B = Ë Á ˜ (amount of solid mixture) (7.6.2)
BF ¯ Ë pA ¯
It may also be seen from Fig. 7.6.1 that solid B can be recovered only
when the original composition does not exceed the composition K. Once this
composition is exceeded towards C, then the line joining the given point to the
apex representing water will pass through the region of saturated solution of C
and hence only C can be recovered from the mixture. If the original composition
corresponds to the point K, the two substances cannot be recovered separately
in pure forms from the system.
Examples Examples of systems exhibiting triangular plot of Fig. 7.6.1 are
NH4Cl–NH4NO3–Water
NaCl–NaNO3–Water
NH4Cl–(NH4)2SO4–Water
NaNO3–KNO3–Water

Example 7.6.1 For the system KNO3–NaNO3–H2O, a ternary point exists at 5 °C at which the two
anhydrous salts are in equilibrium with a saturated solution containing 9.04% by mass
of KNO3 and 41.01% NaNO3. Determine analytically the maximum mass of KNO3
which could be recovered pure from a salt mixture containing 70 g of KNO3 and 30 g
of NaNO3 by crystallization from an aqueous solution at 5 °C.
Solution First of all, the point a corresponding to the given composition of the ternary point, viz.,
9.04% by mass of KNO3 and 41.01% NaNO3, was located (Fig. 7.6.2). Then the point
b corresponding to the given salt mixture, viz., 70 g of KNO3 and 30 g of NaNO3, was
located. Points a and b were joined with the apexes B and A, respectively. The lengths
bc, cA, Bc and ca were measured and found to be 2.3 cm, 6.6 cm, 4.1 cm and 3.7 cm,
respectively. At the point c, we have
Mass of water 2.3
=
Total mass of salt 6.6
378 A Textbook of Physical Chemistry

A (H2O)

6.6 cm
a

cm
3.7

cm
4.1
2.3 cm

B (KNO3) b C (NaNO3)
Fig. 7.6.2

Ê 2.3 ˆ 2.3
Mass of water = Ë (Total mass of salt) = ¥ 100 g
6.6 ¯ 6.6
= 34.83 g

Total mass of the system at c = 100 g + 34.83 g = 134.83 g.

The point c represents solid KNO3 in equilibrium with the ternary solution a. Applying
the lever rule on the line Bca, we have

Mass of the ternary solution 4.1

=
Mass of KNO3 3.7

Mass of the ternary solution + mass of KNO3 7.8

or =
Mass of KNO3 3.7
Mass of KNO3 3.7
or =
Total mass of the system at c 7.8

Ê 3.7 ˆ 3.7
or Mass of KNO3 = Ë ¯ (Total mass of the system at c) = ¥ 134.83 g
7.8 7.8
= 63.96 g
63.96 g
Per cent of KNO3 recovered = ¥ 100 = 91.37
70 g
 Phase Diagrams of Three-Component Systems 379

7.7 FORMATION OF BINARY COMPOUNDS SUCH AS HYDRATES

Description of the Let B nH2O be the stable hydrate which is formed by salt B in contact with
Diagram water. The composition of the hydrate can be shown on the line BA(H2O)
and is given by the point D in Fig. 7.7.1. Let the saturation solubility of this
stable hydrate in the presence of a salt C varies along the line EF. The point
G represents the saturation solubility of the salt C in water and the line GF is
the corresponding solubility curve in the presence of the salt B. The two curves
EF and GF meet each other at the point F and thus this point F gives a system
where the stable hydrate D and the salt C are in equilibrium with the solution
F. With these facts, the labelling of rest of the lines and various areas can be
done without any difficulty as summarized below.
A (H2O)

Unsaturated
soln G

Solid D + F
soln Solid C +
soln

D Solids
C and D + soln F
P
Solids
Fig. 7.7.1 Triangular B, C and D
plot for system where the q
salt-hydrate is formed B C

Area AEFGA: A point in this area represents an unsaturated aqueous solution

of B and C.
Area DEFD: A point in this area represents a system in which stable hydrate D
is in equilibrium with the solution. The composition of the solution lies on the
line EF. Various tie lines start from the line EF and will merge at the point D.
Area CGFC: A point in this area represents a system in which solid C is in
equilibrium with the solution. The composition of the solution lies on the line GF.
Obviously, various tie lines start from the line FG and will merge at the apex C.
Line DC: All possible mixtures of D and C will lie on the line DC.
Area DFCD: Since the line DC represents the lowest limit up to which both
solids D and C can exist, a point in this area represents a system in which solids
D and C are in equilibrium with the solution of composition corresponding to
the point F. Various tie lines in this region start from the line DC and will merge
at the point F.
380 A Textbook of Physical Chemistry

The relative amounts of solids D and C, and also of the total solid and
the solution F can be determined by using the lever rule twice. For example,
at the point p, we have
Total amount of solid Fp
=
Amount of solution F pq

Amount of solid D Cq
=
Amount of solid C Dq

From these, the respective amounts of solids C and D and the solution can be
determined.
Area BDCB: Since the liquid phase disappears on the line DC, a point below the
line DC will represent a solid mixture of B, D and C. The respective amounts
of B, D and C can be determined by the method given above.
Example The system sodium sulphate-sodium chloride-water at 15 °C exhibits phase
diagram as given in Fig. 7.7.1. The stable salt formed is Na2SO4 10H2O.
Formation of Two Sometimes both the salts form stable hydrates. For example, in the system
Hydrates magnesium chloride-calcium chloride-water at 0 °C, the two salts MgCl2 6H2O
and CaCl2 6H2O are formed. The triangular plot of such a system will have an
appearance as shown in Fig. 7.7.2. Labelling of various lines and areas can be
done as usual, but attention must be paid to the lowest region of the plot where
either the line CD (as shown) or the line BE (but not together) is observed
depending upon the vapour pressure data of the system. If the vapour pressure
of the system (E + C) has a value greater than that of the system (B + D), the
hydrate E begins to dehydrate as soon as last drop of the solution disappears and
A (H2O)

Unsaturated H
soln
F

G Solid E +
Solid D + soln
soln
Solid D + E E
and soln G

D
Solids
C, D and E

Fig. 7.7.2 Triangular

plot for system where Solids B, C and D
two hydrates are formed B C
 Phase Diagrams of Three-Component Systems 381

we get a system consisting of (C + D + E). Consequently, the line CD is observed.

When all of E has dehydrated, we reach the line CD and the pressure of the
system falls to the vapour pressure of (B + D). After this, D starts dehydrating
and we move into a region of (B + D + C). Conversely, if the vapour pressure of
the system (B + D) has a value greater than that of (E + C), then D dehydrates
first and E starts dehydrating on the dashed line BE.
Formation of One Sometimes, under certain condition of temperature, the stable hydrate as well as
Hydrate and Two the anhydrous salt can exist in equilibrium with the solution. In such cases, the
Anhydrous Salts triangular plot has an appearance as shown in Fig. 7.7.3. The labelling of various
points, lines and areas is straightforward and is being summarized now.
Point E: Saturation solubility of the hydrate D.
Line EF: Saturation solubility curve of the hydrate D observed in the solution
in the presence of C.
Point H: Saturation solubility of the component C.
Line HG: Saturation solubility curve of the component C observed in the solution
in the presence of B.
Line FG: Saturation solubility curve for the pure component B.
Point F: Invariant point where solid hydrate D and solid B are in equilibrium
with solution F.
Point G: Another invariant point where solid B and solid C are in equilibrium
with the solution G.
Area AEFGHA: A point in this region represents an unsaturated solution.
Area DEFD: A point in this region represents solid hydrate D in equilibrium
with the solution; composition of the solution lies on the line EF.
Area BFGB: A point in this region represents solid B in equilibrium with the
solution; composition of the solution lies on the line FG.
A (H2O)

Unsaturated
soln
H
E

G
F Solid C +
Solid D soln
Solids B +
+
soln soln

Fig. 7.7.3 Triangular Solids B + D D

and soln F
plot where both stable Solids B + C
hydrate and the and soln G
anhydrous salt crystallize
together B C
382 A Textbook of Physical Chemistry

Area BDFB: Invariant region, where solid hydrate D and solid B are in equilibrium
with solution of composition corresponding to the point F.
Area HGCH: A point in this region represents solid C in equilibrium with the
solution; composition of the solution lies on the line HG.
Area BGCB; Another invariant region, where solid B and solid C are in equilibrium
with solution of composition corresponding to the point G.
Example The system Na2SO4–NaCl–H2O between 17.9 °C and 32.4 °C exhibits the
triangular plot as shown in Fig. 7.7.3.

7.8 FORMATION OF A DOUBLE SALT

Description of In some cases the two salts B and C combine with each other to form a double
Diagram salt of general formula BmCn. Its composition will be represented by a point
such as D on the line BC as shown in Fig. 7.5.5. The triangular plot will now
include three solubility curves corresponding to the salts B, D and C. These are
shown in Fig. 7.8.1 by the curves EF, FG and GH, respectively.

Fig. 7.8.1 Triangular

plot of a system where
congruently saturating
double salt is formed

The points F and G are the two invariant points where we have
(i) At point F: Solid B and solid double salt D are in equilibrium with the
solution of F.
(ii) At point G: Solid C and solid double salt D are in equilibrium with the
solution of G.
Various tie lines start from the lines EF, FG and GH will meet at the points
B, D and C, respectively. With this information, labelling of the triangular plot
can be done without any difficulty and is summarized below.
Area AEFGHA; A point in this region represents an unsaturated solution of B
and C.
 Phase Diagrams of Three-Component Systems 383

Area BEFB: A point in this region represents a system in which solid B is in

equilibrium with the solution whose composition lies on the line EF.
Area HGCH: A point in this region represents a system in which solid C is in
equilibrium with the solution whose composition lies on the line HG.
Area DFGD: A point in this region represents a system in which solid double salt
D is in equilibrium with the solution whose composition lies on the line FG.
Area BFDB: This region represents solids B and D in equilibrium with the
solution F and, therefore, a point in this region represents an invariant system.
Various tie lines in this region on starting from the line BD will merge at the
point F. With the help of the lever rule, we can determine the relative amounts
of the total solid (B + D) and the solution and those of solid B and solid D in
the total solid mixture.
Area CDGC: A point in this area represents a system of solids C and D in
equilibrium with solution G. Various tie lines start from the line CD and meet
together at the point G.

Example 7.8.1 The following data are available for the system nickel sulphate-sulphuric acid-water at
25 °C. Sketch the triangular plot and label it.

Liquid phase Solid phase

NiSO4/mass % H2SO4/mass %
28.13 0 NiSO4 7H2O
27.34 1.79 NiSO4 7H2O
27.16 3.86 NiSO4 7H2O
26.15 4.92 NiSO4 6H2O
15.64 19.34 NiSO4 6H2O
10.56 44.68 NiSO4 6H2O
9.65 48.46 NiSO4 H2O
2.67 63.73 NiSO4 H2O
0.12 91.38 NiSO4 H2O
0.11 93.74 NiSO4
0.08 96.80 NiSO4

Solution The state points corresponding to the given data are chosen and then a smooth curve
passing through these points is drawn. On this curve, different regions of solubility curve
are selected. Each solubility curve is then joined to the appropriate point representing
composition of the corresponding solid phase (Fig. 7.8.2). Labelling of the triangular
plot is shown in the figure itself.

Stability of a Double The stability of a double salt in the presence of water depends on the placements
Salt of its composition point and its solubility curve. If the apex representing water
in Fig. 7.8.1 is joined with the two invariant points F and G and the resultant
lines are extended right up to the line BC, we get two lines AFI and AGJ.
For congruently saturating salt If the composition of the double salt (represented
by the point D) lies anywhere between I and J, then on gradually adding water
to the double salt, the state of the overall system will move along DA which will
384 A Textbook of Physical Chemistry

Fig. 7.8.2 The required

phase diagram:
(1) NiSO4 and NiSO4 · H2O
+ soln. G
(2) NiSO4 6H2O and
NiSO4 H2O + soln. F;
(3) NiSO4 7H2O and
NiSO4 6H2O + soln. E;
(4) NiSO4 7H2O
+ soln.(DE);
(5) unsaturated soln.;
(6) NiSO4 6H2O
+ soln.(EF);
(7) NiSO4 H2O
+ soln.(FG), and
(8) NiSO4 + soln.(GH)

pass through the region DFGD. This implies that on adding water, a saturated
solution of the double salt can be prepared and thus the double salt remains intact
in the presence of water. In other words, the double salt is stable in the presence of
water. Such a double salt is called congruently saturating.
Incongruently Saturating Salt If composition of the salt lies outside the range
IJ, then the line connecting the point under study with the apex A(H2O) will not
pass through the region DFGD but will pass initially through the area BFDB or
CGDC and then through BEFB or CGHC and finally through AEFGHA depending
upon whether the point D lies on the left of the point I or to the right of the point
J. In such a case, it is obvious that a saturated solution of the double salt alone
cannot be prepared and the double salt on adding water will undergo partial or
complete decomposition. Such a salt is known as incongruently saturating.
Illustration Let us illustrate the stability of double salt with the help of a specific example
as shown in Fig. 7.8.3.
The point D representing the composition of the double salt lies outside
the region of stability. On adding water, we move into the region BDFB where
both solid B and the double salt are in equilibrium with the solution F. Thus the
double salt besides dissolving in water also dissociates to give solid salt B. In
other words, the double salt is no longer stable in the presence of water. As more
and more of water is added, composition of the solution will remain unaltered
corresponding to the point F while the relative amounts of solid B and double
salt are shifted more and more in favour of B. This implies that more and more
of double salt decomposes as the state point moves from D to b. At the latter
 Phase Diagrams of Three-Component Systems 385

Fig. 7.8.3 Triangular

plot for a system where
incongruently saturating
double salt is formed

point, the double salt completely decomposes to give a saturated solution of B of

composition F in equilibrium with solid B only. On adding more water, we move
along ba where more and more of solid B dissolves and the composition of the
solution moves along Fa. At the point a, there is a complete dissolution of B and
the addition of more of water gives the unsaturated solution of B and C.

Process of Isothermal Evaporation

We now consider the process of isothermal evaporation in which water is
gradually removed until the system becomes one of solid mixture. In fact, this
process is just the reverse of the above process and the effects produced can be
conveniently described with the help of a triangular plot. We consider some of
the typical cases for both congruently saturating and incongruently saturating
double salts. These are discussed below.
For Congruently In general, the effects produced will depend on the original composition of the
Saturating Double unsaturated solution and can be predicted by drawing lines from the apex
Salt representing water to the point under study and then extending it to a point
where it meets the side BC. We shall consider four typical solutions x1, x2, x3
and x4 as shown in Fig. 7.8.4.
For the solution x1 This solution contains the same proportion of B and C as
that of the double salt. Thus the line Ax1 will on extending meet at the point
D corresponding to composition of the double salt. From x1 to a, the solution
remains unsaturated, at the point a, the double salt starts appearing and continues
to appear till the point D is reached.
For the solution x2 This system contains more than the requisite amount of B
(corresponding to the point x1) to form the double salt. Thus, the end-products
386 A Textbook of Physical Chemistry

A (H2O)

x2
x3
x4
x1

H
E f a G
F b

g c

Fig. 7.8.4 The process

of isothermal evaporation
as applied to four
systems involving
congruently saturating
B C
double salt h e d D

consist of the double salt and the excessive amount of solid B. Form x2 to b, the
solution remains unsaturated, at b the double salt starts appearing and continues
to appear till the point c is reached. Since the double salt contains more of C as
compared to the amount present in the solution, removal of more and more of
double salt along bc shifts the composition of the solution along the line bF. At
c, the composition of the solution is F. From c to d both the solids, i.e. B and the
double salt, start precipitating simultaneously from the solution, keeping all the
while composition of the solution to a constant value of F.†
For the solution x3 Here the line Ax3 passes through the invariant point F.
From x3 to F, the solution remains unsaturated and from F onwards both the
solids, B and the double salt, appear together till the point e is reached.
For the solution x4 From x4 to f, the solution remains unsaturated. At f, it
is the solid B which appears first and continues to appear till the point g is
reached, while composition of the solution has moved along fF. From g to h,
again both the solids, B and the double salt, appear together keeping all the
while constant composition of the solution at the point F.
The solution F is known as congruently saturated solution.

†
Since the solution F contains more proportion of B than that present in the double salt,
the appearance of solid B from c onwards is due to its precipitation from the solution.
The removal of B from the solution will have to be associated with the removal of
double salt since only then composition of the solution can be kept at a constant value
of F. The appearance of B is not through dissociation of the double salt, since in that
case the solution will become richer in the component C.
 Phase Diagrams of Three-Component Systems 387

For Incongruently Here again the effects produced will depend upon the original composition of the
Saturating Double unsaturated solution. We shall consider six typical solutions x1, x2, x3, x4, x5
Salt and x6 as shown in Fig. 7.8.5.
A (H2O)

x4

x3 x5

x1 x6
x2

F
p
E c H
a k
f G
g
b m
h q
Fig. 7.8.5 Process of
isothermal evaporation as
applied to six systems d i
involving incongruently
saturating double salt B e D j n o r C

For the solution x1 The solution x1 contains the same proportion of B and C
as that of the double salt and thus the line Ax1 on extending will meet at the
point D corresponding to the composition of the double salt. From x1 to a, the
solution remains unsaturated. At a, the salt B starts appearing and continues to
appear till the point b is reached. Removal of B from the solution makes the
solution deficient in B and thus its composition moves along aG. At the point
b, the solution has a composition of G, an invariant point where both the solids,
B and the double salt D, are in equilibrium with the solution.
Since the double salt contains more proportion of B than is present in the
solution, removal of the double salt from the solution will be associated with
the dissolution of already precipitated B, since only then the composition of the
solution can remain constant at the point G. In other words, the solution at G
is incongruently saturated. Further removal of water causes the system to move
on the line bD. The net result observed along the line bD is the dissolution of
more and more solid B and precipitation of more and more double salt, keeping
all the while the composition of the solution at the point G. The fact that the
proportion of solid B decreases whereas that of solid D increases can be seen
from the composition of the solid mixture which moves from B to D during the
isothermal evaporation from point b to D. Finally, at the point D whole of water
has been removed and the system consists of only double salt D; the composition
of which is the same as that present in the original solution.
388 A Textbook of Physical Chemistry

For the solution x2 This system contains more of B than the requisite amount
of B (corresponding to the point x1) to form the double salt. Thus the end
products of isothermal evaporation are the double salt and the excessive amount
of solid B. From x2 to c, the solution remains unsaturated, at c solid B starts
appearing and continues to appear till the point d is reached. At d, composition
of the solution corresponds to the point G and thus the system now contains
solid B and double salt D in equilibrium with the solution. From d to e, more
and more of double salt appears and simultaneously more and more of the salt
B dissolves in order to keep the composition of the solution at the point G.
Finally at e, the system contains solid mixture consisting of double salt and the
excess amount of B. The relative amount of two solids is given as
Amount of solid double salt Be
=
Amount of solid B eD
For the solution x3 The system contains more of C than the requisite amount of
C to form the double salt and thus the end products of isothermal evaporation are
the double salt and the excessive amount of C. From x3 to f, the solution remains
unsaturated. At f, the salt B starts appearing and continues to appear till the point
g is reached. From g to h, more and more of the double salt is formed with the
dissolution of more and more of the salt B. At h, practically whole of solid B has
dissolved and the system consists of solid double salt of D and solution G. The
system once again becomes univariant as only one solid phase is present in contact
with the solution. The removal of more water causes the system to move along hi.
Here more and more of the double salt is precipitated out. This may be verified
from the increasing length of the portion of various tie lines (if drawn) lying right
above the line hi relative to those lying left below it. The composition of the solution
changes along the line GH. At the point i, the system again becomes invariant as
now two solids, namely, double salt and C, are in contact with the solution H. From
i to j, both the solids, C and the double salt, precipitate simultaneously from the
solution, keeping all the while composition of the solution to a constant value H.†
Thus the solution H is a congruently saturated solution.
For the solution x4 From x4 to k, the solution remains unsaturated. At k, solid
double salt starts appearing and continues to appear till the point m is reached.
The composition of the solution will move along kH. At the point m, the system
becomes invariant and thus removal of more and more water causes the separation
of more and more of the solids C and D from the solution, keeping all the while
the composition of the solution H to a constant value. The composition of the
solid mixture will move along Dn as one moves from m to n and finally at the
point n, complete evaporation of water has taken place and the system consists
of a solid mixture of C and D with the relative proportion as given below:

†
The solution of composition H contains more proportion of C than is present in the
double salt. Thus, the appearance of solid C from i onwards is due to its precipitation
from the solution. The removal of solid C from the solution will have to be associated
with the removal of double salt since only then the solution can be kept at constant
composition H. The appearance of C cannot be through the dissociation of the double
salt, since in that case the solution will become richer in the component B.
 Phase Diagrams of Three-Component Systems 389

Amount of solid C Dn
=
Amount of solid D Cn
For the solution x5 Here the line Ax5 on extending will pass through the
invariant point H. Thus from x5 to H, the solution remains unsaturated. At the
point H, both salts, C and D, appear together and this continues till the point
o is reached where the system consists of a solid mixture of C and D.
For the solution x6 From x6 to p, the solution remains unsaturated, from p
to q more and more of salt C appears and from q to r both the salts, that is,
C and the double salt, appear together. Finally, we reach to the point r where
only a solid mixture of C and D is present.
Examples The system NH4NO3–AgNO3–H2O at 30 °C forms congruently saturating double
salt NH4NO3 AgNO3 and the system KNO3–AgNO3–H2O at 30 °C forms
incongruently saturating double salt.

7.9 FORMATION OF A TERNARY COMPOUND

Expected Triangular In some systems a ternary compound consisting of all three components (two
Plot salts and water) is formed which may be congruently saturating or incongruently
saturating. The triangular plot for such type of systems will include a solubility
curve corresponding to the ternary compound and the various tie lines start from
this curve and meet together at a point D which represents the composition of
the ternary compound. Obviously, such a point will lie within the triangle as it
includes all the three components. The general appearance of the triangular plot is
of the type shown in Fig. 7.9.1. The labelling of various areas is straightforward
and is shown along with Fig. 7.9.1.
A (H2O)

Unsaturated
soln

E Solid C +
H
G soln
Solid
B + soln Solid D +
soln
Solids
Solids B + D C and D
and soln G + soln H
Fig. 7.9.1 Triangular
D
plot for a system in
which a ternary Solids B, C and D
compound is formed B C
390 A Textbook of Physical Chemistry

Many systems form binary as well as ternary compounds. In such cases

the triangular plot takes the form as shown in Fig. 7.9.2.

Fig. 7.9.2 Description of

different areas in the
obtained triangular plot

Examples Examples of systems exhibiting congruently saturating ternary compound are

the various alums with the general formula B2(SO4) C2(SO4)3 24H2O and
examples of systems exhibiting incongruently saturating ternary compound are:
CaCl2–MgCl2–H2O at 25 °C (compound CaCl2 MgCl2 12H2O)
MgSO4–Na2SO4–H2O at 25 °C (compound MgSO4 Na2SO4 H2O).

Example 7.9.1 The following data give compositions of the liquid and solid phase in equilibrium at
25 °C in the system ammonium sulphate-beryllium sulphate-water.

Liquid phase Wet solid phase

(NH4)2SO4 BeSO4 (NH4)2SO4 BeSO4
mass % mass % mass % mass %
43.45 0000 — —
38.60 8.62 82.29 2.82
35.88 16.04 71.09 7.59
37.56 19.72 — —
34.26 22.08 42.93 32.83
32.20 24.04 42.84 33.64
28.09 26.79 — —
24.99 26.68 9.12 46.90
15.66 27.26 3.07 52.18
5.77 28.56 1.37 51.16
000 29.94 0 59.35
 Phase Diagrams of Three-Component Systems 391

In each case the difference from 100% represents water, (a) Plot the phase diagram
identifying all phases, (b) What will be the composition of the first crystals to deposit
when solutions containing 10 mass % (NH4)2SO4 + 25 mass % BeSO4 and 20 mass %
(NH4)2SO4 + 10 mass % BeSO4 are evaporated?

Solution (a) Plotting of the triangular diagram can be conveniently done as follows:
(i) Draw an equilateral triangle of an edge length of 100 mm.
(ii) Designate the corners as shown in Fig. 7.9.3.
(iii) The perpendicular distance A to BC is
3
100 mm × sin 60° = 100 mm × = 86.6 mm
2
Now this length 86.6 mm represents the various proportions of water. It is zero on
the line BC and 100% at the corner A. First of all, the point on this perpendicular line is
chosen corresponding to the given proportion of water. Taking, for example, the data of the
liquid phase containing 38.60 mass % of (NH4)2SO4 and 8.62 mass % BeSO4, we have
Water composition = 100 – (38.60 + 8.62) = 52.78 mass %
The length representing this percentage on the perpendicular line

52.78
= ¥ 86.6 mm = 45.7 mm
100
A point at a length 45.7 mm perpendicularly from the side BC is chosen and then a
line parallel to the side BC passing through the chosen point is drawn (not shown in the
figure). Then on this line, a point at a distance of 38.6 mm (mass % of (NH4)2SO4 from

Fig. 7.9.3 Triangular

plot for a system where
both binary as well
ternary compounds
are formed
392 A Textbook of Physical Chemistry

the side AC) or at a distance of 8.6 mm from the side AB is chosen. This point represents
the required composition.
Alternatively, a point at a distance of 52.78 mm (equal to the water composition)
on the side BA or CA (i.e. from B or C towards A) is chosen. A scale at this point
parallel to the side BC is placed and a point at a distance of 38.6 mm (equal to the
composition of ammonium sulphate) from the side AC is located. This point represents
the required composition.
Following either of the above procedures, the various points corresponding to given
compositions are chosen. The nature of the solid present in the wet solid phase can be
determined by following the method of wet residues (see, page 398). Figure 7.9.3 depicts
the triangular plot obtained from the given data along with the description of different
areas.
(b) When the solution containing 10 mass % (NH4)2SO4 + 20 mass% BeSO4 (point
x) is subjected to the isothermal evaporation, the system will move along xm, the first
crystals which appear will be of salt hydrate BeSO4 4H2O. For the system containing
20 mass % (NH4)2SO4 + 10 mass % BeSO4 (point x ), it is the solid (NH4)2SO4 that
separates first as shown in Fig. 7.9.3.

7.10 FORMATION OF SOLID SOLUTIONS

If the two solid components B and C are completely miscible in each other,
they will form a continuous series of solid solutions ranging from pure B to
pure C. If the components A and B and A and C form eutectic phase diagram
and temperature of the system is below the melting points of B and C but
above that of A, the ternary phase diagram will have an appearance as shown in
Fig. 7.10.1. The system have only two phases in equilibrium and thus will never
be invariant. Consequently, in the triangular plot, we have only one solubility
curve corresponding to the solid solution of B and C as shown by the line DE
in Fig. 7.10.1.
A point in the area below DE represents a system of unsaturated solution
whereas that above DE represents a system in which the solid solution is in
equilibrium with the corresponding saturated solution. The compositions of
the two phases, as usual, are connected through various tie lines. The system
Ba(NO3)2–Pb(NO3)2–H2O exhibits the phase diagram as shown in Fig. 7.10.1
Consider a case in which all the three pairs A-B, B-C and C-A form a
complete series of solid solution both in the solid and liquid phases. Each of
the three faces of a three-dimensional triangular prism will include the phase
diagram of complete series of solid solution of the respective binary system as
shown in Figs 7.10.2 to 7.10.4.
Figure 7.10.2 depicts the ternary triangular phase diagram in which
TC* > TB* > T > TA*. The horizontal triangle at temperature T intersects the binary
phase diagrams of A-B and A-C as shown in Fig. 7.10.2. The solidus and liquidus
lines obtained in this intersection when projected on the base of triangular prism
gives the expected ternary phase diagram of the system. The labelling of the phase
diagram is straight forward and is shown in the figure itself.
Figures 7.10.3 and 7.10.4 depict the ternary triangular phase diagrams in
which (i) TC* > TB* = T > TA* and (ii) TC* > T > TB* > TA*, respectively. The
expected phase diagrams are shown in the bottom triangle of the respective
triangular prisms along with the labelling of the phase diagrams.
 Phase Diagrams of Three-Component Systems 393

Fig. 7.10.1 Triangular plot for a system exhibiting Fig. 7.10.2 Triangular plot for a system exhibiting
only one pair B-C of solid solution three pairs A-B, B-C and C-A of solid solutions with
TC* > TB* > T > TA*
394 A Textbook of Physical Chemistry

Fig. 7.10.3 Triangular plot for a system exhibiting Fig. 7.10.4 Triangular plot for a system exhibiting
three pairs A-B, B-C and A-C of solid solutions with three pairs A-B, B-C and A-C of solid solutions with
TC* > TB* = T > TA* TC* > T > TB* > TA*
 Phase Diagrams of Three-Component Systems 395

7.11 FORMATION OF SOLID SOLUTIONS WITH PARTIAL MISCIBILITY

Expected Triangular If the two components B and C form solid solutions with partial miscibility, then
Plot within certain range of concentrations they will form two solid solutions, one
of C in B and the other of B in C. Both these solutions will have definite
compositions. Beyond this range, both the components will be completely
miscible and will form a single solid solution. Thus along the line BC of the
triangular, we will have two points corresponding to the compositions of the
two solid solutions such as shown by the points D and E in Fig. 7.11.1.
A (H2O)

Unsaturated H
soln
Solid soln
F +
Solid soln liquid soln
G
+ liquid soln

Solid solns
D + E and
soln
X
Fig. 7.11.1 Triangular G
plot exhibiting solid
solution with partial
B D Y E C
miscibility

Description of the From B to D and E to C, the two components are completely miscible and from
Diagram D to E they are partially miscible and thus form two solid solutions D and E,
respectively. The lines FG and GH are the corresponding solubility curves of
the two solid solutions. With this information the labelling of various areas of
Fig. 7.11.1 can be done as usual and is summarized below.
Area AFGHA: A point in this region represents a system of an unsaturated
solution.
Area FGDBF: A point in this region represents a system of solid solution of C
in B in equilibrium with the saturated solution. The composition of the latter
lies on the line FG.
Area GHCEG: A point in this region represents a system of solid solution of B
in C in equilibrium with the saturated solution. The composition of the solution
lies on the line GH.
Area DEGD: A point in this region represents an invariant system of solid
solutions D and E in equilibrium with the saturated solution G. The relative
amounts of the two solid solutions D and E and that of total solid and the liquid
solution can be calculated as follows.
396 A Textbook of Physical Chemistry

Join the point G with the given point (say, X) and then extend it to the
point Y where it meets the side BC. Thus, we have
Amount of solid solution rich in C DY
=
Amount of solid solution rich in B EY
Amount of total solid GX
=
Amount of solution G YX

7.12 SALTING OUT PHENOMENON

Sometimes two liquids which show complete miscibility become partially miscible
in the presence of a third component. This type of behaviour is common among
organic solvents where a single solution of organic liquid in water splits into two
layers in the presence of sufficient quantity of a salt. One such example is the
ternary system of H2O–K2CO3–CH3OH where H2O and CH3OH are completely
miscible in each other but become partially miscible in the presence of sufficient
quantity of K2CO3. The triangular plot of the above system is shown in Fig. 7.12.1.
The points D and E represent the saturation solubility of K2CO3 in water and
CH3OH, respectively. Thus from D to A, we have an unsaturated solution of
K2CO3 in water, whereas that from D to B, solid K2CO3 is in equilibrium with
the saturated solution D. Similarly, from E to C, we have an unsaturated solution
of K2CO3 in CH3OH and from E to B, a saturated solution E in equilibrium
with solid K2CO3 is formed.

Fig. 7.12.1 Triangle

plot for the system
H2O–K2CO3–CH3OH
 Phase Diagrams of Three-Component Systems 397

The line DF is the saturation solubility curve of K2CO3 in water in the

presence of CH3OH and the line EG is the corresponding curve of K2CO3
in CH3OH in the presence of water. Between these two curves, we have the
formation of two layers along the curve FCG. As usual, the compositions of the
two conjugate layers are connected through various tie lines. With this information,
the labelling of different areas can be done as usual and is described below.
Area above the curve DFCGE: A point in this region represents one liquid layer
consisting of all the three components.
Area BDFB: A point in this region represents solid K2CO3 in equilibrium with
a saturated solution whose composition lies on the line DF.
Area BGEB: A point in this region represents solid K2CO3 in equilibrium with
a saturated solution whose composition lies on the line EG.
Area FCGF: A point in this area represents the two conjugate solutions.
Area BFGB: A point in this region represents an invariant system where solid
K2CO3 is in equilibrium with the two conjugate liquid layers F and G, respectively.

Effect of Adding Salt With the help of Fig. 7.12.1 we can describe the behaviour of the binary system
consisting of H2O and CH3OH when solid K2CO3 is added to it. Let us start
with a system as represented by the point X. On adding K2CO3, the state of the
system will move long X-B(K2CO3). The system remains of one liquid layer up
to the point Y, where it splits into two layers Y and y . The former is present
in major amount while the latter is just formed. On moving from Y to Z, the
system continues to have two layers of varying compositions—the composition
of the layer rich in water will move from y to F, whereas that rich in CH3OH
will move along YG. At the point Z, K2CO3 no longer dissolves and thus the
system from Z to B consists of three phases—solid K2CO3 and two liquid layers
F and G, respectively.

Effect of Adding In a similar manner, behaviour of the system when CH3OH(or H2O) is added to
Organic Solvent binary system of K2CO3 and H2O (or K2CO3 and CH3OH) can be explained from
Fig. 7.12.1. The addition of organic compound to an aqueous solution of a salt
is often employed for salting out the dissolved salt in the solution. The principle
underlying this method can be easily explained from the triangular plot of
Fig. 7.12.1. We will have to simply enter into the region of BDFB or BFGB or
BGEB where solid salt is present in equilibrium with the solution of different
compositions. The behaviour of the system when H2O is added to a system
represented by the point X1 is interesting; from X1 to Y1, the system continues
to be a single layer, at Y1 sol id K2CO3 precipitates and remains in equilibrium
with the solution up to the point Z1 where it redissolves to give once again a
single solution. From Z1 onwards, the system continues to be of a single layer.

7.13 EXPERIMENTAL METHODS EMPLOYED FOR OBTAINING TRIANGULAR PLOTS

For systems of three liquids showing partial mutual solubilities To a mixture
of the two partially miscible liquids, the third component is added until the
system previously consisting of two layers becomes homogeneous, i.e. forms a
398 A Textbook of Physical Chemistry

single layer. The amounts of three components are noted and the corresponding
point in the triangle is determined. This point must lie on the binodal curve. The
experiment is repeated with different proportions of the two partially miscible
liquids and many more such points are determined. A smooth curve passing
through these points gives the required binodal curve. To obtain the various tie
lines, definite amounts of the three liquids are mixed up corresponding to any
point within the binodal curve and then the amount of one of the components
in either of the two solutions is determined. The point corresponding to this
composition is determined on the binodal curve. The determined point is joined
with the point representing the overall composition of the solution within the
binodal curve. This gives one tie line. The experiment is repeated at different
points and similar lines are then drawn.
For systems consisting of two salts and water To plot a triangular plot for
such a system, the method of wet residues of F.A.H. Schreinmakers is most
commonly employed. In this method, first of all a system consisting of a
saturated solution in equilibrium with solid is prepared. Then the saturated
solution and the wet crystals are analysed and the corresponding points on the
triangle are plotted and joined together by a line. The above experiment is
repeated over many other systems of different compositions and various such
lines are drawn. In the method of wet residues, the wet crystals are considered
as the mixture of dry solid and the corresponding saturated solution. Hence the
point representing the dry solid must lie on the extension of the line joining
the state point of the saturated solution with that of the wet crystals. Moreover,
as several solutions may have the same solid phase, all the tie lines for such
solutions must intersect at a common point, which is the composition of the solid
phase. Thus all lines are extended and the intersection points are determined.
These intersection points give the compositions of various solid phases.

REVISIONARY PROBLEMS

7.1 (a) Determine the variance of a three-component system having number of phases
equal to one, two and three, respectively.
(b) Outline the salient features of the scheme of triangular plot employed for three-
component systems.
7.2 Draw typical phase diagrams for the following cases:
(a) Systems exhibiting formation of one pair of partially miscible liquids,
(b) systems exhibiting formation of two pairs of partially miscible liquids, and
(c) systems exhibiting formation of three pairs of partially miscible liquids.
7.3 (a) What do you understand by the terms binodal curve and plait point?
(b) Explain why, in general, the various tie lines within the binodal curve are parallel
neither to the sides of the triangle nor to each other? Under what conditions will the
various tie lines be parallel to each other?
(c) Explain why, in general, the plait point lies either to the left or to the right of
the maximum point in the binodal curve. Under what condition will the plait point
coincide with the maximum point?
(d) What are the variances of the system within and outside the binodal curve?
 Phase Diagrams of Three-Component Systems 399

7.4 (a) Describe the sequence of events that takes place when the component A (assumed
to be in liquid form) is added to a binary system of two partially immiscible liquids
B and C.
(b) What is the retrograde solubility?
7.5 (a) Describe the changes observed in the binodal curves when temperature of the
system exhibiting one pair of partially miscible liquids is changed? Under what
conditions will the above system exhibit true critical solution temperature?
(b) Justify the statement that it is not possible to predict the behaviour of a system
exhibiting binodal band when its temperature is raised, that is, whether it will form
a system containing only one pair or two pairs of partially miscible liquids.
7.6 Draw phase diagrams of a three-component system involving water and two solid
salts with an ion in common for the following typical cases:
(a) Crystallization of pure components.
(b) Formation of binary compounds such as hydrates.
(c) Formation of a double salt.
(d) Formation of a ternary compound.
(e) Formation of complete series of solid solutions.
(f) Formation of solid solutions with partial miscibility.
7.7 Taking a few typical cases, discuss the sequence of events that takes place in the
following cases when the system is subjected to isothermal evaporation and/or
isothermal addition of water:
(a) Crystallization of pure components.
(b) Formation of a double salt with special emphasis on the stability of the double salt.
7.8 What do you understand by the congruently saturating double salt and incongruently
saturating double salt? Support your answer by drawing typical phase diagrams.
7.9 What do you understand by the phenomenon of salting out? Describe this by drawing
the triangular plot of K2CO3–CH3OH–H2O system.
7.10 Describe the method of wet residues of the F.A.H. Schreinmakers employed in
constructing the phase diagram of three-component systems involving two salts and
water.

TRY YOURSELF PROBLEMS

7.1 For the phase diagram given in Fig. 7.6.1 which of the following temperature
conditions are true?
(i) T > or < or = 0 °C
(ii) T > or < or = eutectic temperature of A-B system.
(iii) T > or < or = eutectic temperature of B-C system.
(iv) T > or < or = eutectic temperature of A-C system.
(v) T > or < or = ternary eutectic temperature of A-B-C system.
7.2 A ternary system consists of a solid and two partially miscible liquids. The solid is
soluble in both the liquids. Construct the probable triangular plot when the solubility
curves (i) overlap (ii) do not overlap the region of partial miscibility.
7.3 If a binary system A-B forms a congruently melting compound AxBy and the systems
A-C and B-C exhibit simple eutectic behaviour, the phase diagram of the ternary system
A-B-C takes the form as shown in Fig. 1. Label the diagram with adequate explanation.
(Hint: Label, as usual, the two triangles ACD and BCD separately.)
7.4 If in a ternary system A-B-C, a ternary congruently melting compound is formed, the
phase diagram of the system takes the form as shown in Fig. 2. Label the diagram
with adequate explanation.
(Hint: Label, as usual, the three triangles ABD, ACD and BCD separately.)
400 A Textbook of Physical Chemistry

e1 D e2
A B

E1
e5

E2

e3 e4

Fig. 1

Fig. 2

7.5 If the temperature of the system exhibiting the phase diagram of Fig. 1 is greater
than both the ternary eutectic temperatures, the phase diagram has an appearance of
Fig. 3. Label the diagram with adequate explanation.
7.6 Construct a ternary plot of a three-component system exhibiting the crystallization of
A H2O, A, B and A B substances.
7.7 Construct a ternary plot of a three-component system exhibiting the crystallization of
A H2O, B 2H2O, A, B, A 2B and A B H2O substances.
 Phase Diagrams of Three-Component Systems 401

AxBy
e1 D e2
A B

e3

e4

C
Fig. 3
7.8 Given a point within the triangle DEF of Fig. 7.3.9. How many phases are present
at this point? What are their compositions? How will you determine the relative
amounts of the different phases at this point?

NUMERICAL PROBLEMS

7.1 The following data, in amount per cent, were obtained for the ternary system; aniline,
toluene, n-heptane at 25 °C.

Aniline-rich phase Heptane-rich phase

aniline n-heptane aniline n-heptane
95.6 4.4 8.4 91.6
89.1 7.2 12.2 81.3
74.0 13.2 21.0 60.7
62.6 19.3 32.5 45.4

(a) Plot these data in a triangular graph and indicate 1- and 2-phase regions.
(b) Using this graph, indicate the changes that occur when successive increments of
toluene are added to a system containing equal amounts of aniline and n-heptane.
7.2 The following hydrates may under proper conditions be crystallized from the system
Ba(OH)2–NaOH–H2O at 30 °C.
Ba(OH)2 8H2O, Ba(OH)2 3H2O, Ba(OH)2 H2O, NaOH H2O
Sketch and interpret the phase diagram for this system.
7.3 The following data are available for the system Na2SO4–Al2(SO4)3–H2O at 42 °C.
Draw the phase diagram on triangular coordinate paper, and draw appropriate tie lines.
402 A Textbook of Physical Chemistry

Liquid phase Solid phase

mass % of Na2SO4 mass % of A12(SO4)3
33.20 0 Na2SO4
32.00 1.52 Na2SO4
31.79 1.87 Na2SO4
28.75 1.71 Na2SO4 Al2(SO4)3 14H2O
24.47 2.84 Na2SO4 Al2(SO4)3 14H2O
16.81 5.63 Na2SO4 Al2(SO4)3 14H2O
10.93 10.49 Na2SO4 Al2(SO4)3 14H2O
4.72 17.11 Na2SO4 Al2(SO4)3 14H2O
1.75 18.59 Al2(SO4)3
0 16.45 Al2(SO4)3

7.4 Draw the triangular plot for the system NH4C1–NH4NO3–H2O at 25 °C from the
following data.

Saturated solution Wet residue

mass % of NH4NO3 mass % of NH4C1 mass % of NH4NO3 mass % of NH4C1
67.73 0 — —
66.27 2.0 88.20 0.79
64.73 3.82 88.00 1.34
62.24 5.58 90.25 1.65
61.68 6.97 87.65 2.28
53.49 11.08 23.31 62.22
36.99 15.80 13.63 66.29
19.05 21.81 7.09 72.75
0 28.33 — —

Answer the following with the help of the plot obtained.

(1) What is the ternary composition?
(2) Is there evidence of hydrate or double salt formation?
(3) Determine the maximum theoretical recovery of NH4Cl from a dry salt mixture
of NH4Cl–NH4NO3 containing 80% by mass of NH4Cl.
7.5 The following data are given for the system Na2SO4–MgSO4–H2O at 40 °C and
1 atm.

Composition of saturated Nature of solid phase in

solution equilibrium
(1) 35 mass % Na2SO4 Na2SO4
0 mass % MgSO4
(2) 0 mass % Na2SO4 MgSO4
30 mass % MgSO4
(3) 25 mass % Na2SO4 Na2SO4 + Na2SO4 MgSO4 4H2O
15 mass % MgSO4
(4) 5 mass % Na2SO4 MgSO4 + Na2SO4 MgSO4 4H2O
28 mass % MgSO4
 Phase Diagrams of Three-Component Systems 403

Composition of Na2SO4 MgSO4 4H2O is 42.4 mass % Na2SO4 and 36 mass %

MgSO4.
(a) Sketch the phase diagram.
(b) If a solution containing 10 mass % Na2SO4 and 10 mass % MgSO4 is evaporated,
what solid will appear first, and what is the composition of the last solution to exist
before the system becomes entirely solid?
(c) If equal masses of Na2SO4 and of solution (b) above are mixed, how many phases
will be present at equilibrium and what will be their compositions?
7.6 (a) The following data were obtained for the ternary system sodium nitrate-potassium
nitrate-water at 50 °C.

Composition of saturated solution Solid phase

NaNO3 KNO3 Water
mass % mass % mass %
53.2 0 46.8 NaNO3
47.6 12.3 40.1 NaNO3
43.3 21.6 35.1 NaNO3
39.8 28.9 31.3 NaNO3 + KNO3
31.7 31.3 37.0 KNO3
19.1 35.9 45.0 KNO3
0 46.2 53.8

Construct the ternary phase diagram on an equilateral triangle. What is the nature
of the system at each of the following compositions?

Constituents Percentage compositions by mass

(1) (2) (3) (4) (5) (6)
Sodium nitrate 20 43.7 15 70 16.0 47.0
Potassium nitrate 25 20.0 28 6 60.0 41.0
Water 55 36.3 57 24 24.0 12.0

If the system consists of more than one phase, determine also their compositions
and relative amounts.
(b) Given is the system containing 10 mass % NaNO3 and 30 mass % KNO3. What
will be the nature of first crystal obtained during the isothermal evaporation of the
above system? Up to what limit the above evaporation should be carried out so that
the yield of separated crystals is maximum?
(c) Given is the system containing 30 mass % NaNO3 and 60 mass % KNO3. Describe
if it is possible to get the pure crystals of KNO3 by adding more of water. If so, indicate
up to what limit the dilution should be carried out to get the maximum amount of KNO3
crystals.
(d) Describe the sequence of effects that are produced during the isothermal evaporation
of the system 1 (i.e. 20 mass % NaNO3, 25 mass % KNO3).
404 A Textbook of Physical Chemistry

(e) Given the system containing 30 mass % NaNO3 and 60 mass % KNO3. To this
system a solution of 20 mass % KNO3 is added. Indicate on which line composition
of the resultant solution would move.
(Ans. (a)(l) unsaturated solution of KNO3 and NaNO3, (2) saturated solution of
NaNO3 in the presence of KNO3, (3) saturated solution of KNO3 in the presence of
NaNO3, (4) solid NaNO3 in equilibrium with a solution of composition 48.5 mass
% NaNO3, 10.0 mass % KNO3 and 41.5 mass % water; relative amounts are 41.7
parts by mass of solid NaNO3 and 58.3 parts by mass of liquid, (5) solid KNO3 in
equilibrium with a solution of composition 27 mass % NaNO3, 33 mass % KNO3
and 40.0 mass % water; relative amounts are 40.3 parts by mass of solid KNO3 and
59.7 parts by mass of water, and (6) solid mixture of 51.5 mass % NaNO3 and 48.5
mass % KNO3 in equilibrium with a solution of composition 39.8 mass % NaNO3,
28.9 mass % KNO3 and 31.3 mass % water; relative amounts are 38% by mass of
liquid and 62% by mass of solid;
(b) KNO3, 21 mass % NaNO3, 63 mass % KNO3 and 16 mass % water, and
(c) 25 mass % NaNO3, 53 mass % KNO3 and 22 mass % water.)
7.7 (a) In the ternary system potassium sulphate-sodium sulphate-water, a double salt of
composition 3K2SO4 Na2SO4 (known as Glaserite, 78.6 mass % K2SO4 and 21.4
mass % Na2SO4) is formed. The following compositions of the saturated solutions
were obtained.

Composition of saturated solution Solid phase

K2SO4 Na2SO4 Water
mass % mass % mass %
14.19 0 85.81 K2SO4
13.8 5.68 80.52 K2SO4-Glaserite
5.85 29.4 64.75 Na2SO4-Glaserite
0 31.6 68.4 Na2SO4

Construct the phase diagram and determine the nature of system at the following
compositions.

Constituent Percentage compositions by mass

(1) (2) (3) (4)
Potassium sulphate 8 38 75 30
Sodium sulphate 17 22 10 45
Water 75 40 15 25

If the system consists of more than one phase, determine also their compositions
and relative amounts.
(b) Is the double salt stable in the presence of water?
(c) Show that the solution at which Na2SO4 and glaserite are in equilibrium is a
congruently saturated whereas the solution at which K2SO4 and glaserite are in
equilibrium is an incongruently saturated.
(d) Suppose the apex representing water is joined with the point representing the
composition of the double salt. Take a point on the line in the unsaturated solution
region and describe the sequence of effects that is produced if the above system is
subjected to the isothermal evaporation.
 Phase Diagrams of Three-Component Systems 405

(e) Take a point corresponding to the binary system containing solid Na2SO4 and
the saturated solution of Na2SO4. Describe the sequence of effects that is produced
if K2SO4 is added to this binary system.
7.8 In the ternary system NaCl–Na2SO4–H2O, a stable hydrate Na2SO4 10H2O (44.1
mass % Na2SO4 and 55.9 mass % H2O) is formed. The following compositions of
saturated solutions were obtained at 25 °C.

Composition of saturated solution Solid phase

NaCl Na2SO4 Water
mass % mass % mass %
0 21.6 78.4 Na2SO4 10H2O
7.6 16.0 76.4 Na2SO4 10H2O
14.5 14.5 71.0 Na2SO4 + Na2SO4 10H2O
18.4 10.4 71.2 Na2SO4
22.7 7.1 70.2 Na2SO4 + NaCl
24.65 3.35 72.0 NaCl
26.6 0 73.4 NaCl

Construct the phase diagram and determine the nature of system at the following
compositions.

Constituent Percentage composition by mass

(1) (2) (3) (4) (5) (6)
NaCl 8 5 5 24.5 40 24
Na2SO4 8 30 55 30.5 40 6
Water 84 65 40 45 20 70

If the system consists of more than one phase, determine also their compositions
and relative amounts.
7.9 In the ternary system NaCI–Na2SO4–H2O at 17.5 °C, it is found that solid Na2SO4
is never in equilibrium with the solution. The following compositions of saturated
solutions were obtained:

Composition of saturated solution Solid phase

Na2SO4 NaCl Water
mass % mass % mass %
13.8 0 86.2 Na2SO4 10H2O
8.5 8.1 83.4 Na2SO4 10H2O
6.8 16.9 76.3 Na2SO4 10H2O
7.4 22.3 70.3 Na2SO4 10H2O + NaCl
0 26.5 73.5 NaCl

Construct the phase diagram and determine the nature of system at the following
compositions.
406 A Textbook of Physical Chemistry

Constituent Percentage composition by mass

(1) (2) (3) (4) (5)
NaCl 10 5 50 24 45
Na2SO4 10 35 10 6 45
Water 80 60 40 70 10

If the system consists of more than one phase, determine also their compositions
and relative amounts.
7.10 (a) In the ternary system NaNO3–Na2SO4–H2O, a simple hydrate Na2SO4 10H2O
and the hydrated double salt (ternary compound) NaNO3 Na2SO4 H2O (darapskite
34.6 mass % NaNO3, 58.0 mass % Na2SO4 and 7.4 mass % H2O) are formed. The
following compositions of saturated solutions were obtained:

Composition of saturated solution Solid phase

NaNO3 Na2SO4
mass % mass %
47.9 0 NaNO3
46.5 1.57 NaNO3
45.2 3.05 NaNO3 + Darapskite
44.6 3.40 Darapskite
43.1 3.74 Darapskite
37.7 6.17 Darapskite
31.1 10.2 Darapskite
29.5 11.3 Darapskite
27.7 12.7 Darapskite
26.8 13.4 Darapskite + Na2SO4
25.0 14.6 Na2SO4 + Na2SO4 10H2O
21.2 14.8 Na2SO4 10H2O
12.6 16.5 Na2SO4 10H2O
0 21.6 Na2SO4 10H2O

Construct the phase diagram and label it.

(b) Show that the ternary salt is unstable in the presence of water.
(c) Show that the solution at which NaNO3 and the ternary compound are in
equilibrium is a congruently saturated whereas the solution at which Na2SO4 and
the ternary compound are in equilibrium is an incongruently saturated.
7.11 (a) Figure 4 shows the solubility curves of A H2O, A, A B and B. Complete the
phase diagram and label it.
(b) Given a point X in Fig. 4. What does it represent? Describe the sequence of
events that is produced when the system X is subjected to the isothermal dehydration.
(c) Is it possible to obtain the crystals of pure A on evaporating the system X? If
yes, at what point will the yield of crystal A be maximum?
(d) Is the double salt A B congruently saturating?
(e) How does Fig. 4 help in obtaining the crystals of A H2O from a solution
containing both A and B?
(f) Is the temperature of the phase diagram of Fig. 4 greater than, equal to or less
than 0 °C?
 Phase Diagrams of Three-Component Systems 407

H2O

b e
c
d

A B
Mole per cent
Fig. 4

7.12 The following data were obtained on the system CaCl2–KCl–H2O at 75 °C.

Composition of saturated solution Solid phase

CaCl2 KCl
mass % mass %
0 33.16 KCl
11.73 21.68 KCl
18.27 16.10 KCl
28.47 9.62 KCl
37.65 6.77 KCl
47.65 8.43 KCl
50.19 11.32 KCl and 2KCl CaCl2 2H2O
50.92 9.36 2KCl CaCl2 2H2O
53.85 6.21 2KCl CaCl2 2H2O
56.33 4.51 2KCl CaCl2 2H2O
57.62 3.60 2KCl CaCl2 2H2O
and CaCl2 2H2O
57.77 2.56 CaCl2 2H2O
58.58 0 CaCl2 2H2O

Construct the triangular plot and label each area. Describe what would happend on
isothermal evaporation at 75 °C of a solution initially containing 85 mass % water,
10 mass % CaCl2 and 5 mass % KCl. Assume 100 g of solution. What mass of H2O
have been evaporated when half the mass of the system is in solids?
408 A Textbook of Physical Chemistry

7.13 The following data refer to the system K2SO4–(NH4)2SO4–H2O at 30 °C.

Composition of saturated solution Composition of moist solid solution

K2SO4 (NH4)2SO4 K2SO4 (NH4)2SO4
mass % mass % mass % mass %
0 44.2 only (NH4)2SO4
1.2 42.7 1.6 90.3
2.4 40.9 22.1 69.3
4.1 37.8 33.9 57.8
4.9 33.5 50.8 42.3
6.4 31.0 62.2 30.0
9.1 18.5 84.0 12.7
10.7 8.4 93.2 3.1
11.2 0 only K2SO4

Draw the phase diagram and label each area. A system containing 90 g of water and
10 g each of K2SO4 and (NH4)2SO4 is evaporated isothermally at 30 °C. (i) What
is the composition of the solution when a precipitate first appears and what is the
composition of the precipitate? (ii) What is the composition of the last solution to
exist before the system solidifies? Give the compositions and amounts of the solid
(s) present. (iii) When the system reaches the point containing 40% by mass of water
what phases are present and in what amounts?
 8 Electrochemical Cells

8.1 INTRODUCTION
Electrochemical cells can be broadly classified into two categories, viz., electrolytic
cells and galvanic (or voltaic) cells. In the former, a chemical reaction (more
precisely electrolysis) is carried out with the help of an electrical current, whereas
in the latter an electrical current is produced as a result of some spontaneous
chemical reaction. Thus, an electrolytic cell is a device to convert electrical
energy into chemical energy whereas in the galvanic cell, the reverse of this
process takes place. In this section, we will outline the working of these two
types of cells along with their sign conventions.
Electrolytic Cell Consider an electrolytic cell involving the electrolysis of molten sodium chloride
using platinum electrodes as shown in Fig. 8.1.1.

Fig. 8.1.1 Electrolysis of

molten sodium chloride

The left-side electrode is connected to the negative terminal of an external

battery which supplies electrons to this electrode. It is because of this, the left-
side electrode becomes negatively charged. Electrons are being sucked but of
the right-side electrode by the positive terminal of the battery and thus this
electrode acquires a positive charge. Within the solution, electricity is carried
out by the movements of ions. The positive ions (i.e. cations) are attracted
towards the negative electrode and the negative ions (i.e. anions) towards the
positive electrode. Since cations are attracted towards the negative electrode, the
latter is known as the cathode. Similarly the positive electrode is known as the
410 A Textbook of Physical Chemistry

anode. Electrode reactions involve reduction at the cathode and oxidation at the
anode. Thus in the present case, we have
At cathode Na+(l) + e– Na(s)
–
At anode Cl (l) 1
2
Cl2(g) + e–

The overall transformation is

Na+(l) + Cl–(l) Na(s) + 1

2
Cl2(g)

Galvanic Cell As stated above, in the galvanic cell, electric current is generated as a result of
some spontaneous chemical reaction that takes place in the cell.
Working of Daniell To understand how electric current is generated, let us consider an example of
Cell Daniell cell where the following reaction is produced:
Zn(s) + CuSO4(aq) Cu(s) + ZnSO4(aq)
or, in ionic form
Zn(s) + Cu2+(aq) Cu(s) + Zn2+(aq)
This reaction occurs at a very fast speed, i.e. the moment zinc is added
in copper sulphate solution, copper is immediately formed. In this reaction, we
have basically the following two partial reactions:
Zn(s) Zn2+(aq) + 2e– (oxidation)
2+ –
and Cu (aq) + 2e Cu(s) (reduction)
If the two partial reactions are carried out in two physically separate
places, the electrons will have to flow from a place where oxidation occurs to
a place where reduction occurs through an external wire. This flow of electrons
constitutes a current, which can be used to drive a motor, lift a mass, or do
any other work.
Formulation of The most obvious way to separate the partial reactions occurring in Daniell cell
Daniell Cell is to insert the Zn electrode into a solution containing Zn2+ ions (but not Cu2+
ions) and the Cu electrode (or some unreactive metal) into a solution containing
Cu2+ ions as shown in Fig. 8.1.2. From Zn electrode, a minute amount of Zn
can go into the solution as Zn2+ ions leaving a negative charge on the electrode
(because of electrons left behind) and a positive charge in the solution. These
charges stop the ionization process of zinc almost immediately; for every Zn2+
ion entering the solution, it or another ion will be driven back to the Zn electrode
by the attraction of the negative electrode and the repulsion of the positive
solution. Similarly, on the Cu electrode a few Cu2+ ions from the solution may
be deposited as Cu atoms. This process will make the electrode positive and the
solution negative and thus the deposition process is stopped.† However, these

†
It may be that both Cu and Zn electrodes give up positive ions to solution and become
negatively charged or they may both become positively charged by neutralization of positive
ions from the solution. But from the knowledge that Zn is more electropositive than Cu, we
can say that Zn has a greater tendency to dissolve as Zn2+ than Cu has to dissolve as Cu2+.
 Electrochemical Cells 411

processes at the two electrodes, namely, oxidation at Zn electrode and reduction

at Cu electrode, can be resumed provided we connect the two electrodes by a
wire to allow the electrons to flow from Zn electrode to the electron-deficient
Cu electrode and bring the two solutions into contact through a porous plug or
a salt bridge† so as to neutralize the charges of the two solutions and prevent
a direct flow of Cu2+ ions towards Zn electrode.

Fig. 8.1.2 Daniell cell

Sign and Nomencla- In the cell shown in Fig. 8.1.2, the Zn electrode becomes negatively charged as
ture of Electrodes the electrons released in the oxidation reaction (Zn Zn2+ + 2e–) reside at
this electrode. Similarly, the Cu electrode becomes positively charged as the
electrons are taken out of this electrode for the reduction reaction (Cu2+ + 2e–
Cu) which takes place at this electrode. As in the electrolytic cell, the electrode
at which oxidation reaction takes place is known as the anode and that where
reduction reaction occurs is known as the cathode. Thus, the negative electrode
of the galvanic cell is known as anode and the positive one as the cathode.
Galvanic Cell In the above example of Daniell cell, we have two solutions which have to be
Without a Salt connected so that no intermixing takes place. An example in which this difficulty
Bridge does not arise is due to the following spontaneous reaction:

Zn(s) + 2AgCl(s) 2Ag(s) + Zn2+(aq) + 2Cl–(aq)

If the two solids Zn and AgCl are brought into contact, the reaction will
take place very slowly owing to the difficulty of establishing sufficient intimate
contact between them. But the reaction has a strong tendency to take place and
can be carried out by using the cell shown in Fig. 8.1.3.
The reaction at the Zn electrode is
Zn(s) Zn2+(aq) + 2e–

†
The salt bridge is an agar jelly saturated with either KCl or NH4NO3 and is used to
connect the two electrode compartments. See also Section 8.21.
412 A Textbook of Physical Chemistry

Fig. 8.1.3 Another

example of a galvanic cell

The two electrons left behind on the Zn can travel through the external
wire to the silver-silver chloride electrode where the following reaction occurs.
2AgCl(s) + 2e– 2Ag(s) + 2Cl–(aq)
Thus, the overall process is given by the reaction:
Zn(s) + 2AgCl(s) 2Ag(s) + Zn2+(aq) + 2Cl–(aq)
Resume of Sign In a galvanic cell, electrons are fed into the anode by the oxidation reaction that
Conventions takes place at the electrode. The anode pushes these electrons into the external
circuit and is, therefore, regarded as the negative electrode—the source of
negative charge. The cathode is an electron sink and is, therefore, called the
positive electrode.
In an electrolytic cell, the cathode is still the electron sink, but, this time,
we are forcibly feeding electrons into the cathode by connecting it to the negative
terminal of a generator or a galvanic cell. It is because of this that the cathode
of an electrolytic cell is a negative electrode. Since electrons are being sucked
out of the anode by the positive terminal of the external battery, the anode is
considered a positive electrode.
Oxidation takes place at anode and reduction at cathode in a cell of either
type. The only difference is about the sign of the electrodes. Table 8.1.1 gives
the sign convention and electrode reactions in both cells.

Table 8.1.1 Sign Convention and Electrode Reactions in a Cell

Anode Cathode
Cell Sign Type of Sign Type of
reaction reaction
Galvanic Negative Oxidation Positive Reduction
Electrolytic Positive Oxidation Negative Reduction

Diagrammatic Figure 8.1.4 illustrates the distinction between the sign conventions of the two
Distinction between types of cells.
Galvanic and
Electrolytic Cells
 Electrochemical Cells 413

Fig. 8.1.4 Sign conven-

tions in the galvanic and
the electrolytic cells

8.2 REVERSIBLE AND IRREVERSIBLE CELLS

The use of thermodynamic principles when applied to a system is subject to
one important restriction, namely, that the system must be reversible in the
thermodynamic sense. This requires that:
(1) the driving and opposing forces be infinitesimally different from each
other, and
(2) it should be possible to reverse any change taking place by applying
a force infinitesimally greater than the acting one.
A cell satisfying the above two requirements constitutes a reversible
cell. The potential difference of the cell can be substituted into the relevant
thermodynamic relations and hence the values of thermodynamic properties such
as free energy change, entropy change and enthalpy change of the cell reaction
can be determined. When the above conditions are not satisfied, the cell is said
to be irreversible, and thermodynamic relations do not apply.
The difference between reversible and irreversible cells may be illustrated
with the following two examples.
An Example of Consider a cell composed of Zn and Ag-AgCl electrodes dipping into an aqueous
Reversible Cell solution of zinc chloride. As seen earlier, the following reactions take place on
connecting the electrodes externally
414 A Textbook of Physical Chemistry

Anode 1
2
Zn(s) 1
2
Zn2+(aq) + e–

Cathode AgCl(s) + e– Ag(s) + Cl–(aq)

with the net reaction
1
2
Zn(s) + AgCl(s) Ag(s) + 1
2
Zn2+(aq) + Cl–(aq)

The above process continues as long as the external opposing potential is

infinitesimally smaller than that of the cell. However, if the opposing potential
becomes slightly larger than that of the cell, the direction of current flow is
reversed, and so is the cell reaction. Now zinc ions are converted to zinc at one
electrode, silver chloride is formed from silver and chloride ions at the other,
and the overall cell reaction becomes

Ag(s) + 1
2
Zn2+(aq) + Cl–(aq) 1
2
Zn(s) + AgCl(s)

Thus, it is obvious that the second condition of reversibility mentioned

above is satisfied. The first condition can be satisfied by drawing from or passing
through the cell a very minute current. Hence, the cell is reversible.
An Example of Consider a cell composed of zinc and silver electrodes immersed in a solution
Irreversible Cell of sulphuric acid. When the two electrodes are short circuited, (i.e. connected
externally by a wire) zinc dissolves with the evolution of hydrogen to form zinc
sulphate according to the reaction:
Zn(s) + H2SO4 ZnSO4 + H2(g)
However, when the cell is connected with an external source of potential slightly
greater than its own, silver dissolves at one electrode, hydrogen is evolved at
the other, and the cell reaction becomes
2Ag(s) + H2SO4 Ag2SO4 + H2(g)
Thus, it is obvious that though the first condition of reversibility can be
satisfied, the second cannot. Hence, the cell is an irreversible cell. The potential
of such a cell does not have any definite thermodynamic significance.

8.3 ELECTROMOTIVE FORCE AND ITS MEASUREMENT

In the Daniell cell, electrons flow from Zn electrode to Cu electrode. This is due
Electromotive Force to the fact that Zn atom can be more easily oxidized to Zn2+ ion than Cu atom to
Cu2+ ion. On the other side, Cu2+ ion can be more easily reduced than the Zn2+
ion. Consequently, Zn atom is oxidized to Zn2+ ion and the electrons set free at the
Zn electrode move towards Cu electrode where Cu2+ ion is reduced to Cu atom.
Basically, we can say that the flow of electrons is due to the difference of oxidation
tendencies of the two atoms, or it is due to the difference of reduction tendencies
of the two ions. The relative oxidation tendencies of atoms can be represented by
the oxidation potentials. A more easily oxidizable atom will have a larger value
of oxidation potential and a less easily oxidizable atom will have a low value of
oxidation potential. Thus, Zn atom has a larger oxidation potential than the Cu
 Electrochemical Cells 415

atom. Electrons in the external circuit flow from the electrode of higher oxidation
potential to the electrode of lower oxidation potential. The difference of potential
which causes a current to flow from the electrode of higher potential to the lower
one is known as the electromotive force, abbreviated as emf, of the cell and is
expressed in volts. We will represent emf of a cell by the symbol Ecell. Thus
Ecell = Higher oxidation potential – Lower oxidation potential (8.3.1a)
EMF in Terms of By convention, Ecell is expressed in terms of reduction potentials (known as
Reduction Potentials standard potentials) of the two electrodes. The reduction potentials measure the
relative reduction tendencies of ions and their values are simply negative of
oxidation potentials of the corresponding atoms. This follows from the fact that
an atom with the maximum tendency of oxidation (i.e. highest value of oxidation
potential) will yield an ion with the least tendency of reduction (i.e. the minimum
reduction potential) and vice versa. Thus, Eq. (8.3.1a) may be written as
Ecell = – (– Higher oxidation potential) + (– Lower oxidation potential)
= – Lower reduction potential + Higher reduction potential
i.e. Ecell = Higher reduction potential – Lower reduction potential (8.3.1b)
Measurement of To determine the accurate emf of a cell, direct use of voltmeter cannot be made,
EMF since it draws some current from the cell, which will change the emf due to
the changes in the concentrations of species caused by the electrode reactions.
Again, with appreciable current flow part of the emf will have to be utilized to
overcome the internal resistance of the cell, and hence the potential measured
on the voltmeter will not be the accurate cell emf.
The precise value of the emf of a cell can be determined by using
potentiometric method. In this method, an unknown emf is opposed by another
emf until the two are equal. Figure 8.3.1 illustrates the experimental set up for
determining the emf of a cell with the potentiometric method, where we have:
W
R
– +
F

S S¢
b
a
C
SC
– +

D K

Fig. 8.3.1 Experimental

set up for determining
– +
the emf of a cell X
416 A Textbook of Physical Chemistry

ab is a uniform wire. The resistance offered by the wire is directly proportional

to its length and is calibrated in volts.
SC is the standard cell, whose emf is reproducible, constant with time.
Usually a standard cadmium cell is used whose emf is 1.018 3 V at 20 °C.
X is an unknown cell, whose emf is to be determined.
W is a working cell, whose potential is larger than SC and X. All the three
cells have their negative terminals attached to one end of the wire ab.
R is a resistor of variable resistance.
G is a galvanometer.
Because of the working cell W, there is a uniform potential gradient along
the wire ab. First, the pointer C is set at a point S along ab corresponding to the
value of the emf of the standard cell, say 1.018 3 V. Next SC is thrown into the
circuit and F is moved along the resistor R until the galvanometer G shows no
deflection. When this balance is established, the current flowing through ab is of
such a magnitude as to make the potential drop between a and S exactly 1.018 3 V
and the voltage drop anywhere along ab is the same as the voltage marking on the
slide wire. Now the given cell is thrown into circuit and the pointer C is moved
along ab until a point S is found at which the galvanometer G again shows no
deflection. The reading of the slide wire at S gives the voltage directly.
Standard Cell The standard cell should be such that its potential should be reproducible,
constant with time and also it should be reversible. It should not suffer permanent
damage due to passage of current and should preferably have a low temperature
coefficient of emf. The cells that most closely approximate these requirements
are Weston unsaturated and saturated standard cells.
This type of cell consists of a H-shaped glass vessel containing in each arm
one of the electrodes as shown in Fig. 8.3.2. The positive electrode consists of
a platinum wire dipped into mercury that is covered with a paste of mercurous
sulphate and mercury. The negative electrode consists of a platinum wire dipped
into cadmium amalgam containing 12 to 14 mass % of cadmium. Over both
electrodes are sprinkled some crystals of solid CdSO4 (8/3) H2O. The entire cell
is filled with a saturated solution of cadmium sulphate, and the cell is closed with
corks and sealing wax. The function of the solid crystals of CdSO4 (8/3) H2O
is to keep the solution saturated with CdSO4 at all temperatures.
The working of the Weston saturated cell depends on the following
reversible reactions:

Cd(s) + SO42– (aq) + 8

3
H2O(l) CdSO4 8
3
H2O(s) + 2e–

Hg2SO4(s) + 2e– 2Hg(l) + SO42– (aq)

with the overall reaction as
8 8
Cd(s) + Hg2SO4(s) + 3
H2O(1) CdSO4 3
H2O(s) + 2Hg(1)

The reaction occurs when the cell is acting as a source of current, while reverse
reaction takes place when current is passed through the cell.
 Electrochemical Cells 417

Sealing

Wax
cork

Saturated
CdSO4
solution

CdSO4 × –8 H 2 O
3
CdSO4 × –8 H 2 O Hg + Hg2SO4
3
Cd Hg
Fig. 8.3.2 The standard amalgam
Pt – + Pt
Weston saturated cell

The potential of the cell at any temperature is given by the equation

E/V = 1.018 30 – 4.06 × 10–5 {(θc/°C) – 20} – 9.5 × 10–7 {(θc/°C) – 20}2

8.4 FORMULATION OF A GALVANIC CELL

Half-Cell An electrochemical cell requires two electrodes for a reaction to occur. The
assembly comprising of the electrode and the reagents that are involved with
it is called the half-cell and the component of the total chemical reaction that
occurs in the half-cell is the half-cell reaction or electrode reaction. Thus, we
require two half-cells to produce an electrochemical cell.
Cell Diagram A half-cell or an electrochemical cell can be briefly represented by a cell diagram
following a few rules given below.
The separation of two phases is shown by a verticle line ( | ).
The various materials present in the same phase are shown together with
the help of commas.
The two half-cells are joined with the help of a dashed vertical line ( ) if
the two liquids at the junction are miscible and by a double dashed vertical
lines ( ) if the liquid junction potential at the junction of the two liquids is
assumed to be eliminated.
The significant features of the substances such as fugacity of gas, activity
of ion, etc., are indicated in brackets drawn immediately after writing the
substance.
Illustrations Taking the examples of galvanic cells given in Figs 8.1.4 and 8.1.3, we represent
respectively, the two cells as
Zn | Zn2+(a1) Cu2+(a2) | Cu
Zn | ZnCl2(m) | AgCl | Ag
The Weston cadmium cell shown in Fig. 8.3.2 will be written as
8
Pt Hg Cd(Hg) CdSO4 3
H2O(s) saturated solution of CdSO4
8
CdSO4 3
H2O(s) Hg2SO4, Hg Pt
418 A Textbook of Physical Chemistry

8.5 ELECTRICAL AND ELECTROCHEMICAL POTENTIALS

The electrical potential at a point in space is defined as the work involved in
Potential bringing a unit charge from infinity, where the electric potential is zero, to the
point under study. If wel is the electrical work involved in bringing a charge Q
from infinity to a given point, then the potential V at this point is given by
wel
V = (8.5.1)
Q
Work Involved in If a charge dQ moves from a point at a potential V1 to a point at a potential V2
Moving a Charge the work involved in this process is given by

dwel = (V2 - V1 ) dQ (8.5.2)

If one coulomb of the charge is transferred under the potential difference of

one volt, the work done is 1 volt-coulomb. The latter is numerically equal to
1 J of work.
Electrochemical and The escaping tendency (i.e. chemical potential) of a charged particle (an ion or
Chemical Potentials an electron) in a phase depends on the electrical potential of that phase. To find
of a Species the relation between the electrical potential and the escaping tendency of a
charged particle, we consider a system of two phases M and M of the same
material at two different potentials φ and φ , respectively. If the amount dn of
the ith species carrying zi charge is transferred from M to M , then
dQ = zi F dn (8.5.3)

and dwel = (f ¢ - f ) dQ = (f ¢ - f ) zi F dn (8.5.4)

If the transfer is carried out reversibly, the electrical work dwel will be
equal to the change in the free energy of the system, i.e.
dG = dwel (8.5.5)
Substituting the relation of dwel from Eq. (8.5.4), we get
dG = (f ¢ - f ) zi F dn (8.5.6)

Let m zi and m z¢i be the chemical potentials of the ith species in the phases
M and M , respectively. If the amount dn of this species is transferred from M
to M , the free energy change of the system is given by
dG = m z¢i dn - m zi dn (8.5.7)

Comparing Eqs (8.5.6) and (8.5.7), we get

m z¢i - m zi = (f ¢ - f ) zi F (8.5.8)
Let μzi be the chemical potential of the ith species when the potential of
the phase M is zero. With this, Eq. (8.5.8) becomes
m zi = m zi + zi F f (8.5.9)
 Electrochemical Cells 419

Equation (8.5.9) relates the chemical potential (or the escaping tendency)
of the ith species of charge zi in a phase to its electrical potential. The escaping
tendency is a linear function of φ. Equation (8.5.9) divides the chemical potential
m zi of a charged species in two terms; the first term, μzi is the chemical
contribution and the second term zi Fφ is the electrical contribution. The former
has the same value in two phases of the same chemical composition since its
value is a function of T, p and the composition. The electrical contribution of the
phase depends upon the value of φ. On account of these two contributions, the
chemical potential mi is commonly referred to as the electrochemical potential.
Electrochemical For a metal, zi = 0 and hence its electrochemical and chemical potentials have
Potential of an the same value. For an electron in a metal electrode, Eq. (8.5.9) becomes
Electron in a Metal
me(M) = me(M) - F f (8.5.10)

From Eq. (8.5.10), it follows that the electrochemical potential me(M) and
the electrical potential φ have opposite trends, if the value φ is increased, the
value of me(M) is decreased and vice versa.
Electric Potential Since me(M) in Eq. (8.5.10) represents the escaping tendency of electron from
and Type of the electrode, it is obvious that if a negative electrical potential is applied to an
Reaction Occurring electrode, the electrochemical potential becomes larger than the chemical potential
at the Electrode indicating that the escaping tendency of an electron from the electrode is enhanced.
This, in turn, implies that the tendency of an oxidation reaction to take place at the
electrode is increased. On the other hand, the tendency of electrons to escape from
the electrode is diminished if a positive potential is applied to it. Alternatively, we
may state that the tendency of the electrode to accept electrons is increased and
hence the process that can take place at the electrode is the reduction one. Now, if
two electrodes of different electrical potentials (both positive or both negative or
one positive and the other negative) are coupled to make a cell, it is obvious that
the oxidation reaction will take place at the electrode of higher negative potential
(or lesser positive potential) and the reduction at the electrode of lower negative
potential (or higher positive potential).
Reduction Potentials Since on increasing the value of electrical potential, the tendency of reduction
reaction to occur at the electrode is increased, the electrical potential is commonly
referred to as the reduction potential. It is for this reason, the equilibrium reaction
at the electrode is also written as the reduction reaction.

8.6 DIFFERENT TYPES OF HALF-CELLS AND THEIR REDUCTION POTENTIALS

In this section, we consider various types of half-cells that are employed and
the expressions which relate the half-cell potential with the activity and fugacity
of the constituents of the half-cell.

GAS-ION HALF-CELL
In the gas-ion half-cell, an inert collector of electrons, platinum or graphite is
in contact with gas and a solution containing a specified ion.
420 A Textbook of Physical Chemistry

Hydrogen Gas- One of the most important gas-ion half-cell is the hydrogen gas-hydrogen ion
Hydrogen Ion Half- half-cell (also commonly know as hydrogen electrode). In this half-cell, purified
Cell hydrogen gas at a constant pressure is passed over a platinum electrode which
is in contact with an acid solution (Fig. 8.6.1).

Fig. 8.6.1 Hydrogen

gas-hydrogen ion half-cell

Expression of The expression of Ehalf-cell can be derived by considering the reversible reduction
Reduction Potential reaction that occurs at the electrode. For the present case, we have
(Nernst Equation)
H+(aq) + e– (Pt) 1
2
H2(g)

The equilibrium condition at the electrode is

1
mH+ (aq) + me - (Pt) = 2
mH2 (g) (8.6.1)

Making use of Eq. (8.5.9), the above expression becomes

{mH+ (aq) + F faq } + {me - (Pt) - F fPt } = 1
2
mH2 (g) (8.6.2)

Substituting the expressions

mH+ (aq) = mH∞ + (aq) + RT ln aH+ (aq) (8.6.3)†

and mH2 (g) = mH∞ 2 (g) + RT ln ( f H2 (g) /f ∞) (8.6.4)

in Eq. (8.6.2) and rearranging it, we get

mH∞ + (aq) - 21 mH∞ 2 (g) + me - (Pt) RT ( f H2 (g) /f ∞)1/2

fPt - faq = - ln
F F aH+ (aq)

†
See Annexure I at the end of this chapter for the concept of activity.
 Electrochemical Cells 421

By definition, Ehalf-cell = φ Pt – φ aq. Thus, we have

mH∞ + (aq) - 21 mH∞ 2 (g) + me - (Pt) RT ( f H2 (g) /f ∞)1/2

EH + | H 2 | Pt = - ln (8.6.5)
F F aH+

If the fugacity of the gas is unity and the activity of H+ in solution is unity,
the half-cell is said to be in the standard state and the corresponding potential,
the standard reduction potential (or simply as the standard potential), is given by

mH∞ + (aq) - 21 mH∞ 2 (g) + me - (Pt)

EH∞ + | H 2 | Pt = (8.6.6)
F
With this, Eq. (8.6.5) modifies to

RT ( f H2 (g) /f ∞)
EH + | H 2 | Pt = EH∞ + | H 2 | Pt
- ln (8.6.7)
F aH+

Equation of the above type is known as the Nernst equation.

METAL-METAL ION HALF-CELL

Metal-metal ion half-cell consists of a bar of metal M in contact with a solution
containing Mn+ ions. Examples include zinc-zinc ion, copper-cupric ion, silver-
silver ion and gold-auric ion half-cells.
Expression of The equilibrium reaction at the electrode is
Reduction Potential
Mn+(aq) + ne– M(s)
Equality of electrochemical potentials yields
m Mn + (aq) + nme - (M) = m M(s)

or {m Mn + (aq) + nF faq } + n{me - (M) - F fM } = m M(s) (8.6.8)

Substituting the expression

∞ n + + RT ln a n +
m Mn+ = m M M (aq)

in Eq. (8.6.8) and rearranging the resultant expression, we get

∞ n+
mM + nme - (M) - m M(s) RT 1
(aq)
fM - faq = - ln (8.6.9)
nF nF aMn + (aq)

If the activity of Mn+ is unity, we get the standard potential of M–Mn+ half-cell,
such that
∞ n+
mM + nme - (M) - m M(s)
∞ n + |M =
EM
(aq)
(8.6.10)
nF
422 A Textbook of Physical Chemistry

Substituting the above expression in Eq. (8.6.9), we get

RT 1
EM n + |M ∞ n+
= EM |M - ln (8.6.11)
nF aMn+

METAL AMALGAM-METAL ION HALF-CELL

In this electrode, metal amalgam is placed in contact with a solution containing
metal ion. Electrical contact is made by a platinum wire dipping into the amalgam
pool.
Expression of The equilibrium reaction at the electrode is
Reduction Potential M n+ (aq) + ne - (Pt) Æ M(Hg)
Equality of electrochemical potentials yields
m Mn + (aq) + nme - (Pt) = m M(Hg) (8.6.12)

or {m Mn+ (aq) + nF faq } + n{me - (Pt) - F fPt } = m M(Hg) (8.6.13)

Substituting the expressions

∞ n+
m Mn + (aq) = m M + RT ln aMn + (aq)
(aq)

and ∞ + RT ln aM(Hg)
m M(Hg) = m M
in Eq. (8.6.13) and rearranging the resultant expression, we get
∞ n+
mM ∞
+ nme - (Pt) - m M RT aM(Hg)
(aq)
fPt - faq = - ln (8.6.14)
nF nF aMn +
The reduction potential of Mn+ | M(Hg) | Pt assembly will be given by
EM n + | M(Hg) | Pt = {fPt - fM(Hg) } + {fM(Hg) - faq }
= fPt - faq
Hence Eq. (8.6.14) becomes
∞ n+
mM ∞
+ nme - (Pt) - m M RT aM(Hg)
(aq)
EM n + | M(Hg) | Pt = - ln (8.6.15)
nF nF aMn +
If the activities of M(Hg) and Mn+(aq) are unity, we get the standard potential
of M–Mn+ half-cell, such that

∞ n+
mM ∞
+ nme - (Pt) - m M
∞ n+
EM | M | Pt =
(aq)
nF
With this, Eq. (8.6.15) modifies to

RT aM(Hg)
EM n + | M(Hg) | Pt ∞ n+
= EM | M | Pt - ln (8.6.16)
nF aMn +
 Electrochemical Cells 423

Equation (8.6.16) may be written as

RT RT 1
EM n + | M(Hg) | Pt ∞ n+
= EM | M | Pt - ln aM(Hg) - ln
nF nF aMn +
RT 1
∞ n+
= EM | M(Hg) | Pt - ln (8.6.17)
nF aMn +

º n+ | M(Hg) | Pt is the standard potential of the given metal amalgam. Its

where E M
value may be determined by using a solution of known activity of Mn+.
Alternatively, the following procedure may be employed.
A cell is constructed with the given metal amalgam electrode and the pure
metal electrode dipping into a solution of metal ion, i.e.
Pt | M(Hg) | Mn+(aq) | M
The emf of the cell is determined experimentally. It is given by the
expression

Ecell = EMn + |M - EM n + | M(Hg) | Pt (8.6.18)

RT 1
where EM n + |M ∞ n+
= EM |M - ln (8.6.19)
nF aMn +

RT 1
and EM n + |M(Hg)| Pt
∞ n+
= EM | M(Hg)| Pt - ln (8.6.20)
nF aMn +

Substituting Eqs (8.6.19) and (8.6.20) in Eq. (8.6.18), we get

∞ n+
Ecell = EM |M
∞ n+
- EM | M(Hg)| Pt (8.6.21)

∞ n+
Knowing EM |M from the table of standard potentials and Ecell experimentally,
∞ n+
the value of EM | M(Hg) | Pt may be determined from Eq. (8.6.21).

METAL-INSOLUBLE SALT-ANION HALF-CELL

In this half-cell, a metal coated with its insoluble salt is in contact with a solution
containing the anion of the insoluble salt. Three such half-cells are described
below.

Silver-Silver Chloride- This half-cell is represented as Cl– | AgCl | Ag. The equilibrium reaction that
Chloride Ion Half-Cell occurs at the electrode is
AgCl(s) + e– Ag(s) + Cl–(aq)
424 A Textbook of Physical Chemistry

Expression of The equality of electrochemical potentials gives

Reduction Potential
m AgCl(s) + me - (AgCl | Ag) = m Ag(s) + mCl - (aq)

Making use of Eq. (8.5.9), the above expression becomes

m AgCl(s) + {me - (AgCl | Ag) - F fAgCl | Ag } = m Ag(s) + {mCl - (aq) - Ffaq }

(8.6.22)

Substituting

∞-
mCl - (aq) = mCl + RT ln aCl -
(aq)

in Eq. (8.6.22) and rearranging it, we get

∞-
m Ag(s) + mCl - m AgCl(s) - me - (AgCl | Ag) RT
(aq)
fAgCl | Ag - faq = - - ln aCl -
F F
Defining the standard potential when aCl– = 1, we get

RT
ECl - | AgCl | Ag
∞-
= ECl | AgCl | Ag - ln aCl - (8.6.23)
F
where ECl - | AgCl | Ag = fAgCl | Ag - feq

∞-
m Ag(s) + mCl - m AgCl(s) - me - (AgCl | Ag)
and ∞-
ECl | AgCl | Ag =-
(aq)
F
Mercury-Mercuric In this half-cell, a pool of mercury is covered with a paste of solid HgO and a
Oxide-Hydroxide Ion solution of a base. The equilibrium reaction that takes place at the platinum
Half-Cell electrode is
HgO(s) + H2O(1) + 2e– Hg(1) + 2OH–(aq)

Expression of The equality of chemical potential yields

Reduction Potential
mHgO(s) + mH2 O(1) + 2me - (Pt) = mHg(1) + 2mOH - (aq)

Replacing m in terms of μ, we get

mHgO(s) + mH2 O(1) + {2me - (Pt) - 2F fPt } = mHg(1) + {2mOH - (aq) - 2Ffaq }

Substituting

∞ -
mOH - (aq) = mOH + RT ln aOH -
(aq)
 Electrochemical Cells 425

in the previous expression and rearranging it, we get

∞ -
mHg(1) + 2mOH - mHgO(s) - mH2 O(1) - 2me - (Pt)
(aq)
fPt - faq = -
2F
RT
T
- ln aOH -
F
Defining the standard potential when aOH– = 1, we get
RT
∞ - faq
fPt - faq = (fPt ∞ )- ln aOH - (8.6.24)
F
∞ -
mHg(1) + 2mOH - mHgO(s) - mH2 O(1) - 2me - (Pt)
where ∞ - faq
fPt ∞ =- (aq)
2F
The half-cell potential will be given by
EOH - | HgO | Hg = (fPt - fHgO | Hg ) + (fHgO | Hg - faq )
∫ fPt - faq

Thus, Eq. (8.6.24) becomes

RT
EOH - ∞ -
= EOH - ln aOH -
| HgO | Hg | HgO | Hg
F (8.6.25)

Mercury-Mercurous This half-cell is known as calomel half-cell. The equilibrium reaction is

Chloride-Chloride
Hg2Cl2(s) + 2e– 2Hg(1) + 2Cl–(aq)
Ion Half-Cell
Its Nernst equation is
RT
ECl - | Hg2 Cl2 | Hg
∞-
= ECl | Hg2 Cl2 | Hg - ln aCl - (8.6.26)
F
∞ - - mHg Cl - 2m -
2mHg(1) + 2mCl
where ∞-
ECl | Hg2 Cl2 | Hg =-
2 2 e (Pt)
2F

OXIDATION-REDUCTION HALF-CELL
An oxidation-reduction half-cell has an inert metal collector, usually platinum,
immersed in a solution which contains two ions of the same element in different
states of oxidation.
Ferric-Ferrous Half- One of the examples is ferric-ferrous half-cell. The equilibrium reaction to be
Cell considered is
Fe3+(aq) + e–(Pt) Fe2+(aq)
The Nernst equation is
RT a 2+
EFe3+ , Fe2+ | Pt
∞ 3+ , Fe2+
= EFe | Pt - ln Fe (8.6.27)
F aFe3+
426 A Textbook of Physical Chemistry

∞ 2+ - m ∞ 3+ - m -
m Fe
where ∞ 3+ , Fe2+
EFe | Pt =-
Fe e (Pt)
F

Stannic-Stannous Another example is stannic-stannous half-cell where the reduction reaction to be

Half-Cell considered is

Sn4+(aq) + 2e– Sn2+(aq)

and the Nernst equation is

RT a 2+
ESn 4+ , Sn2+ | Pt
∞ 4+ , Sn2+
= ESn | Pt - ln Sn (8.6.28)
2F aSn 4+

General Expression From the derived expressions of Nernst equation for the various half-cells (Eqs
of Nernst Equation 8.6.5–8.6.28), it may be concluded that the form of Nernst equation for a given
half-cell reaction can be written down without undergoing the explicit derivation
by making use of the relation

E = E∞ -
RT
nF
ln
{ ’ (a ) };
j
j
nj Ï+ve for product species in the reaction
nj ∫ Ì
Ó- ve for reactant species in the reaction
(8.6.29)
where n is the number of electrons involved in the half-cell reaction and νj is the
stoichiometry number of the jth species in the half-cell reaction. The latter has a
positive/negative value for the species appeared on the right/left side of the cell
reaction. The symbol stands for the multiplication of activity or fugacity of
all the j species (except those appeared in the solid and liquid forms) involved
in the cell reaction.

8.7 THE EMF OF A CELL AND ITS CELL REACTION

When the two half cells are combined and their electrodes are connected by an
external electrical conductor, an electrical current will flow and chemical reactions
will occur in the two half-cells. The nature of the reaction proceeding in a cell
can be deduced from the manner in which the electrodes are connected to the
standard cell in order to obtain a balance in the potentiometer.

Electrode connected to the negative side of the standard cell is the negative
electrode while the one connected to the positive side is the positive electrode.
As stated earlier (Section 8.1), oxidation reaction occurs at the negative
electrode and thus electrons are released at this electrode.
The electrons are taken out from the negative electrode by the external
conductor and are absorbed at the positive electrode for the reduction reaction.
Cell Reaction The cell reaction can be determined by writing these oxidation and reduction
reactions with equal number of electrons and then adding the two reactions.
Thus
 Electrochemical Cells 427

Cell reaction = Ê
Reduction reaction ˆ ÊOxidation reaction ˆ
+ (8.7.1)
Ëat cathode ¯ Ëat anode ¯
Taking an example of Daniell cell, we have
Anode: oxidation reaction Zn(s) Zn2+(aq) + 2e–
Cathode: reduction reaction Cu2+(aq) + 2e– Cu(s)
Adding the two, we get
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

Recommendations The emf of the cell under consideration is due to the spontaneous reaction that
for Cell Diagram takes place within the cell. Under balanced reversible conditions a cell reaction
can proceed in either direction. Which process—whether forward or backward—
corresponds to a given cell? This, of course, can be decided experimentally but
not from the manner of writing cell on paper, unless the following recommended
convention in this regard is accepted.
If a cell is written on a piece of paper, then the cell reaction will be written
so that electrons are accepted from the external circuit by the electrode written
on the right and are given out by the electrode written on the left.
In other words, once the cell has been written, it will be understood that
the left electrode (represented by the symbol L) is the anode (where oxidation
reaction takes place and thus electrons are set free) and the right electrode
(represented by the symbol R) is the cathode (where reduction reaction occurs
and thus electrons are absorbed). With this convention, Eq. (8.7.1) may be
written as

Cell reaction = Ê
Reduction reaction ˆ ÊOxidation reaction ˆ
+ (8.7.2)
Ëat right electrode ¯ Ëat left electrode ¯

Illustrations To illustrate the procedure, we write the Daniell cell as

Zn | Zn2+(aq) Cu2+(aq) | Cu (8.7.3)
Now, according to the above stated rule, the left electrode will be considered
as the anode (or the negative terminal) and the right electrode as the cathode
(or the positive terminal). Thus, the cell reaction would be
Right electrode (reduction reaction) Cu2+(aq) + 2e– Cu(s)
Left electrode (oxidation reaction) Zn(s) Zn (aq) + 2e–
2+

Sum Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq) (8.7.4)

Note that if the cell has been written as
Cu | Cu2+(aq) Zn2+(aq) | Zn (8.7.5)
then while writing the cell reaction, the left electrode (i.e. Cu electrode) will be
considered as the negative terminal and the right electrode (i.e. Zn electrode) as
the positive terminal. The cell reaction would be
428 A Textbook of Physical Chemistry

Right electrode (reduction reaction) Zn2+(aq) + 2e– Zn(s)

Left electrode (oxidation reaction) Cu(s) Cu (aq) + 2e–
2+

Sum Zn2+(aq) + Cu(s) Zn(s) + Cu2+(aq) (8.7.6)

EMF of a Cell In Section 8.3, we have stated that the spontaneous cell reaction is due to the
difference of relative reduction tendencies of the two ions at the respective
electrodes. The ion with a higher reduction potential is reduced and the one
with lower reduction potential is formed by the oxidation of the corresponding
atom. Thus, electrons flow from the electrode of lower reduction tendency of
ions to the one of higher reduction tendency of ions. The reduction tendency of
an ion can be represented by reduction potential and hence emf of the cell can
be written as the difference of the two reduction potentials, i.e.

emf = Higher reduction potential – Lower reduction potential

Keeping in view the convention of writing a cell, the above expression

may be written as

Ê Reduction potentialˆ Ê Reduction potentialˆ

emf = Á - (8.7.7)
Ë of right electrode ˜¯ ÁË of left electrode ˜¯

Now if a cell as written produces a spontaneous cell reaction, it is

obvious that the reduction potential of the ion appeared at the right electrode
(where reduction reaction occurs) will be greater than the ion appeared at the
left electrode (where oxidation reaction occurs). Hence emf of such a cell will
be positive. Conversely, if the cell as written has a positive emf, it implies that
it would produce a spontaneous cell reaction with reduction at right electrode
and oxidation at left electrode. On the other hand, if the cell reaction is not
spontaneous, then the reduction potential of right electrode will be smaller than
that of left electrode. Consequently, emf of the cell will have a negative value.

Cell Reaction Equation (8.7.2) may be written in the form similar to that of Eq. (8.7.7). Since
oxidation is just reverse of reduction, it is obvious that
Oxidation reaction = – Reduction reaction
Thus, Eq. (8.7.2) may be written as

Ê Reduction reactionˆ Ê Reduction reactionˆ

Cell reaction = Á - (8.7.8)
Ë at right electrode ˜¯ ÁË at left electrode ˜¯

We shall adopt Eq. (8.7.8) in order to determine the cell reaction.

Illustrations To illustrate the procedure of determining cell reaction and cell potential, we
once again take the example of Daniell cell.

Cell1 Zn | Zn2+ Cu2+ | Cu

 Electrochemical Cells 429

We have
Electrode Reduction reaction Reduction potential
RT 1
Right Cu2+ + 2e– Cu ECu2+ ∞2
= ECu - ln
| Cu | Cu
2F aCu2+

RT 1
Left Zn2+ + 2e– Zn EZn2+ ∞ 2+
= EZn - ln
| Zn | Zn
2F aZn 2+

Subtracting reduction reaction of left electrode from that of right electrode,

we get the cell reaction:
Cu2+ + Zn Cu + Zn2+
Since the emf of the cell is
Ecell1 = ER – EL
we have
Ecell1 = ECu2+ | Cu
- EZn 2+ | Zn

Ê ∞ RT 1 ˆ Ê RT 1 ˆ
= Á ECu - ln - E ∞ 2+ - ln
aCu2+ ˜¯ ÁË Zn aZn2+ ˜¯
2+
| Cu | Zn
Ë 2F 2F
RT a 2+
∞ 2+
= (ECu ∞ 2+
- EZn )- ln Zn
| Cu | Zn
2F aCu2+

RT a 2+
or ∞ -
Ecell1 = Ecell ln Zn (8.7.9)
1
2F aCu2+
Cell2 If the cell were written as
Cu | Cu2+ Zn2+ | Zn
then we would have

Electrode Reduction reaction Reduction potential

RT 1
Right Zn2+ + 2e– Zn EZn2+ ∞ 2+
= EZn - ln
| Zn | Zn
2F aZn 2+

RT 1
Left Cu2+ + 2e– Cu ECu2+ ∞ 2+
= ECu - ln
| Cu | Cu
2F aCu2+

Subtracting reduction reaction of left electrode from that of right electrode,

we get the cell reaction as
Zn2+ + Cu Zn + Cu2+
The emf of the cell is given by
Ecell2 = EZn2+ | Zn – ECu2+ | Cu
430 A Textbook of Physical Chemistry

RT a 2+
∞ -
Ecell2 = Ecell ln Cu
2
2F aZn2+

where ∞ = E ∞ 2+
Ecell ∞ 2+
- ECu
2 Zn | Zn | Cu
Obviously,
Ecell2 = - Ecell1
and the reaction of cell2 is just a reverse of that of cell1.
General Expression The expression of cell potential, in general, can be written down directly from
of Cell Potential the cell reaction by making use of the relation

∞ -
Ecell = Ecell
RT
nF j{ n
} Ï+ve for the right-side species
ln ’ (a j ) j ; n j ∫ Ì
Ó - ve for the left-side species
(8.7.10)
where n is the number of electrons involved in the cell reaction, νj is the
stoichiometry of the jth species and E ºcell is given by
∞ = ER∞ - EL∞
Ecell (8.7.11)
The symbol P stands for the multiplication of activity or fugacity raised
j
to the corresponding stoichiometric number of all the j species (except those
appeared in the solid and liquid forms) involved in the cell reaction.
Criterion for the The connection between the sign of emf of a cell and the nature of the associated
Spontaneity of the cell reaction may be derived thermodynamically. As stated above, the electrons
Cell Reaction flow spontaneously from left electrode to right electrode provided the reduction
potential of right electrode is greater than that of left electrode. The amount of
electrical work involved in moving the amount n of electrons from left electrode
to right electrode as given by Eq. (8.5.4) is
w = – nF(ER – EL) = – nFEcell
where, F is Faraday constant (= 96 500 C mol–1), ER and EL are the reduction
potentials of right electrode and left electrode, respectively, and Ecell is the emf
of the cell. Now, according to thermodynamics, the above work will be equal to
the change in free energy of the cell (i.e. more precisely of the cell reaction).
Hence, we have
G = – nFEcell (8.7.12)
From Eq. (8.7.12), we observe that G and Ecell have opposite signs, i.e. if
G is negative then Ecell is positive and vice versa. Thus, we have the following
criteria about the nature of cell reaction and its emf.

G Nature of cell Sign of Ecell

reaction
Negative Spontaneous Positive
Positive Nonspontaneous Negative
Zero At equilibrium Zero
 Electrochemical Cells 431

From Eq. (8.7.12), we observe that the cell emf is proportional to G/n.
Since G/n is an intensive property, it follows that Ecell is also an intensive
property and hence does not depend upon the size of the cell and the number
of electrons that are associated while writing the half-cell reactions.

Example 8.7.1 Construct the galvanic cell for each of the following reactions and write down the
corresponding expression for the cell potential.
(i) 2Cr(s) + 3Hg2Cl2(s) 2Cr3+(aq) + 6Cl–(aq) + 6Hg(l)
(ii) Ni2+(aq) + H2(g) + 2OH–(aq) Ni(s) + 2H2O(1)
(iii) AgCl(s) + I–(aq) AgI(s) + Cl–(aq)
(iv) Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)
(v) Fe(s) + Cl2(g) FeCl2(aq)
(vi) Ag(s) + 21 Br2(l) AgBr(s)
(vii) Ag+(aq) + Cl–(aq) AgCl(s)
(viii) HgO(s) + H2(g) Hg(l) + H2O(l)

Solution (i) 2Cr(s) + 3Hg2Cl2(s) 2Cr3+(aq) + 6Cl–(aq) + 6Hg(l)

Cr is oxidized to Cr3+ and Hg2+
2 is reduced to Hg. Thus, we would have:

Electrode Reduction reaction

Right Hg2Cl2(s) + 2e– 2Hg(l) + 2Cl–(aq) (i)
3+ –
Left Cr (aq) + 3e Cr(s) (ii)
Multiplying Eq. (i) by 3 and Eq. (ii) by 2 and then subtracting Eq. (ii) from Eq. (i), we
get
2Cr(s) + 3Hg2Cl2(s) 2Cr3+(aq) + 6Hg(1) + 6Cl–(aq)
The required cell would be
Cr | CrCl3(aq) KCl(aq) | Hg2Cl2(s) | Hg(l) | Pt
and the cell potential will be given by
RT
∞ -
Ecell = Ecell ln (aCr3+ )2 (aCl - )6
6F
RT
i.e. ∞ -
Ecell = Ecell ln (aCr3+ ) (aCl - )3
3F

where ∞ = E∞ -
Ecell ∞ 3+
- ECr
Cl | Hg 2 Cl2 | Hg | Cr

(ii) Ni2+(aq) + H2(g) + 2OH–(aq) Ni(s) + 2H2O(1)

2+
Ni is reduced to Ni and hydrogen in alkaline medium is oxidized to H2O. Thus, we
have:

Electrode Reduction reaction

Right Ni (aq) + 2e–
2+
Ni(s) (i)
Left 2H2O(1) + 2e– H2(g) + 2OH–(aq) (ii)
432 A Textbook of Physical Chemistry

Subtracting Eq. (ii) from Eq. (i), we get

Ni2+(aq) + H2(g) + 2OH–(aq) Ni(s) + 2H2O(1)
The required cell would be
Pt | H2(g) | NaOH(aq) Ni2+(aq) | Ni
and the cell potential will be given by
RT 1
∞ -
Ecell = Ecell ln
2F ( f H2 /f ∞)(aOH - )2 (aNi2+ )

where ∞ = E ∞ 2+
Ecell ∞ -
- EOH
Ni | Ni | H 2 | Pt

(iii) AgCl(s) + I–(aq) AgI(s) + Cl–(aq)

The given reaction may be considered to involve the following two half-cell reactions:
AgCl(s) + e– Ag(s) + Cl–(aq)
Ag(s) + I–(aq) AgI(s) + e–
Thus, we have:

Electrode Reduction reaction

Right AgCl(s) + e– Ag(s) + Cl–(aq) (i)
Left AgI(s) + e– Ag(s) + I–(aq) (ii)

Subtracting Eq. (ii) from Eq. (i), we have

AgCl(s) + I–(aq) AgI(s) + Cl–(aq)
The required cell would be
Ag | AgI | KI(aq) KCl(aq) | AgCl | Ag
and the cell potential will be given by

RT a -
∞ -
Ecell = Ecell ln Cl
F aI -

where ∞ = E∞ -
Ecell - EI∞-
Cl | AgCl | Ag | AgI | Ag

(iv) Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)

Zn is oxidized to Zn2+ and H+ is reduced to H2. Thus, we have:

Electrode Reduction reaction

Right 2H+(aq) + 2e– H2(g) (i)
Left Zn2+(aq) + 2e– Zn(s) (ii)

Subtracting Eq. (ii) from Eq. (i), we have

Zn(s) + 2H+(aq) H2(g) + Zn2+(aq)
The cell would be
Zn(s) | Zn2+(aq) H+(aq) | H2(g) | Pt
 Electrochemical Cells 433

and the cell potential will be given by

RT ( f H2 /f ∞)(aZn 2+ )
∞ -
Ecell = Ecell ln
2F (aH+ )2

where ∞ = E∞+
Ecell ∞ 2+
- EZn
H | H 2 | Pt | Zn

(v) Fe(s) + Cl2(g) FeCl2(aq)

2+
Fe is oxidized to Fe and C12 is reduced to Cl–. Thus, we have:

Electrode Reduction reaction

Right Cl2(g) + 2e– 2Cl–(aq) (i)
2+ –
Left Fe (aq) + 2e Fe(s) (ii)

Subtracting Eq. (ii) from Eq. (i), we have

Fe(s) + Cl2(g) Fe2+(aq) + 2Cl–(aq)
The cell would be
Fe | FeCl2(aq) KCl(aq) | Cl2(g) | Pt
and the cell potential is given by

RT (a 2+ )(aCl - )2
∞ -
Ecell = Ecell ln Fe
2F ( f Cl2 /f ∞)

with ∞ = E∞ -
Ecell ∞ 2+
- EFe
Cl | Cl2 | Pt | Fe

1
(vi) Ag(s) + 2
Br2(l) AgBr(s)

Ag in the presence of Br– is changed to AgBr and Br2 is changed to Br–, thus, we have:

Electrode Reduction reaction

Right 1
2
Br2(l) + e– Br–(aq) (i)
–
Left AgBr(s) + e Ag(s) + Br–(aq) (ii)

Subtracting Eq. (ii) from Eq. (i), we have

1
Ag(s) + 2
Br2(l) AgBr(s)
The required cell would be
Ag | AgBr(s) | KBr(aq) | Br2(l) | Pt
and the cell potential is given by

∞ = EBr
Ecell = Ecell ∞- | Br2 | Pt
∞-
- EBr | AgBr | Ag

(vii) Ag+(aq) + Cl–(aq) AgCl(s)

434 A Textbook of Physical Chemistry

This overall reaction may be produced through the following two half-cell reactions:

Electrode Reduction reaction

Right Ag (aq) + e–
+
Ag(s) (i)
Left AgCl(s) + e– Ag(s) + Cl–(aq) (ii)

Subtracting Eq. (ii) from Eq, (i), we have

Ag+(aq) + Cl–(aq) AgCl(s)

The required cell would be

Ag | AgCl(s) | KCl(aq) | NH4NO3 | AgNO3 | Ag

Bridge

and the cell potential is given by

RT 1
∞ -
Ecell = Ecell ln
F (aAg+ )(aCl - )

where ∞ = E∞ +
Ecell ∞-
- ECl
Ag | Ag | AgCl | Ag

(viii) HgO(s) + H2(g) Hg(l) + H2O(l)

This overall reaction may be produced through the following two half-cell reactions:
Electrode Reduction reaction
Right HgO(s) + H2O(1) + 2e– Hg(l) + 2OH–(aq) (i)
–
Left 2H2O(1) + 2e H2(g) + 2OH–(aq) (ii)

Subtracting Eq. (ii) from Eq. (i), we have

HgO(s) + H2(g) Hg(l) + H2O(l)

The required cell would be

Pt |H2(g)| NaOH saturated with HgO |HgO(s)| Hg(l)| Pt

and the cell potential is given by

RT 1
∞ -
Ecell = Ecell ln
2F ( f H 2 /f ∞ )

with ∞ = E∞ -
Ecell ∞ -
- EOH
OH | HgO | Hg | H 2 | Pt

8.8 DETERMINATION OF STANDARD POTENTIALS

Expression of Cell At the very outset, it may be stated that the absolute value for the reduction
Potential potential of any single half-reaction cannot be determined experimentally or
theoretically since the activity of single ionic species, such as hydrogen ion or
 Electrochemical Cells 435

chloride ion, can never be known exactly. However, difference between the two
reduction potentials can be determined by constructing a suitable cell and then
determining its emf experimentally. By definition, the emf of a cell is given by
Ecell = ER - EL (8.8.1)

where ER and EL are the reduction potentials of right and left electrodes,
respectively.
Reference Half-Cell If EL is arbitrarily assigned some value, then the value of ER can be determined
using the expression
ER = Ecell + EL (8.8.2)

In the study of electrochemical cell, the hydrogen-hydrogen ion half-cell

has been adopted as the reference half-cell and its standard potential has been
assigned the value zero at all temperatures. By standard potential of hydrogen-
hydrogen ion half-cell, we mean that the hydrogen ion and hydrogen gas involved
in half-cell
H+(aq) | H2(g) | Pt
are present in their standard states of unit activity and unit fugacity (taken as 1
bar pressure), respectively.
Thus, if we have a cell in which the left half-cell is the standard hydrogen-
hydrogen ion half-cell and the right half-cell constitutes the electrode system
whose potential relative to that of standard hydrogen-hydrogen ion half-cell is
required, then according to Eq. (8.8.2), we have
ER = Ecell + 0
= Ecell
that is, the reduction potential of the given half-cell is numerically equal to the
emf of the cell. Proceeding in this way, the standard potentials of other half-cell
relative to the standard hydrogen-hydrogen ion half-cell can be determined.
Illustrations To illustrate the procedure, we cite below two typical examples of silver-silver
ion and zinc-zinc ion half-cells. If the silver-silver ion half-cell is coupled with
the standard hydrogen-hydrogen ion half-cell (to be kept on left side), we get
a cell
Pt | H2(l bar) | H+(a = 1) Ag+(a = 1) | Ag
The standard emf of the cell is given by
∞ = EAg
Ecell ∞ + | Ag - EH∞ + | H2 | Pt

and its value as determined experimentally is found to be 0.799 1 V. Hence

∞ +
EAg ∞ + E∞+
= Ecell
| Ag H | H 2 | Pt

∞ = 0.799 1 V
= Ecell
436 A Textbook of Physical Chemistry

Taking the example of zinc-zinc ion half-cell, we have

Pt | H2(l bar) | H+(a = 1) Zn2+(a = 1) | Zn
Its emf as determined experimentally is found to be – 0.763 V. Hence
∞ 2+
EZn ∞ + E∞+
= Ecell
| Zn H | H 2 | Pt

∞ = - 0.763 V
= Ecell
Note that the cell emf is negative. It implies that the cell as written above
will not produce spontaneous reaction. In fact, while determining emf of the cell,
the electrode of zinc-zinc ion half-cell will serve as the negative terminal and
Pt electrode of hydrogen-hydrogen ion half-cell as the positive terminal, in
order to get a positive potential of 0.763 V. Since the cell has been written in
the reverse direction (i.e. Pt electrode as the negative terminal and Zn as the
positive terminal), it follows that the emf of the written cell will be – 0.763 V.
Values of Standard Table 8.8.1 records the standard potentials for some of the half-cell reactions
Potentials at 298.15 K along with their respective half-cell assembly.†
Important Comment From the two examples cited above, it may be concluded that if an electrode
of a half-cell with a positive reduction potential is coupled with the standard
hydrogen-hydrogen ion half-cell, it will constitute the positive terminal of the
cell in order to have a spontaneous cell reaction. Similarly, an electrode of a
half-cell with a negative reduction potential will constitute the negative terminal
of the cell so as to get the spontaneous cell reaction. In other words, the nature
of the electrode of half-cell (whether positive or negative) in a cell in which the
other half-cell is the standard hydrogen-hydrogen ion half-cell is determined by
the sign of the reduction potential of the given half-cell.

8.9 SIGNIFICANCE OF STANDARD HALF-CELL POTENTIALS

The standard half-cell potential of the reaction
Cell Potentials
1 n+ 1
M + e- Æ M (8.9.1)
n n
is a measure of reduction tendency of Mn+ to M relative to that of H+ to H2.
The standard potential of the latter reaction, i.e.

H + + e - Æ 21 H 2 (8.9.2)

is taken to be zero (reference level). A positive potential implies that the ion
Mn+ can be more easily reduced to M relative to that of H+ ion to H2. On the
other hand, a negative potential implies that the ion Mn+ is more difficult to
reduce as compared to the H+ ion.

†
The representation of a half-cell corresponds to the right half-cell of the cell diagram
in which the left half-cell is the hydrogen-hydrogen ion half-cell.
 Electrochemical Cells 437

Table 8.8.1 Standard Half-cell Potentials at 298.15 K

Half-cell reaction E°/V Half-cell representation

Li+ + e– Li – 3.045 Li+ | Li
K + + e– K – 2.925 K+ | K
Na+ + e– Na – 2.714 Na+ | Na
Mg2+ + 2e– Mg – 2.37 Mg2+ | Mg
H2 + 2e– 2H– – 2.25 H– | H2 | Pt
Al3+ + 3e– Al – 1.66 A13+ | Al
2H2O + 2e– H2 + 2OH– – 0.828 OH– | H2 | Pt
2+ –
Zn + 2e Zn – 0.763 Zn2+ | Zn
Cd(NH3)42+ + 2e– Cd + 4NH3 – 0.61 Cd(NH3)42+, NH3 | Cd
2CO2 + 2H+ + 2e– H2C2O4 – 0.49 H2C2O4, H+ | CO2 | Pt
Fe2+ + 2e– Fe – 0.44 Fe2+ | Fe
Cr3+ + e– Cr2+ – 0.41 Cr3+, Cr2+ | Pt
2+ –
Cd + 2e Cd – 0.40 Cd2+ | Cd
Ag(CN)2– + e– Ag + 2CN– – 0.31 Ag(CN)–2, CN– | Ag
–
Cu(OH)2 + 2e Cu + 2OH– – 0.224 OH–, Cu(OH)2 | Cu
–
AgI + e Ag + I– – 0.151 I– | AgI | Ag
2+ –
Sn + 2e Sn – 0.136 Sn2+ | Sn
Pb2+ + 2e– Pb – 0.126 Pb2+ | Pb
Cu(NH3)42+ + 2e– Cu + 4NH3 – 0.12 Cu(NH3)42+, NH3 | Cu
Fe3+ + 3e– Fe – 0.036 Fe3+ | Fe
2H+ + 2e– H2 0.000 H+ | H2 | Pt
AgBr + e– Ag + Br– 0.095 Br– | AgBr | Ag
2+ –
Cu + e Cu+ 0.153 Cu2+, Cu+ | Pt
4+ –
Sn + 2e Sn2+ 0.15 Sn4+, Sn2+ | Pt
–
AgCl + e Ag + Cl– 0.222 Cl– | AgCl | Ag
–
Hg2Cl2 + 2e 2Hg + 2Cl– 0.267 6 Cl– | Hg2Cl2 | Hg(Pt)
2+ –
Cu + 2e Cu 0.337 Cu2+ | Cu
Ag(NH3)2+ + e– Ag + 2NH3 0.373 Ag(NH3)+2, NH3 | Ag
O2(g) + 2H2O + 4e– 4OH– 0.401 OH– | O2 | Pt
+ –
Cu + e Cu 0.521 Cu+ | Cu
–
1
I
2 2
+ e I– 0.535 5 I2, I– | Pt
Fe3+ + e– Fe2+ 0.771 Fe3+, Fe2+ | Pt
1
2
Hg22+ + e– Hg 0.789 Hg22+ | Hg(Pt)
Ag+ + e– Ag 0.799 1 Ag+ | Ag
Br2(l) + 2e– 2Br– 1.086 2 Br–, Br2 | Pt
+ –
O2 + 4H + 4e 2H2O 1.229 H+ | O2 | Pt
Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O 1.33 Cr2O 72–, Cr3+, H+ | Pt
1
2
Cl2(g) + e– Cl– 1.359 5 Cl– | C12 | Pt
Ce4+ + e– Ce3+(1 mol dm–3 H2SO4) 1.44 Ce4+, Ce3+ | Pt
3+ –
Au + 3e Au 1.455 Au3+ | Au
MnO4– + 8H+ + 5e– Mn2+ + 4H2O 1.51 MnO–4, Mn2+, H+ | Pt
3+ – 2+
Co + e Co 1.82 Co3+, Co2+ | Pt
438 A Textbook of Physical Chemistry

∞+
If EM is positive, then the cell
M

Pt | H2(l bar) | H+(a = 1) Mn+(a = 1) | M (8.9.3)

will have a positive emf and, therefore, the cell reaction

1 n+ 1 1
M (a = 1) + H 2 (1 bar) Æ M + H + (a = 1)
n 2 n
will be spontaneous and hence Mn+ can be reduced to M by hydrogen gas. On
the other hand, if E ∞ + is negative, the cell emf will also be negative and
M M
hence the cell reaction will not be spontaneous. Thus, Mn+ cannot be reduced
to M by hydrogen gas. In the present case, if the cell as given by Eq. (8.9.3)
is written in the reverse direction, i.e.
M | Mn+(a = 1) H+(a = 1) | H2(l bar) | Pt
the cell will have a positive emf and hence the reaction

1 1 1
M + H + (a = 1) Æ M n + (a = 1) + H 2 (1 bar)
n n 2

will be a spontaneous reaction. Thus, H+ ions can be reduced to hydrogen gas

by the metal M.
Illustration Taking the typical examples of Ag+ | Ag and Zn2+ | Zn half-cells, we find
that

∞ +
EAg = 0.799 V and ∞ 2+
EZn = - 0.763 V
| Ag | Zn

Hence we conclude that under standard conditions, Ag+ ions can be reduced
to Ag by hydrogen gas whereas Zn2+ cannot be reduced. Alternatively, zinc metal
can reduce H+ ions to hydrogen gas whereas silver metal cannot reduce H+ ions.
Active metals such as Zn, Na and Mg have highly negative standard
potentials indicating that their compounds are not reduced by hydrogen but rather
the metal itself can be oxidized by H+ to yield H2. Noble metals such as Cu, Ag
and Au have positive E°s and hence their compounds are readily reduced by H2
gas; the metals themselves are not oxidized in the presence of H+ ions.
Making a Galvanic Table 8.8.1 records the values of standard potentials in increasing order, i.e. at the
Cell top we have the most negative potential with the least tendency for reduction and
at the bottom we have the most positive potential with maximum tendency for
reduction. If a pair of half-cells is coupled to make a cell, the half-cell with more
positive potential will constitute the positive terminal whereas the half-cell with
less positive potential will constitute the negative terminal. In other words, the
half-cell of the higher positive potential (which stands lower in the table) will
constitute the right half-cell with the reduction half-cell reaction and the half-cell
of less positive potential will constitute the left half-cell with the oxidation half-
 Electrochemical Cells 439

cell reaction. Consider, for example, the two half-cells Ni2+ | Ni and Ag+ | Ag.
Their reduction potentials are
∞ 2+ Ni = - 2.250 V
ENi and ∞ +
EAg | Ag = 0.799 V

∞ + | Ag is more positive than ENi

Since EAg ∞ 2+ | Ni , it is obvious that silver
electrode will constitute the positive terminal (i.e. right half-cell) and nickel
electrode as the negative terminal (i.e. left half-cell). Thus the required cell with
the positive emf and hence spontaneous cell reaction would be
Ni | Ni2+(a = 1) Ag+ (a = 1) | Ag

Example 8.9.1 In acid solution the following are true under the standard conditions.
(a) H2S will react with oxygen to give H2O and sulphur.
(b) H2S will not react in the corresponding reaction with selenium and tellurium.
(c) H2Se will react with sulphur giving to H2S and Se but not react with tellurium.
Arrange the hydrides H2O, H2S, H2Se and H2Te in order of their tendency to lose
electrons to form the corresponding elements.
Solution (a) The reaction is
1
H2S + 2
O2 H2O + S
This can be broken into two partial reactions:
Reduction: 2H+ + 1
2
O2+ 2e– H2O

Oxidation: H2S 2H + S + 2e–

+

A cell corresponding to the given reaction can be constructed with the oxidation reaction
at anode and reduction reaction at cathode. The cell potential would be

∞ = ER∞ - EL∞ = E ∞ +
Ecell - EH∞ +
H | O2 | Pt | H2S | S

Since the cell reaction is spontaneous, it follows that

EH∞ + | O2 | Pt
> EH∞ + | H2S | S

(b) Proceeding similarly as in the part (a), we have

EH∞ + | H2S | S
> EH∞ + | H and EH∞ + > EH∞ +
2 Se | Se | H2S | S | H 2 Te | Te

(c) Similarly in this case, we have

EH∞ + | H2S | S
> EH∞ + | H 2 Se | Se
and EH∞ + | H 2 Se | Se
> EH∞ + | H 2 Te | Te

Arranging the above reduction potentials in the decreasing order, we get

EH∞ + | O2 | Pt
> EH∞ + | H2S | S
> EH∞ + | H 2 Se | Se
> EH∞ + | H 2 Te | Te

The above order implies that the tendency for the reduction reaction
1
2H + + X n + 2e - Æ H 2 X
n
440 A Textbook of Physical Chemistry

to take place is the greatest for oxygen and least for Te. The tendency for the reverse
reaction, i.e. the oxidation of hydride to the corresponding element will be greatest for
H2Te and least for H2O.

Example 8.9.2 Answer whether under standard conditions the following reactions are possible or not.
(i) Will Fe reduce Fe3+ to Fe2+?
(ii) Will the permanganate ion MnO4– liberate O2 from water in the presence of an
acid?
(iii) Will O2 oxidize gold to Au(CN)2– in the presence of CN– and OH– ions?
(iv) Would you use silver spoon to stir a solution of Cu(NO3)2?
(v) Will ceric sulphate react with KI?
(vi) Will lead react with AgNO3 solution?
(vii) Will permanganate ions in acidic medium oxidize oxalic acid?
(viii) Will dichromate ions in acidic medium oxidize Fe2+ to Fe3+?
(ix) Will Fe3+ ions be reduced to Fe2+ by Sn2+ ions?
(x) Will Fe3+ ions in acidic medium oxidize diphenylbenzidine and N-phenylanthranilic
acid indicators?

Solution (i) The reactions would be

Reduction Fe3+ + e– Fe2+
Oxidation Fe Fe2+ + 2e–
The cell giving these half-cell reactions would be
Fe | Fe2+ Fe3+, Fe2+ | Pt

with ∞ = E ∞ 3+ 2+
Ecell ∞ 2+
- EFe = 0.771 V - (- 0.440 V) = 1.211 V
Fe , Fe | Pt | Fe

º is positive, the reduction of Fe3+ to Fe2+ by Fe is possible,

Since E cell
(ii) The reactions would be
Reduction MnO4– + 8H+ + 5e– Mn2+ + 4H2O

Oxidation H2O 2H+ + 1

2
O2 + 2e–

The cell giving these half-cell reactions would be

Pt | O2 | H+, H2O MnO–4, Mn2+, H+ | Pt

with ∞ = E ∞ - 2+ +
Ecell - EH∞ + = 1.510 V - 1.223 V = 0.287 V
MnO , Mn , H
4 | Pt | O2 | Pt

The reaction is possible.

(iii) The reactions would be
Reduction O2 + 2H2O + 4e– 4OH–
Oxidation Au + 2CN– Au(CN)–2 + e–
The cell giving these half-cell reactions would be

Au | Au(CN)–2, CN– OH– | O2 | Pt

 Electrochemical Cells 441

with ∞ = E∞ -
Ecell ∞
- EAu(CN) - = 0.401 V - (- 0.601 V) = 1.002 V
OH | O2 | Pt , CN -2 | Au

The reaction is possible.

(iv) The reactions would be
Reduction Cu2+ + 2e– Cu
Oxidation Ag Ag+ + e–
The cell giving these half-cell reactions would be
Ag | Ag+ Cu2+ | Cu

with ∞ = E ∞ 2+
Ecell ∞ +
- EAg = 0.337 V - 0.799 = - 0.462 V
Cu | Cu | Ag

Since E°cell is negative, the cell reaction will not be spontaneous. Hence, we can use the
silver spoon to stir a solution of Cu(NO3)2.
(v) The reactions would be
Reduction Ce4+ + e– Ce3+

Oxidation I– 1
2
I2 + e–

The cell giving these half-cell reactions would be

Pt | I2 | I– Ce4+, Ce3+ | Pt

with ∞ = E ∞ 4+ 3+
Ecell - EI∞- = 1.44 V - 0.536 V = 0.904 V
Ce , Ce | Pt | I 2 | Pt

The reaction is possible.

(vi) The reactions would be
Reduction Ag+ + e– Ag
2+
Oxidation Pb Pb + 2e–
The cell giving these half-cell reactions would be
Pb | Pb2+ Ag+ | Ag

with ∞ = E∞ +
Ecell ∞ 2+
- EPb = 0.799 V - (- 0.126 V) = 0.925 V
Ag | Ag | Pb

The reaction is possible.

(vii) The reactions would be
Reduction MnO–4 + 8H+ + 5e– Mn2+ + 4H2O
Oxidation COOH CO2 + 2H+ + 2e–

COOH
The cell giving these half-cell reactions would be
Pt | CO2 | oxalic acid, H+ MnO–4, Mn2+, H+ | Pt
442 A Textbook of Physical Chemistry

with ∞ = E ∞ - 2+ +
Ecell ∞
- Eoxalic
MnO , Mn , H4 | Pt acid, H + | CO2 | Pt

= 1.51 V - (- 0.49 V) = 2.00 V

The reaction is possible.

(viii) The reactions would be
Reduction Cr2O72– + 14H+ + 6e– 2Cr3+ + 7H2O
Oxidation Fe2+ Fe3+ + e–
The cell giving these half-cell reactions would be
Pt | Fe2+, Fe3+ Cr2O72–, Cr3+, H+ | Pt

with ∞ = E∞
Ecell ∞ 3+ 2+
- EFe
Cr 2
O27 - , Cr 3+ , H + | Pt , Fe | Pt

= 1.33 V - 0.771 V = 0.559 V

The reaction is possible.

(ix) The reactions would be
Reduction Fe3+ + e– Fe2+
Oxidation Sn2+ Sn4+ + 2e–
The cell giving these half-cell reactions would be
Pt | Sn4+, Sn2+ Fe3+, Fe2+ | Pt

with ∞ = E ∞ 3+ 2+
Ecell ∞ 4+ 2+
- ESn
Fe , Fe | Pt , Sn | Pt
= 0.771 V - 0.150 V = 0.621 V

The reaction is possible.

(x) The reactions for the diphenylbenzidine indicator would be
Reduction Fe3+ + e– Fe2+
Oxidation Diphenylbenzidine Diphenylbenzidine violet + 2H+ + 2e–
(DPB) (DPBV)
The cell producing these half-cell reactions would be
Pt | DPB, DPBV, H+ Fe3+, Fe2+ | Pt

with ∞ = E ∞ 3+ 2+
Ecell ∞
- EDPB,
Fe , Fe | Pt DPBV, H + | Pt
= 0.771 V - 0.76 V = 0.011 V
The reaction is possible.
The reactions for the N-phenylanthranilic acid would be
Reduction Fe3+ + e– Fe2+
Oxidation Reduced from of indicator Oxidized form of
indicator + 4H+ + 4e–
The cell producing these half-cell reactions would be
Pt | Reduced and oxidized forms of indicator, H+ Fe2+, Fe3+ | Pt
 Electrochemical Cells 443

with ∞ = E ∞ 3+ 2+
Ecell ∞
- Eindicator
Fe , Fe | Pt
= 0.771 V - 1.080 V = - 0.309 V

The reaction is not possible.

Example 8.9.3 Ascertain, with a little calculation, whether or not each of the following reactions will
proceed to the forward or backward direction at 25 °C when all concentrations and
pressures are unity.
(a) 2Cr + 3Cu2+ 2Cr3+ + 3Cu (b) Zn + Mg2+ Zn2+ + Mg
(c) Fe + Cl2(g) Fe2+ + 2Cl– 2+
(d) 2Fe + Cl2(g) 2Fe3+ + 2Cl–
(e) 2Ag + Cu2+ 2Ag+ + Cu 2+
(f) 2Ag + Cu + 2Cl –
2AgCl(s) + Cu

Solution (a) Cr is oxidized to Cr3+ and Cu2+ is reduced to Cu, the cell giving this reaction would
be

Cr | Cr3+ Cu2+ | Cu

with ∞ = E ∞ 2+
Ecell ∞ 3+
- ECr = 0.337 V - (- 0.774) = 1.111 V
Cu | Cu | Cr

Since E° is positive, the given reaction will proceed in the forward direction.
We can proceed similarly for other reactions. The given reaction, the corresponding
cell, Eºcell and conclusion regarding whether the reaction proceeds in the forward or
backward direction are tabulated below:

Reaction Cell Eºcell Direction

V of reaction

(b) Zn + Mg2+ Zn2+ + Mg Zn | Zn2+ Mg2+ | Mg – 2.37 – ( – 0.763) Backward

2+ – 2+ –
(c) Fe + Cl2(g) Fe + 2Cl Fe | Fe Cl | C12 | Pt 1.359 5 – ( – 0.440) Forward
2+ 3+ – 2+ 3+ –
(d) 2Fe + Cl2(g) 2Fe + 2Cl Pt | Fe , Fe Cl | C12 | Pt 1.359 5 – 0.771 Forward
2+ + + 2+
(e) 2Ag + Cu 2Ag + Cu Ag | Ag Cu | Cu 0.337 – 0.799 1 Backward
2+ – – 2+
(f) 2Ag + Cu + 2Cl 2AgCl(s) + Cu Ag | AgCl | Cl Cu | Cu 0.337 – 0.222 Forward

Example 8.9.4 (a) Which of the following half-reactions will oxidize Cu(s) to Cu2+ under standard
conditions?
(i) Cl2(g) to Cl–; (ii) MnO4–(aq) to Mn2+(aq); (iii) Ag+ to Ag.
(b) Which of the following half-reactions will reduce Fe3+ to Fe2+ under standard
conditions?
(i) Sn2+ to Sn4+; (ii) Mn2+(aq) to MnO4– (aq); (iii) Pb(s) to Pb2+(aq)

Solution (a) Since Cu is to be oxidized to Cu2+, it will constitute the left electrode. Each of the
given reactions with which this oxidation reaction is to be carried out will constitute the
right electrode. Thus, we have
444 A Textbook of Physical Chemistry

(i) Right electrode Cl2 + 2e– 2Cl–

Left electrode Cu Cu2+ + 2e–
The cell reaction would be Cl2 + Cu Cu2+ + 2Cl–

and its emf would be ∞ = E∞ -

Ecell ∞ 2+
- ECu
Cl | Cl2 | Pt | Cu

= 1.359 5 V - 0.337 V = 1.022 5 V

Since Eºcell is positive, Cl2 can oxidize Cu to Cu2+.

(ii) Right electrode 2MnO4– + 16H+ + 10e– 2Mn2+ + 8H2O
Left electrode 5Cu 5Cu2+ + 10e–
The cell reaction would be 2MnO4– + 16H+ + 5Cu 2Mn2+ + 8H2O + 5Cu2+

and its emf would be ∞ = E ∞ - 2+ +

Ecell ∞ 2+
- ECu
MnO , Mn , H
4 | Pt | Cu

= 1.510 V - 0.337 V = 1.173 V

Thus oxidation of Cu to Cu2+ is possible.

(iii) Right electrode 2Ag+ + 2e– 2Ag
Left electrode Cu Cu2+ + 2e–
The cell reaction would be Cu + 2Ag+ 2Ag + Cu2+

and its emf would be ∞ = E∞ +

Ecell ∞ 2+
- ECu
Ag | Ag | Cu

= 0.779 1 V - 0.337 V = 0.442 1 V

Thus oxidation of Cu to Cu2+ is possible.

(b) In this case, we would have
(i) Right electrode 2Fe3+ + 2e– 2Fe2+
Left electrode Sn2+ Sn4+ + 2e–
The cell reaction would be 2Fe3+ + Sn2+ Sn4+ + 2Fe2+

and its emf would be ∞ = E ∞ 3+ 2+

Ecell ∞ 4+ 2+
- ESn
Fe , Fe | Pt , Sn | Pt
= 0.771 V - 0.150 V = 0.621 V

º is positive, Sn2+ can reduce Fe3+ to Fe2+.

Since E cell
(ii) Right electrode 5Fe3+ + 5e– 5Fe2+
Left electrode Mn2+ + 4H2O MnO4– + 8H+ + 5e–
The cell reaction would Mn2+ + 4H2O + 5Fe3+ MnO–4 + 8H+ + 5Fe2+
 Electrochemical Cells 445

and its emf would be ∞ = E ∞ 3+ 2+

Ecell ∞ - 2+ +
- EMnO
Fe , Fe | Pt , Mn , H
4 | Pt

= 0.771 V - 1.51 V = - 0.739 V

Thus, reduction of Fe3+ to Fe2+ by Mn2+ ions is not possible.

(iii) Right electrode 2Fe3+ + 2e– 2Fe2+
Left electrode Pb Pb2+ + 2e–
The cell reaction would be Pb + 2Fe3+ Pb2+ + 2Fe2+

and its emf would be ∞ = E ∞ 3+ 2+

Ecell ∞ 2+
- EPb
Fe , Fe | Pt | Pb
= 0.771 V - (- 0.126 V) = 0.897 V

Thus reduction of Fe3+ to Fe2+ by Pb is possible.

Example 8.9.5 The four elements W, X, Y, Z form diatomic molecules and also form singly charged
negative ions. The following observations are made in a series of experiments:
(a) 2X– + Y2 2Y– + X2 (b) 2W– + Y2 No reaction
(c) 2Z– + X2 2X– + Z2
Use these observations to write equation for each half-reaction. Arrange them in the
decreasing reduction potential series. Which ion is the strongest reducing agent? Which
molecule is the strongest oxidizing agent?
Solution (a) The given reaction is
2X– + Y2 2Y– + X2
Here Y2 is reduced to Y– and X– is oxidized to X2, therefore, the half-reactions would
be
Right electrode Y2 + 2e– 2Y–
Left electrode 2X– X2 + 2e–
The cell emf would be Ecell = EY - | Y2 | Pt
- EX - | X 2 | Pt

Since the reaction is feasible, Ecell will be positive. This yields

EY - | Y2 | Pt
> EX - | X 2 | Pt
(1)

(b) We have
2W– + Y2 No reaction
Had the reaction occurred, then Y2 would have been reduced to Y– and W– would have
been oxidized to W2. The cell emf for these half-reaction would be
Ecell = EY – | Y2 | Pt
– EW – | W2 | Pt

Since the reaction is not possible, it means Ecell is negative and thus
EW – | W2 | Pt
> EY – | Y2 | Pt
(2)

(c) Here, we have

2Z– + X2 2X– + Z2
446 A Textbook of Physical Chemistry

X2 is reduced to X – and Z – is oxidized to Z2. The half-cell reactions are

Right electrode X2 + 2e– 2X–
Left electrode 2Z– Z2 + 2e–

The cell emf would be Ecell = EX – | X 2 | Pt

– EZ – | Z 2 | Pt

Since the reaction is possible, Ecell will be positive and hence

EX – | X 2 | Pt
> EZ – | Z 2 | Pt
(3)

Combining Eqs (1), (2) and (3), we get

EW – | W2 | Pt
> EY – | Y2 | Pt
> EX – | X 2 | Pt
> EZ – | Z 2 | Pt

Out of these, W2 will have the greatest tendency for reduction and, therefore, will be the
strongest oxidizing agent. Z2 will have the least tendency for reduction or Z– will show
the greatest tendency for oxidation. Thus, Z– is the strongest reducing agent.

Example 8.9.6 Sometimes a species in a given oxidation state undergoes self-oxidation reduction reaction
(disproportionation) in aqueous medium to give products of lower and higher oxidation
states. For example, when Br2 is added in an alkaline solution ([OH–] = 1 mol dm–3), it
disproportionates to give bromide and hypobromide ions. Rationalize the above results
from the standard potentials given below:
(i) 1
2
Br2 + e– Br– E º = 1.07 V
– – 1 –
(ii) BrO + H2O + e 2
Br2 + 2OH E º = 0.45 V
(iii) 2BrO– + 2H2O + 4e– 2Br– + 4OH– E º = 0.71 V
(iv) BrO3– + 2H2O + 4e– BrO– + 4OH– E º = 0.54 V
The above data may be presented in a condensed form as

What would be the overall reaction of Br2 in an alkaline solution?

Solution The self-reduction oxidation reactions of Br2 are

Reduction 1
2
Br2 + e– Br– (1)

Oxidation 1
2
Br2 + 2OH– BrO– + H2O + e– (2)

The cell producing the above two half-cell reactions would be

Pt | Br2, BrO–, OH– Br–, Br2 | Pt

with the cell potential given as

∞ = ER∞ - EL∞ = 1.07 V - 0.45 V = 0.62 V

Ecell
 Electrochemical Cells 447

Since the cell potential is positive, it is obvious that Br2 can be converted to Br– and
BrO– simultaneously. Hence, Br2 disproportionates in the alkaline solution to give Br–
and BrO–.
Similarly, the self-reduction oxidation reactions of BrO– are
Reduction 2BrO– + 2H2O + 4e– 2Br– + 4OH– (3)
Oxidation BrO– + 4OH– BrO3– + 2H2O + 4e– (4)
Thus, a cell producing the above two half-cell reactions would be
Pt | BrO–, BrO–3, OH– BrO–, Br–, OH– | Pt
with the cell potential given as

∞ = ER∞ - EL∞
Ecell 0.71 V - 0.54 V = 0.17 V

Since the cell potential is positive, it is obvious that BrO– can be converted to Br– and
BrO3– simultaneously. Hence BrO– disproportionates in alkaline solution to give Br– and
BrO3–.
The overall reaction of Br2 in an alkaline solution may be obtained by adding the
two disproportionate reactions.
Disproportionate reaction of Br2 Adding Eqs (1) and (2), we get
–
2OH + Br2 Br + BrO– + H2O
–
(5)
Disproportionate reaction of BrO– Adding Eqs (3) and (4), we get
3BrO– 2Br– + BrO3– (6)
Hence multiplying Eq. (5) by 3 and then adding it to Eq. (6), we have
6OH– + 3Br2 5Br– + BrO3– + 3H2O

Example 8.9.7 Determine the cell reaction and Ecell for each of the following cells at 25 °C. Assume
activity and fugacity equal to molar concentration and pressure (bar), respectively.
(i) Mg | MgI2(0.1 mol dm–3) | I2(s) | Pt
(ii) Ag | AgBr(s) | HBr(0.02 mol dm–3) | H2(0.5 bar) | Pt
(iii) Fe | Fe(NO3)2 (0.05 mol dm–3) Cu(NO3)2(0.01 mol dm–3) | Cu
(iv) Pt | H2(g, 0.127 bar) | H+Cl– | H2(g, 6.43 bar) | Pt
(v) Pt | Hg(1) | Hg2Cl2(s) | KC1(0.1 mol dm–3) Zn2+(0.733 mol dm–3) | Zn
Solution Throughout this chapter c° represents unit concentration and p° represents unit pressure,
(i) Mg | MgI2(0.1 mol dm–3) | I2(s) | Pt
We have

Electrode Reduction reaction Half-cell potential

RT
Right I2(s) + 2e– 2I–(aq) EI - | I2
= EI∞- | I2
- ln ([I - ]/c∞)2
2F
RT 1
Left Mg2+(aq) + 2e– Mg(s) EMg2+ ∞ 2+
= EMg - ln
| Mg | Mg
2F ([Mg2+ ]/c∞)
448 A Textbook of Physical Chemistry

Since
cell reaction = reduction reaction at (right – left) electrode
and Ecell = ER – EL
we have
Mg(s) + I2(s) Mg2+(aq) + 2I–(aq)

RT ÈÊ [Mg2+ ] ˆ Ê [I - ] ˆ 2
˘
Ecell = (EI∞- ∞ 2+
- EMg )- ln ÍÁ ˜Á ˜ ˙
| I2 | Mg
2F ÍÎË c∞ ¯ Ë c∞ ¯ ˙˚

Substituting the data, we get

Ê 0.059 15 V ˆ
Ecell = {0.535 V - (- 2.363 0 V)} - Á ˜¯ log (0.1 ¥ 0.2 )
2
Ë 2
= 2.898 5 V + 0.070 8 V = 2.969 V

(ii) Ag | AgBr(s) | HBr(0.02 mol dm–3) | H2(0.5 bar) | Pt

We have

Electrode Reduction reaction

Right H (aq) + e–
+ 1
2
H2(g)
–
Left AgBr(s) + e Ag(s) + Br–(aq)

The cell reaction (reduction reaction at right electrode – reduction reaction at left electrode)
is
Ag(s) + Br–(aq) + H+(aq) AgBr(s) + 1
2
H2(g)

RT ( pH2 /p∞)1/2
Hence Ecell = (EH∞ + ∞-
- EBr )- ln
| H 2 | Pt | AgBr | Ag
F {[H + ]/c∞}{[Br - ]/c∞}

Substituting the data, we get

Ê 0.51/2 ˆ
Ecell = (0.0 V - 0.071 3 V) - (0.059 15 V) log Á
Ë 0.02 ¥ 0.02 ˜¯
= - 0.071 3 V - 0.192 1 V = - 0.263 4 V

(iii) Fe | Fe(NO3)2(0.05 mol dm–3) Cu(NO3)2(0.01 mol dm–3) | Cu

We have

Electrode Reduction reaction

Right Cu2+(aq) + 2e– Cu(s)
Left Fe2+(aq) + 2e– Fe(s)
The cell reaction is
Fe(s) + Cu2+(aq) Fe2+(aq) + Cu(s)
 Electrochemical Cells 449

Ê 0.059 15 V ˆ Ï [Fe 2+ ]/c∞ ¸

Hence ∞ 2+
Ecell = (ECu ∞ 2+
- EFe
)-Á ˜ log Ì ˝
| Cu Ë | Fe
2 ¯ Ó[Cu ]/c∞ ˛
2+

Ê 0.059 15 V ˆ Ê 0.05 ˆ
= {0.337 V - ( - 0.441 V)} - Á ˜¯ log ÁË ˜
Ë 2 0.01¯
= 0.778 V - 0.020 7 V = 0.757 3 V

(iv) Pt | H2(g) (0.127 bar) | H+Cl– | H2(g) (6.43 bar) | Pt

We have

Electrode Reduction reaction

Right H+(aq) + e– 1
2
H2(g)R

Left H+(aq) + e– 1
2
H2(g)L

The cell reaction is

1
H (g)L
2 2
Æ 21 H 2 (g)R

1/2
Ê 0.059 15 V ˆ ÔÏ pH2 (R) /p∞) Ô¸
Hence Ecell =-Á ˜¯ log Ì ˝
Ë 1 ÓÔ pH2 (L) /p∞ Ô˛
Ê 0.059 15 V ˆ ÔÏ pH2 (R) /p∞) Ô¸
=-Á ˜¯ log Ì ˝
Ë 2 ÓÔ pH2 (L) /p∞ ˛Ô

Substituting the given data, we get

Ê 0.059 15 V ˆ Ê 6.43 ˆ
Ecell = - Á ˜¯ log ÁË ˜
Ë 2 0.127 ¯
= - (0.029 57 V) (1.704 4) = - 0.503 7 V

(v) Pt | Hg(l) | Hg2Cl2(s) | KC1(0.1 mol dm–3) Zn2+(0.732 mol dm–3) | Zn

We have

Electrode Reduction reaction

Right Zn (aq) + 2e–
2+
Zn(s)
Left Hg2Cl2(s) + 2e– 2Hg(l) + 2Cl–(aq)

The cell reaction is

2Hg(l) + 2Cl–(aq) + Zn2+(aq) Hg2Cl2(s) + Zn(s)

RT 1
Hence ∞ 2+
Ecell = (EZn ∞-
- ECl )- ln -
| Zn | Hg 2 Cl 2 | Hg
2F {[Cl ]/c∞} {[Zn 2+ ]/c∞}
2

RT
∞ 2+
= (EZn | Zn
∞-
- ECl | Hg 2 Cl 2 | Hg
)+ ln ({[Cl - ]/c∞}2 {[Zn 2+ ]/c∞})
2F
450 A Textbook of Physical Chemistry

Substituting the data, we get

Ê 0.059 15 V ˆ
Ecell = (- 0.763 V - 0.337 V) + Á ˜¯ log (0.1 ¥ 0.733)
2
Ë 2
= - 1.1 V - 0.063 V = - 1.163 V

8.10 INFLUENCE OF IONIC ACTIVITY ON REDUCTION POTENTIAL

The reduction potential for the reaction
Mn+ + ne– M
as given by the Nernst equation is

RT Ê 1 ˆ
∞ n+
E1 = EM - ln Á ˜ (8.10.1)
|M
nF Ë aMn + ¯

From Eq. (8.10.1), it follows that the reduction potential EMn+ | M depends
on the activity of Mn+; it increases as the activity of Mn+ is increased. If the
activity of Mn+ is decreased to one-tenth of its original activity, then the reduction
potential becomes

RT Ê 1 ˆ
∞ n+
E2 = E M - ln Á ˜ (8.10.2)
|M
nF Ë 0.1 aMn + ¯

The resulting change in potential is given by

RT Ê 1 ˆ RT Ê 1 ˆ
E2 - E1 = - ln Á ˜ + ln Á ˜ (8.10.3)
nF Ë 0.1 aMn + ¯ nF Ë aMn + ¯
RT 2.303 RT
=- ln 10 = -
nF nF

At 298 K, we have
(0.0592 V)
E2 - E1 = - (8.10.4)
n

Thus every ten-fold decrease in the activity of cation produces a decrease of

(0.059 2/n) volt of the reduction potential, where n is the valence of the cation.
For univalent cations n is 1, and hence reduction potential decreases by a factor
of 0.059 2 V. For bivalent cations n is 2, and hence reduction potential decreases
by a factor of (0.059 2/2) V, i.e. 0.029 6 V. The magnitude of reduction potential
will change by the same factor (= (0.059 2 V)/n) for every ten-fold change in
the activity of cation. For a hundred-fold change in the activity; the change
of potential will be (2 × 0.059 2 V)/n) volt and for a thousand-fold change in
activity, the potential will change by a factor of (3 × 0.059 2 V)/n) volt.
The change in reduction potential on dilution is determined by the ratio
of activities of ions before and after dilution. Thus, if two solutions containing
 Electrochemical Cells 451

different amounts of a cation are diluted by the same factor (say, 10 times), the
change in potential will be the same for both cases. For example, a change of
concentration of a cation from 1.0 mol dm–3 to 0.1 mol dm–3 will produce the
same change in potential as a decrease from 10–6 mol dm–3 to 10–7 mol dm–3
since the ratio of the two concentrations is the same, viz., 10 to 1.
Molecular Formula The mercurous chloride is written as Hg2Cl2 instead of HgCl and hence the
of Mercurous Salts mercurous cation is represented as Hg22+. One argument for writing the double
formula for mercurous ion comes from the effect of dilution on the reduction
potential of the half-cell reaction
Mercurous ion + ne– Mercury
It is found that the reduction potential changes by a factor of 0.029 6 V for a
ten-fold change in concentration of mercurous ions. This result indicates that
for mercurous ions n is 2, so that they carry two unit charges per ion and hence
its formula must be written as Hg22+ and not as Hg+.
The above principle can also be extended to other ions. For example,
cuprous iodide is written as Cu2I2 and not as CuI. This can be derived from
the change of reduction potential with dilution for the reaction
Cuprous ion + ne– Copper

Example 8.10.1 The emf of the cell

Hg | Mercurous nitrate (0.01 M) Mercurous nitrate (0.1 M) | Hg
is found to be 0.029 5 V at 25 °C. Determine the molecular formula of mercurous
nitrate.

Solution For the given cell, we have

Electrode Reduction reaction Reduction potential

RT 1
Right Hg nn+ + ne– nHg ER = ER∞ - ln (i)
nF ([Hg nn+ ]R /c∞)

RT 1
Left Hg nn+ + ne– nHg EL = EL∞ - ln (ii)
nF ([Hg nn+ ]L /c∞)

Since E ºcell = ERº – E ºL, on subtracting Eq. (ii) from Eq. (i), we get

RT ([Hg nn+ ]R /c∞) 0.059 15 V Ê 0.1 ˆ

Ecell = ER - EL = log Á
Ë 0.01˜¯
ln =
nF ([Hg nn+ ]L /c∞) n
0.059 15 V
= = 0.029 5 V
n

Thus n=2
Hence, the molecular formula is Hg2(NO3)2.
452 A Textbook of Physical Chemistry

8.11 EFFECT OF COMPLEX FORMATION ON REDUCTION POTENTIAL

In general, a reduction reaction may be represented as

oxidized form + ne– reduced form (8.11.1)

The corresponding Nernst equation is

RT Ê [reduced form]/ c∞ ˆ
E = E∞ - ln Á
Ë [oxidized form]/ c∞ ˜¯
(8.11.2)
nF

Thus, if the concentration of the oxidized form is lowered by some means

keeping the concentration of the reduced form unchanged, a decrease in the
reduction potential will be observed. On the other hand, if the concentration of
the reduced form is lowered, an increase in the reduction potential will be
observed.
The number of electrons n involved in Eq. (8.11.1) can be determined by
plotting a graph between E and ln ([reduced form]/[oxidized form]). According
to Eq. (8.11.2), a straight line will be obtained with a slope equal to – RT/nF.
Hence knowing the slope and temperature T, the value of n can be determined.
Substance which forms the soluble complex (or precipitate) with the
oxidized member of the couple (Eq. 8.11.1) will decrease the effective
concentration of the oxidized form. Consequently, the reduction potential
of the system is lowered. For example, if some CN– is added to the half-cell
Ag+ | Ag, its reduction potential is decreased owing to the formation of complex
between Ag+ and CN– ions. Thus, a metal which otherwise behaves as a noble
metal may be converted into an active metal by lowering its reduction potential
by some means. Hence whether a metal is a noble metal or an active metal,
it all depends upon its environments. For example, ordinarily silver is a
noble metal but in the presence of I–, S2– and CN– ions, it becomes an active
metal.
In an analogous way, if the concentration of the reduced form of the couple
is lowered, the potential of the electrode is increased. If the reduced form is
a metal, the most useful method of lowering its activity is to form an alloy of
the metal with another metal. In amalgam electrodes, mercury is used for this
purpose.

Example 8.11.1 A cell consists of a Pt electrode immersed in the redox system Ax+ A(x+n)+ + ne– is
combined with a saturated calomel electrode (right-side electrode). From the following
data at 303 K, determine the value of n.
Per cent of reduced form 24.4 48.8 73.2 84.5
emf/V 0.101 0.116 0.129 0.139
The standard potential of the calomel electrode at 303 K is 0.238 V.
Solution For the given half-cells, we have

2.303 RT/F = (2.303) (8.314 J K –1 mol –1 ) (303 K)/(96 500 C mol –1 )

= 0.060 1 V
 Electrochemical Cells 453

Electrode Reduction reaction Expression of reduction potential

0.060 1 V
Right Hg2Cl2 + 2e– 2Hg + 2Cl– ER = ER∞ - log ([Cl - ]/c∞)2 (i)
2

0.060 1 V ([A x + ]/c∞)

Left A(x+n)+ + ne– Ax+ EL = EL∞ - log (ii)
n ([A(x +n)+ ]/c∞)

Subtracting Eq. (ii) from Eq. (i), we get

Ecell = ER - EL
Ê 0.060 1 V ˆ
= Á ER∞ - log ([Cl - ]/c∞)2 ˜
Ë 2 ¯
Ê 0.060 1 V ([A x + ]/c∞) ˆ
- Á EL∞ - log
Ë n ([A(x +n)+ ]/c∞) ˜¯

Ê 0.060 1 V ˆ 0.060 1 V ([A x + ]/c∞)

or Ecell = Á ER∞ - EL∞ - log ([Cl - ]/c∞)2 ˜ + log
Ë 2 ¯ n ([A(x +n)+ ]/c∞)
0.060 1 V ([reduced form]/ c∞)
or Ecell = constant + log
n ([oxidized form]/ c∞)
If a plot is made between Ecell and log ([reduced]/[oxidized]) a straight line will
be obtained. The slope of the line will be equal to 0.060 1 V/n and hence the value of
n can be calculated.
From the given data, we have

Per cent reduced form 24.0 48.8 73.2 85.4

Ê [reduced] ˆ
log Á
Ë [oxidized] ˜¯
– 0.491 1 – 0.020 9 0.436 4 0.767 1

Ecell/V 0.101 0.116 0.129 0.139

A plot between Ecell and log ([reduced]/[oxidized]) is shown in Fig. 8.11.1

Fig. 8.11.1 Graph

between Ecell and log
([reduced]/[oxidized])
454 A Textbook of Physical Chemistry

The slope of the line was found to be 0.030 V. Thus

0.060 1 V 0.060 1
= 0.030 0 V which gives n = =2
n 0.0300

8.12 RELATION BETWEEN METAL-METAL ION HALF-CELL AND THE

CORRESPONDING METAL-INSOLUBLE SALT-ANION HALF-CELL
Consider a silver electrode dipped into a solution of silver nitrate. The potential
of the electrode as given by the Nernst equation is

RT Ê 1 ˆ
EAg+ | Ag
∞ +
= EAg | Ag - ln Á ˜ (8.12.1)
F Ë aAg+ ¯

with ∞ +
EAg | Ag = 0.799 V.

If now NaCl is added, the following equilibrium will be established:

AgCl(s) Ag+(aq) + Cl–(aq)
with its standard solubility product K sº as

Ks∞ = (aAg+ )(aCl - )

Multiplying and dividing the term within parantheses in Eq. (8.12.1) by

aCl–, we get

RT Ê aCl - ˆ
EAg+ | Ag
∞ +
= EAg | Ag - ln Á ˜
F Ë aAg+ aCl - ¯

RT Ê aCl - ˆ
∞ +
= EAg | Ag - ln Á ˜
F Ë Ks∞ (AgCl) ¯

Ê ∞ + RT ˆ RT
or EAg+ = Á EAg + ln Ks∞ (AgCl)˜ - ln aCl - (8.12.2)
| Ag Ë | Ag
F ¯ F

Now the electrode can also be treated as Cl– | AgCl | Ag since part of
AgCl will deposit on solid Ag. Writing the reaction for this electrode, we have
AgCl(s) + e– Ag(s) + Cl–(aq)
The corresponding Nernst equation gives
RT
ECl - ∞-
= ECl - ln aCl - (8.12.3)
| AgCl | Ag | AgCl | Ag
F

Equations (8.12.2) and (8.12.3) must be identical (i.e. E Ag + | Ag

= ECl– |AgCl | Ag) and hence on comparing these two equations, we get
 Electrochemical Cells 455

RT
∞-
ECl ∞ +
= EAg + ln Ks∞ (AgCl)
| AgCl | Ag | Ag F
2.303 RT
or ∞-
ECl ∞ +
= EAg - pKs∞ (AgCl) (8.12.4)
| AgCl | Ag | Ag
F
where pK sº (AgCl) = – log K sº (AgCl)
Alternative Equation (8.12.4) can also be derived by the following two methods.
Procedures
(i) Consider the cell
Ag | saturated solution of AgCl | AgCl | Ag
Its cell reaction is
AgCl(s) Ag+(aq) + Cl–(aq)
and the cell-potential is
RT
∞-
E = (ECl ∞ +
- EAg )- ln (aAg+ )(aCl - )
| AgCl | Ag | Ag
F
For the reaction at equilibrium, we will have E = 0 (see Section 8.18) and thus
RT
∞-
ECl ∞ +
- EAg = ln (aAg+ )(aCl - )
| AgCl | Ag | Ag F
RT
or ∞-
ECl ∞ +
= EAg + {ln Ks∞ (AgCl)}
| AgCl | Ag | Ag
F
(ii) We have

AgCl(s) + e - Æ Ag(s) + Cl - (aq); DG1∞ = - FECl

∞-
| AgCl | Ag
(8.12.5)

Ag+ (aq) + e - Æ Ag(s); DG2∞ = - FEAg

∞ + | Ag (8.12.6)

Subtracting Eq. (8.12.6) from Eq. (8.12.5), we get

AgCl(s) Æ Ag + (aq) + Cl - (aq);

with ∞-
DG∞ = - FECl | AgCl | Ag
∞ +
+ FEAg | Ag

Since DG∞ = - RT ln Ks∞ , we will have

RT
∞-
ECl ∞ +
= EAg + ln Ks∞ (AgCl)
| AgCl | Ag | Ag
F
Computation of At 298 K, we have
Potentials
∞-
ECl ∞ +
= EAg - (0.059 15 V) pKs∞ (AgCl)
| AgCl | Ag | Ag
456 A Textbook of Physical Chemistry

Now ∞ +
EAg = 0.799 V and pKs∞ (AgCl) = 9.75. Thus, we have
| Ag

∞-
ECl = 0.799 V - (0.059 15 V) (9.75)
| AgCl | Ag

= 0.222 V

Equation (8.12.4) may also be used to calculate the solubility product of

silver chloride by measuring the standard potentials of Ag+ |Ag and Cl– | AgCl | Ag
half-cells.
Generalization of Equation (8.12.4) may be generalized as
Eq. (8.12.4)
2.303 RT
EX∞ - | AgX | Ag
∞ +
= EAg | Ag
- {pKs∞ (AgX)} (8.12.7)
F

where X– stands for the halide ion (Cl–, Br– and I–). From Eq. (8.12.7) it follows
that larger the pK ºs, lesser the reduction potential of silver halide-silver electrode.
Table 8.12.1 records the standard potentials for some of the metal-insoluble
salt-anion electrodes.

Table 8.12.1 Standard Potentials of Some of the Metal-Insoluble

Salt-Anion Electrodes

Electrode reaction E°/V

AgCl(s) + e– Ag + Cl– 0.222
–
AgBr(s) + e Ag + Br– 0.03
– –
AgI(s) + e Ag + I – 0.151
– 2–
Ag2S(s) + 2e 2Ag + S – 0.69

It follows from Table 8.12.1 that

pK ºs(Ag2S) > pK ºs(AgI) > pK ºs(AgBr) > pK ºs(AgCl) (8.12.8)
which implies that

K s(AgCl) > Ks(AgBr) > Ks(AgI) > Ks(Ag2S) (8.12.9)

From Eq. (8.12.8), it follows that silver chloride is more soluble than
silver bromide which, in turn, is more soluble than silver iodide. The fact that
the silver-silver iodide couple has a negative potential means that silver should
dissolve in HI with the release of hydrogen gas. This, in fact, occurs, but the
action ceases promptly due to the layer of insoluble AgI which forms and protects
the silver surface from further attack.

Example 8.12.1 Calculate E° for the following reactions at 298 K.

Ag(NH3)2+ + e– Ag + 2NH3
 Electrochemical Cells 457

Ag(CN)2– + e– Ag + 2CN–

Given: ∞ +
EAg | Ag = 0.799 1 V, ∞ (Ag(NH3 )2+ ) = 6.02 ¥ 10 -8 and
K Ins

∞ (Ag(CN)2- ) = 1.995 ¥ 10 -19 .

K Ins

Solution ∞ +
The equation which relates EAg | Ag with E° of the given expression is

∞ +
E ∞ = EAg | Ag
∞
- (0.059 15 V) pK Ins

Thus ∞ , Ag(NH )+
ENH 3 3 2 | Ag = 0.799 1 V - (0.059 15 V)(- log 6.02 ¥ 10 -8 )
= 0.799 1 V - 0.427 V
= 0.372 1 V

and ∞ -
ECN | Ag(CN)2- | Ag
= 0.799 1 V - (0.059 15 V)(- log 1.995 ¥ 10 -19 )
= 0.799 1 V - 1.106 1 V
= - 0.307 V

Example 8.12.2 Show that the standard potential of the reaction

H 2O + e - Æ 21 H 2 + OH -

is given as

RT
E∞ = ln K w∞
F
Determine its value at 298 K.
Solution The reduction potential of the reaction

H 2O + e - Æ 21 H 2 + OH -

RT
is given by E = E∞ - ln {( f H2 /f ∞)1/2aOH - } (1)
F

Since K w = (aH+ )(aOH - ), Eq. (1) may be written as

RT ( f H2 /f ∞)1/2 RT
E = E∞ - ln - ln K w∞ (2)
F aH+ F

The cell in which the given half-cell reaction occurs may equally be considered as the
hydrogen-hydrogen ion half cell. Hence, its potential will be given as

RT ( f H2 /f ∞)1/2
E =- ln (3)
F aH+
458 A Textbook of Physical Chemistry

Comparing Eqs (2) and (3), we get

RT
E∞ = ln K w∞ (4)
F
At 298 K, the value of Eº is

RT (2.303)(8.314 J K -1 mol -1 )(298 K)

ln K w∞ = log (10 -14 )
F (96 500 C mol -1 )
= - 0.828 V

8.13 CELL REACTION AND ITS RELATION WITH CELL POTENTIAL

The electrical work that is obtainable when the amount n of electrons flow
from left electrode to right electrode of a cell will be equal to the change in
free energy of the cell reaction. The relation between the cell potential and the
free energy change of the associated cell reaction was derived in Section 8.5
and may be derived from Eq. (8.5.6) by replacing dn by n and z by –1. Thus,
we have
DG = - nF (ER - EL ) = - nFEcell

Superficially, it might appear that G and E differ only by a numerical factor,

but actually they also differ in a qualitative sense. G is uniquely determined
by the overall cell reaction; Ecell is determined by the overall reaction and the
make up of the cell. To illustrate this difference, we consider the various ways
in which the following three half-cell reactions

Fe 2+ + 2e - Æ Fe; ∞ 2+
EFe | Fe
= - 0.440 V (8.13.1)

Fe3+ + 3e - Æ Fe; ∞ 3+
EFe | Fe
= - 0.036 V (8.13.2)

Fe3+ + e - Æ Fe 2 + ; ∞ 3+ 2+
EFe , Fe | Pt
= - 0.771 V (8.13.3)

may be combined to form a cell with the following overall cell reaction.

Fe + 2Fe3+ Æ 3Fe 2+ (8.13.4)

Combination of Eqs The overall cell reaction (Eq. 8.13.4) may be obtained from Eqs (8.13.1) and
(8.13.1) and (8.13.2) (8.13.2) by multiplying the former by 3 and the latter by 2 (so that the electrons
involved in the two half-cell reactions are same) and then subtracting the resultant
Eq. (8.13.1) from the resultant Eq. (8.13.2). Thus, we have
Eq. (8.13.2): 2Fe3+ + 6e– 2Fe; ∞ 3+
EFe = - 0.036 V
| Fe

Eq. (8.13.1): 3Fe2+ + 6e– 3Fe; ∞ 2+

EFe = - 0.440 V
| Fe

with the overall reaction

Fe + 2Fe3+ 3Fe2+; ∞ = 0.404 V
Ecell
 Electrochemical Cells 459

The cell producing this reaction would be

Fe | Fe2+ Fe3+ | Fe (8.13.5)
Combination of Eqs In this case, we multiply Eq. (8.13.3) by 2 and then subtract from it Eq. (8.13.1).
(8.13.1) and (8.13.3) Thus, we have

Eq. (8.13.3): 2Fe3+ + 2e– 2Fe2+; ∞ 3+ 2+

EFe = 0.771 V
, Fe | Pt

Eq. (8.13.1): Fe2+ + 2e– Fe; ∞ 2+

EFe = - 0.440 V
| Fe

with the overall reaction

Fe + 2Fe3+ 3Fe2+ E ºcell = 1.211 V
The cell producing this reaction would be
Fe | Fe2+ Fe3+, Fe2+ | Pt (8.13.6)
Combination of Eqs In this case, we multiply Eq. (8.13.3) by 3 and then subtract from it Eq. (8.13.2).
(8.13.2) and (8.13.3) Thus, we have

Eq. (8.13.3): 3Fe3+ + 3e– 3Fe2+; ∞ 3+ 2+

EFe = 0.771 V
, Fe | Pt

Eq. (8.13.2) Fe3+ + 3e– Fe; ∞ 3+

EFe = - 0.036 V
| Fe

with the cell reaction

Fe + 2Fe3+ 3Fe2+; E ºcell = 0.807 V
The cell producing this reaction would be
Fe | Fe3+ Fe3+, Fe2+ | Pt (8.13.7)
Thus, we observe that the voltage developed by a cell depends on the half-
cell reactions, i.e. what occurs at the electrodes (or in other words on the make
up of the cell) as well as on the overall reaction. But G depends only on the
overall cell reaction as may be seen from the G values recorded in Table8.13.1.
Conclusion From Table 8.13.1, it is obvious that for all the three cells, Gº is the same but
n and E ºcell vary from cell to cell. The variations in n and E ºcell are such that the

Table 8.13.1 Cell, E ºcell and Gº Values

Ecell Number of electrons

Cell associated in the
V half-cell reactions G° = – nFE°
n

Fe | Fe2+ Fe3+ | Fe 0.404 6 – 2.424 F

Fe | Fe2+ Fe3+, Fe2+ | Pt 1.211 2 – 2.422 F
Fe | Fe3+ Fe3+, Fe2+ | Pt 0.807 3 – 2.421 F
460 A Textbook of Physical Chemistry

product of two always remains constant. Thus, we conclude that Gº depends

º depends on the make up of the cell. It may
only on the cell reaction but E cell
be emphasized once again here that E cell
º is an intensive property (being equal
to Gº/n) and thus its value does not depend upon the size of the cell and the
extent to which the cell reaction is carried out. To make the latter point more
clear, we take up the cell as given by Eq. (8.13.5). If the overall cell reaction
Fe + 2Fe3+ 3Fe2+
is written as
2Fe + 4Fe3+ 6Fe2+
then E cell
º remains the same but Gº changes from – 2.424 F to – 4.848 F. This
change in Gº will be brought about by the change in the number of electrons
involved in the two-half reactions. Thus, n changes from 6 to 12.

8.14 CALCULATION OF STANDARD POTENTIAL FOR AN UNKNOWN HALF-CELL

REACTION
A given reaction may be obtained from other reactions by carrying out the
simple mathematical manipulations such as addition, subtraction, multiplication
by a number and so on. Since G º is a state function, the G º of the given
reaction may be obtained by carrying out the corresponding manipulations on
G ºs values of the reactions. This procedure, however, cannot be adopted while
calculating Eº of a half-cell reaction from the values of other half-cell reactions.
Nevertheless, we can determine the potential of a half-cell reaction from the
potentials of other half-cell reactions via the associated Gº values. First of all,
we write
Gº = – nFE º
for each and every half-cell reaction and then carry out the appropriate
manipulations of the reactions along with the corresponding G ºs values to
give the given half-cell reaction and its G º value. Knowing the number n
of electrons involved in the given reaction and the obtained value of Gº, the
value Eº may be determined. To illustrate the procedure, we compute E º for
the reaction
Fe3+ + e– Fe2+ (8.14.1)
from E ºs of the reactions

Fe3+ + 3e– Fe; ∞ 3+

EFe = - 0.036 V (8.14.2)
| Fe

Fe2+ + 2e– Fe; ∞ 2+

EFe = - 0.440 V (8.14.3)
| Fe

The half-cell reaction of Eq. (8.14.1) can be obtained by subtracting the

half-cell reaction of Eq. (8.14.3) from that of Eq. (8.14.2). Accordingly, G º
for the reaction of Eq. (8.14.1) may be obtained by subtracting the Gº of the
reaction of Eq. (8.14.3) from that of Eq. (8.14.2). Thus, we have
 Electrochemical Cells 461

Eq. (8.14.2): Fe3+ + 3e– Fe; DG1∞ = - 3FEFe

∞ 3+
| Fe
= (0.108 V) F

Eq. (8.14.3): Fe2+ + 2e– Fe; DG2∞ = - 2FEFe

∞ 2+
| Fe
= (0.880 V) F

Subtracting, we get
Eq. (8.14.1): Fe3+ + e– Fe2+; Gº = G 1º – G2º
= (0.108 V) F – (0.880 V) F
= (– 0.772 V) F
Since the number of electrons involved in Eq. (8.14.1) is one, it follows that

∞ 3+ 2+
DG∞ = (- 0.772 V) F = - 1 F EFe , Fe | Pt

Hence ∞ 3+ 2+
EFe = 0.772 V
, Fe | Pt

Note that if we had subtracted the two half-cell potentials, we would have
got 0.404 V, a wrong result.

Example 8.14.1 From the standard potentials shown in the following diagram, calculate the potentials
E1º and E2º.

Solution The reaction corresponding to the potential E 1º is

BrO3- + 3H 2 O + 5e - Æ 21 Br2 + 6OH - (1)

This reaction can be obtained by adding the following two reduction reactions:

BrO3- + 2H 2O + 4e - Æ BrO - + 4OH - (2)

BrO - + H 2O + e - Æ 21 Br2 + 2OH - (3)

Hence the free energy change of reaction (1) will be

∞
DGreaction ∞ ∞
(1) = DGreaction (2) + DGreaction (3)
462 A Textbook of Physical Chemistry

Replacing G ºs in terms of potentials, we get

-5FE1∞ = - 4F (0.54 V) - 1F (0.45 V)

= (- 2.61 V) F

2.61 V
Hence E1∞ = = 0.52 V
5
Now the reaction corresponding to the potential Eº2 is

BrO3- + 3H 2 O + 6e - Æ Br - + 6OH - (4)

This reaction can be obtained by adding the following three reactions.

BrO3- + 2H 2O + 4e - Æ BrO - + 4OH - (Eq. 2)

BrO - + H 2O + e - Æ 21 Br2 + 2OH - (Eq. 3)

1
2
Br2 + e - Æ Br - (5)

Hence ∞
DGreaction ∞ ∞ ∞
(4) = DGreaction (2) + DGreaction (3) + DGreaction (5)

or - 6F (E2∞ ) = - 4F (0.54 V) - 1F (0.45 V) - 1F (1.07 V)

= (- 3.68 V)F
3.68 V
or E2∞ = = 0.61 V
6

8.15 REFERENCE HALF-CELLS

Desirability of a In Section 8.8, we have seen that the standard potential of a given half-cell may
Reference Half-Cell be determined by constructing a cell in which the left half-cell is the standard
hydrogen-hydrogen ion half-cell and the right side is the given half-cell and
determining its emf experimentally. By definition, the standard potential of the
given half-cell will be equal to the obtained value of emf of the cell. However,
the hydrogen-hydrogen ion half-cell suffers from a large number of limitations.
For example, it is very inconvenient to use it in practice as a constant supply of
hydrogen gas at 1 bar pressure is required. Moreover, the potential of hydrogen-
hydrogen ion half-cell is very sensitive to dissolved oxygen, hydrogen sulphide
and the reducible species. The hydrogen-hydrogen ion half-cell is also very
susceptible to electrode poisoning. It is for these reasons, the hydrogen-hydrogen
ion half-cell may be replaced by a suitable reference half-cell whose potential
has been accurately determined with respect to the hydrogen-hydrogen ion
half-cell.
Reference half-cell systems are chosen to give reproducible potentials over
a long period of time.
Common Examples The most common type of reference half-cell has the following form:
of Reference Half-
saturated solution of sparingly + additional strongly ionized
Cell Metal
soluble salt of metal salt with a common anion
 Electrochemical Cells 463

Examples include:
(1) Calomel half-cell: KCl(aq) | Hg2Cl2(s) | Hg
(2) Silver-silver chloride half-cell: KCl(aq) | AgCl(s) | Ag
(3) Mercury-mercurous sulphate half-cell: K2SO4(aq) | Hg2SO4(s) | Hg
The potential adopted by each of these reference half-cells is controlled
by the activity of the anion in solution. We give below a brief discussion of
these three half-cells.
Calomel Half-Cell The half-cell set up is shown in Fig. 8.15.1.

Fig. 8.15.1 Calomel

half-cell

The half-cell reaction is

1
2
Hg2Cl2(s) + e– Hg(1) + Cl–(aq)
and the Nernst equation has the form
RT
ECl - ∞-
= ECl - ln (aCl - )
| Hg2 Cl2 | Hg | Hg2 Cl2 | Hg F
with ∞-
ECl = 0.267 6 V
| Hg2 Cl2 | Hg

Thus, the calomel half-cell functions as the reversible chloride electrode.

Three types of calomel half-cell are commonly used. These are corresponding to
0.1 mol dm–3, 1 mol dm–3 and saturated KCl solution having potentials 0.336 V,
0.283 V and 0.244 V, respectively at 25 °C.
Silver-Silver The half-cell reaction is
Chloride-Chloride AgCl(s) + e– Ag(s) + Cl–(aq)
Ion Half-Cell
Hence, the half-cell potential is given by
RT
ECl - ∞-
= ECl - ln (aCl - )
| AgCl | Ag | AgCl | Ag
F
with ∞-
ECl = 0.222 V
| AgCl | Ag
464 A Textbook of Physical Chemistry

This half-cell cannot be used in a solution which contains HNO3, I– and

–
CN ions.
Mercury-Mercurous The half-cell set up is very similar to that of calomel half-cell. The cell-reaction
Sulphate-Sulphate is
Ion Half-Cell Hg2SO4(s) + 2e– 2Hg(l) + SO42–(aq)
Hence the half-cell potential is given by
RT
ESO2- ∞ 2-
= ESO - ln (aSO2- )
4 | Hg2 SO 4 | Hg 4 | Hg2 SO 4 | Hg 2F 4

with ∞ 2-
ESO = 0.615 1 V
4 | Hg2 SO 4 | Hg

This half-cell potential depends upon the activity of SO42– ions.

Mercury-Mercuric Another half-cell which finds its utility in strongly alkaline solutions is the
Oxide-Hydroxide mercury-mercuric oxide half-cell. It consists of a pool of mercury in contact with
Ion Half-Cell a solution of NaOH or KOH which is saturated with HgO.
The half-cell reaction is
1
2
HgO(s) + 1
2
H 2 O + e - Æ 21 Hg(1) + OH - (aq)

and thus the Nernst equation has the form

RT
EOH - ∞ -
= EOH - ln (aOH - )
| HgO | Hg | HgO | Hg F

8.16 EXPRESSION OF Ecell IN THE UNIT OF MOLALITY

If the emf of a cell has to be written in terms of mean activity of the electrolytes,
we will have to consider the cell involving the electrolytes rather than the ions.
For example, the Daniell cell
Zn | Zn2+(aq) Cu2+(aq) | Cu
will be written as
Zn | ZnSO4(aq) CuSO4(aq) | Cu
The emf of the cell as given by Eq. (8.7.9) is
RT aZn2+
∞ -
Ecell = Ecell ln
2F aCu2+
Expressing a in terms of molality and activity coefficient, we get
RT m ¢ 2+ RT g 2+
∞ -
Ecell = Ecell ln Zn - ln Zn (8.16.1)
2F ¢ 2+ 2 F
mCu g Cu2+

†
See Annexure I at the end of this Chapter for the discussion on activity and its relation
with molality. Throughout this Chapter, m represents m/mº, where m is the molality and
mº is the unit molality.
 Electrochemical Cells 465

The expression of m and γ in terms of mean molality and mean activity coefficient
are as follows. In the present case
x = y = 1, ν=2 and m + = m–
Hence ¢ 2+ = m±¢ (ZnSO 4 )
mZn ¢ 2+ = m±¢ (CuSO 4 )
mCu

g Zn2+ = g ± (ZnSO 4 ) g Cu2+ = g ± (CuSO 4 )

(8.16.2)

Thus, Eq. (8.16.1) become

RT m ¢ (ZnSO 4 ) RT g (ZnSO 4 )
∞ -
Ecell = Ecell ln ± - ln ±
2F m±¢ (CuSO 4 ) 2F g ± (CuSO 4 )

Example 8.16.1 Calculate the potential at 25 °C for the cell

Pt | H2( p = 1 bar) | HBr(a± = 0.2) | Hg2Br2(s) | Hg
Solution We have

Electrode Reduction
Right Hg2Br2(s) + 2e– 2Hg(1) + 2Br–(aq)
Left 2H+(aq) + 2e– H2(g)

The cell reaction is

Hg2Br2(s) + H2(g) 2Hg(1) + 2Br–(aq) + 2H+(aq)

RT (a + )2 (aBr - )2
Hence ∞-
Ecell = (EBr - EH∞ + | H )- ln H
| Hg 2 Br2 | Hg 2
| Pt 2F ( p(H 2 )/p∞)

RT (aH+ ) (aBr - )
or ∞-
Ecell = EBr - ln
| Hg2 Br2 | H 2 F ( p(H 2 )/p∞)1/2

RT {(a± (HBr)}2
or ∞-
Ecell = EBr - ln
| Hg 2 Br2 | Hg F ( p(H 2 )/p∞)1/2

Substituting the data, we get

Ecell = 0.138 5 V - (0.059 15 V) (2) log (0.2)

= 0.138 5 V + 0.082 7 V = 0.221 2 V

Example 8.16.2 The potential of the cell

Cd | CdI2(a2) | AgI(s) | Ag
is 0.286 0 V at 25 °C. Calculate the mean ionic activity of the ions in the solution, and
the activity of electrolyte.
466 A Textbook of Physical Chemistry

Solution We have

Electrode Reduction reaction

Right 2AgI(s) + 2e– 2Ag(s) + 2I–(aq)
Left Cd2+(aq) + 2e– Cd(s)

The cell reaction is

2AgI(s) + Cd(s) Æ 2Ag(s) + Cd 2+ (aq) + 2I - (aq)

RT
Hence Ecell = (EI∞- | AgI | Ag
∞ 2+
- ECd | Cd
)- ln (aCd2+ )(aI - )2
2F

RT
or Ecell = (EI∞- | AgI | Ag
∞ 2+
- ECd | Cd
)- ln (a± )3
2F
Substituting the data, we get

Ê 3 ¥ 0.059 15 V ˆ
0.286 0 V = { - 0.152 2 V - (- 0.403 V)} - Á ˜¯ log a±
Ë 2

or 0.286 0 V = 0.250 8 V - (0.088 72 V) log a±

0.250 8 - 0.286 0 0.035 2

or log a± = =- = - 0.396 7
0.088 72 0.088 72
Thus a± = 0.401 2
Now since a2 = a±3, we get
a2 = (0.401 2)3 = 0.064 55

Example 8.16.3 The potential of the cell

Zn(s) | ZnCl2(0.010 21 mol kg–1) | AgCl(s) | Ag(s)
is found to be 1.156 6 V. What is the mean ionic activity coefficient of ZnCl2 in the
solution?

Solution We have

Electrode Reduction reaction

Right 2AgCl(s) + 2e– 2Ag(s) + 2Cl–(aq)
Left Zn2+(aq) + 2e– Zn(s)

The cell reaction is

2AgCl(s) + Zn(s) 2Ag(s) + Zn2+(aq) + 2Cl–(aq)

RT
Hence ∞-
Ecell = (ECl ∞ 2+
- EZn )- ln (aZn 2+ )(aCl - )2
| AgCl | Ag | Zn
2F
 Electrochemical Cells 467

RT
∞-
= (ECl ∞ 2+
- EZn )- ln a±3
| AgCl | Ag | Zn
2F
RT
∞-
= (ECl ∞ 2+
- EZn )- ln (m±¢ )3g ±3
| AgCl | Ag | Zn
2F

Now (m±¢ )3 = (m+¢ )(m-¢ )2

= (0.010 21) (2 ¥ 0.010 21)2
= 4 ¥ 0.010 213 = 4.257 ¥ 10 -6

Substituting this along with other data in the expression of Ecell, we have

Ê 0.059 15 V ˆ
1.156 6 V = {0.222 V - (- 0.762 V)} - Á 3
˜¯ log m±
Ë 2
Ê 0.059 15 V ˆ
-Á 3
˜¯ log g ±
Ë 2
= 0.984 V - (0.029 57 V) log (4.257 ¥ 10 -6 )
- 3(0.029 57 V) log g ±
= 1.143 V - (0.088 7 V) log g ±

1.156 6 - 1.143 0.013 6

or log g ± = - =- = - 0.153 3
0.088 7 0.088 7

Hence γ ± = 0.702 6

8.17 DETERMINATION OF ACCURATE VALUE OF HALF-CELL POTENTIAL

The standard half-cell potentials are employed for calculating accurate values
of various quantities such as equilibrium constant of a weak acid and ionic
product of water. It is, therefore, essential to know their accurate values. For
this purpose, the method of extrapolation is employed. To illustrate the method,
we consider the following cell.

Pt | H2(1 bar) | HCl(a) | AgCl(s) | Ag (8.17.1)

The cell reaction is

AgCl + 1
2
H 2 Æ Ag + Cl - + H + (8.17.2)

and the cell potential is given by

RT (a + )(aCl - )
E = E∞ - ln H (8.17.3)
F ( f H2 /f ∞)1/2
468 A Textbook of Physical Chemistry

Assuming ideal behaviour for the gas, we get

RT
E = E∞ - ln (aH+ )(aCl - ) (8.17.4)
F

Since individual ionic activities cannot be determined, we express aH+ and

aCl– in terms of mean activity a± of hydrochloric acid by the relation

a±2 = (aH+ )(aCl - ) (8.17.5)

Now the mean activity may be expressed in terms of mean molality m±

of the ions and the mean activity coefficient γ± by the relation

a± = m±¢ g ± (8.17.6)†

For HCl solution

m±¢ = m ¢ = m/m∞ (8.17.7)

where m is the molality of the solution. Using Eqs (8.17.5), (8.17.6) and (8.17.7)
in Eq. (8.17.4), we get

2 RT 2 RT
E = E∞ - ln m ¢ - ln g ± (8.17.8)
F F

If the measurements are done in dilute solutions, than γ± can be expressed in

terms of the ionic strength of the solution using the Debye-Hückel limiting law††

log g ± = - Az+ | z- | m1/2 (8.17.9)

where A is equal to 0.514 (mol dm–3)–1/2, z+ and z_ are the charge numbers of
ions, and μ is the ionic strength of the solution. The latter is defined as

1
m= Â ci zi2
2 i
(8.17.10)

where ci is the molar concentration of the ith ions. The summation is to be

carried over all the ions present in the solution. For uni-univalent electrolyte
such as the given one
μ=c=m (8.17.11)
Thus for HCl solution, Eq. (8.17.9) becomes

log g ± = - 0.509 m ¢1/2 (8.17.12)

†Throughout this chapter, m = m/mº.

††
See Annexure II for the derivation of Debye-Hückel limiting law.
 Electrochemical Cells 469

Substituting Eq. (8.17.12) in Eq. (8.17.8), we get

2 RT 2.303 ¥ 2 RT
E = E∞ - ln m ¢ - (- 0.509 m ¢1/2 )
F F
2 RT 2.303 ¥ 2 RT
or E+ ln m ¢ = E ∞ + (0.509 m ¢1/2 )
F F
At 25 ºC, the above equation becomes
E + (0.118 3 V) log m ¢ = E ∞ + (0.060 2 V) m ¢

The value E of the cell is determined at various values of m and then

a plot between E + (0.118 3 V) log m and m ¢ is made. The plot will be a
straight line at lower values of m ¢ which can be extended to m ¢ = 0 as
shown in Fig. 8.17.1. The intercept at m ¢ = 0 gives the value of E º.
E + (0.118 3 V) log m¢

Eº = 0.222 5 V
Fig. 8.17.1 A graph of
E + (0.118 3) log m
versus m ¢
m¢

Since the standard potential of the cell (Eq. 8.17.1) is given by

∞ = E∞ -
Ecell - EH∞ +
Cl | AgCl | Ag | H2

and the fact that

EH∞ + | H2
=0

it follows that

∞-
ECl ∞ = 0.222 5 V
= Ecell
| AgCl | Ag

Following the method outlined above, the accurate values of half-cell

potentials of other electrodes can be determined.
470 A Textbook of Physical Chemistry

8.18 APPLICATIONS OF ELECTROCHEMICAL CELLS

The emf measurement of electrochemical cells provides one of the convenient
methods to determine the values of various physical quantities such as the
equilibrium constant, ionization constant, ionic product of water, pH of a solution,
and the values of thermodynamic properties of ions. Besides these, the quantitative
estimation of species can be carried out with the help of potentiometric titration.
In this section, we describe the above applications with specific examples.

1. DETERMINATION OF THERMODYNAMIC DATA

Expression of Free The free energy change accompanying a cell reaction can be obtained from the
Energy Change emf of the cell through the relation
G = – nFEcell (8.18.1)
Expression of The changes in enthalpy and entropy of the cell reaction can also be determined
Enthalpy Change if the temperature dependence of the emf of the cell is available. For this, we
make use of the Gibbs–Helmholtz equation
È ∂(DG ) ˘
DG = DH + T Í (8.18.2)
Î ∂T ˙˚ p
Now since
G = – nFE
we, therefore, get

È ∂(DG ) ˘ Ê ∂E ˆ
ÍÎ ∂T ˙˚ = - nF ÁË ∂T ˜¯ (8.18.3)
p p

Substituting Eqs (8.18.1) and (8.18.3) in Eq. (8.18.2), we get

Ê ∂E ˆ
– nFE = DH – nFT Á ˜
Ë ∂T ¯ p

Rearranging, we have

È Ê ∂E ˆ ˘
DH = - nF Í E - T Á ˜ ˙ (8.18.4)
Î Ë ∂T ¯ p ˚

Thus, H of the cell reaction can be determined from the knowledge of

E and E/ T)p. Since E and F are expressed respectively in volt and coulomb,
the units of H is in volt-coulomb and is equal to the joule unit.
Expression of Now since G = H – T S, therefore
Entropy Change
DH - DG
DS = (8.18.5)
T
Substituting the expressions of H and G from Eqs (8.18.4) and (8.18.1), we
get
 Electrochemical Cells 471

Ê ∂E ˆ
DS = nF Á ˜ (8.18.6)
Ë ∂T ¯ p

Thus knowing ( E/ T)p, S of the cell reaction can be computed from

Eq. (8.18.6).

1. STANDARD FREE ENERGIES AND ENTROPIES OF AQUEOUS IONS

Free Energy of The assignment of zero potential to the standard hydrogen-hydrogen ion half-
H+(aq) cell provides the conventional zero for free energy of formation of hydrogen
ions in aqueous solution. This follows immediately from the potential expression
of the standard hydrogen-hydrogen ion half-cell (Eq. 8.6.6). We have

mH∞ + - 21 mH∞ + me - (Pt)

E∞+
H | H2
= 2
(Eq. 8.6.6)
F

Since the electrons are not emitted as such from the neutral metal, we set
μe–(Pt) = 0. Also μ Hº 2 at 298 K and 1 bar is zero. Hence

mH∞ +
EH∞ + | H2
=
F

Now since EH∞ + | H2

is assigned a zero value, it follows that

mH∞ + = 0

(Alternatively, we may assume mH∞ + = 0 and proceed to prove that EH∞ + |H = 0 .)

2 |Pt

Thus the reference standard for free energies of formation of ions in

solution is the hydrogen ion at a = 1, which is assigned a zero value.
Free Energy of The standard free energies of formation of ions relative to the above reference
Other Ions may be determined as follows.
Let the free energy of formation of Cd2+ ion be required. We construct a
cell involving Cd2+ | Cd half-cell and the standard hydrogen-hydrogen ion half-cell:

Cd | Cd2+(a = 1) H+ (a = 1) | H2(l bar) | Pt

The cell reaction is

Cd + 2H+ Cd2+ + H2
The cell potential is given by

∞ = E∞+
Ecell ∞ 2+
- ECd
H | H 2 | Pt | Cd

= 0 - (- 0.403 V) = 0.403 V
472 A Textbook of Physical Chemistry

The change in the standard free energy of the cell reaction

Cd + 2H+ Cd2+ + H2
is given by

DG º = – nFEcell
º
= – 2 (96 487 C mol –1 )(0.403 V) = – 77 769 J mol –1

Gº will also be given by

DGº = mCd
º 2+ + mHº – mCd
2
º – 2m º +
H

By convention,
∞ = 0;
mCd mH∞ 2 = 0 and mH∞ + = 0

Thus ∞ 2+ = - 77 769 J mol -1

DG∞ = mCd

Proceeding this way, we can determine the free energy of formation or

other ions in the solution.
Standard Entropy of The standard ionic entropies in solution is also determined relative to that of
Formation of Ions hydrogen ion at unit activity. By convention, the latter is assigned a zero value†,
i.e.
SH∞ + = 0

To illustrate the procedure of calculating standard ionic entropy, we take

an example of Cd2+. Consider again the reaction
Cd + 2H+ Cd2+ + H2
The standard entropy change is
∞ 2+ + SH∞ - 2S ∞ + - SCd
DS ∞ = SCd ∞
2 H

Since SH∞ + = 0, we have

∞ 2+ + SH∞ - SCd
DS ∞ = SCd ∞
2

The standard entropies of Cd and H2 at 298 K are 51.46 and 130.58 J K–1
–1
mol , respectively.

Hence SCd ∞ - SH∞ = DS ∞ - 79.12 J K -1 mol -1

∞ 2+ = DS ∞ + SCd
2

The value of Sº can be obtained from the relation

†
The absolute value of third law entropy of proton in water is – 20.99 J K–1 mol–1.
 Electrochemical Cells 473

DG∞ = DH ∞ - T DS ∞

DH ∞ - DG∞
i.e. DS ∞ =
T
The values of Gº of the reaction as determined above is – 77.769 kJ mol–1.
The standard enthalpy change Hº can be determined experimentally by
dissolving 1 mol of Cd2+ in a large excess of dilute acid. The value obtained
is – 69.83 kJ mol–1. Hence

- 69 830 J mol -1 + 77 769 J mol -1

DS∞ = = 26.64 J K -1 mol -1
298 K

Thus ∞ 2+ = DS ∞ - 79.12 J K -1 mol -1 = (26.64 - 79.12) J K -1 mol -1

SCd
= - 52.48 J K -1 mol -1

It may be pointed here that the above standard entropy of formation of

Cd2+ is not the absolute entropy of the Cd2+ ion in aqueous solution, but refers
∞ 2+ - S ∞ + .
to a neutral combination of the given ion with H3O+ ion, i.e. SCd H

Example 8.18.1 The emf of the cell

Ag | AgCl(s) | KCl(aq) | Hg2Cl2(s) | Hg
is 0.045 5 V at 298 K and the temperature coefficient is 3.38 × 10–4 V K–1. What is the
reaction taking place in the cell and what are free energy, enthalpy and entropy changes
at 298 K?
Solution For the given cell, we have

Electrode Reduction reaction

Right Hg2Cl2(s) + 2e– 2Hg(l) + 2Cl–(aq) (i)
Left 2AgCl(s) + 2e– 2Ag(s) + 2Cl–(aq) (ii)

Subtracting Eq. (ii) from Eq. (i), we get

Hg2Cl2(s) + 2Ag(s) 2Hg(l) + 2AgCl(s)
The number of electrons involved at the electrode reactions is 2.
Thus DG = - nFE
= - 2(96 500 C mol -1 ) (0.045 5 V) = - 8 782 J mol -1
È Ê ∂E ˆ ˘
DH = - nF Í E - T Á ˜ ˙
Î Ë ∂T ¯ p ˚

= - 2(96 500 C mol -1 ) [0.045 5 V - (298 K) (3.38 ¥ 10 -4 V K -1 )]

= 2(96 500 C mol -1 ) (0.055 2 V) = 10 650 J mol -1

Ê ∂E ˆ
and DS = nF Á ˜ = 2(96 500 C mol -1 ) (3.38 ¥ 10 -4 V K -1 )
Ë ∂T ¯ p

= 65.23 J K -1 mol -1
474 A Textbook of Physical Chemistry

Example 8.18.2 At 298 K, the emf of the cell

0.01 mol dm -3 KCl 1 mol dm -3 KNO3 0.01 mol dm -3 KOH

Hg Hg
sat. with Hg2 Cl2 salt bridge sat. with HgO

is found to be 0.163 4 V and the temperature coefficient of the emf to be 0.000 837 V K–1.
Calculate the enthalpy and entropy changes of the reaction. What is the reaction that occurs
in the cell?

Solution For the given cell, we have

Electrode Reduction reaction

Right HgO(s) + H2O(1) + 2e– Hg(l) + 2OH–(aq) (i)
–
Left Hg2Cl2(s) + 2e 2Hg(l) + 2Cl–(aq) (ii)

Subtracting Eq. (ii) from Eq. (i), we get

HgO(s) + H2O(l) + Hg(l) + 2Cl–(aq) Hg2Cl2(s) + 2OH–(aq)
The number of electrons involved in the electrode reactions is 2.

Thus DG = - nFE = - 2(96 500 C mol -1 ) (0.163 4 V) = - 31 536.2 J mol -11

È Ê ∂E ˆ ˘
DH = - nF Í E - T Á ˜ ˙
Î Ë ∂T ¯ p ˚

= - 2(96 500 C mol -1 ) [(0.163 4 V) - (298 K ¥ 0.000 837 V K -1 )]

= 16 603 J mol -1
Ê ∂E ˆ
DS = nF Á ˜
Ë ∂T ¯ p

= 2(96 500 C mol -1 ) (0.000 837 V K -1 ) = 161.54 J K -1 mol -1

Example 8.18.3 For the cell

Ag(s) | AgBr(s) | KBr(aq) | Hg2Br2(s) | Hg(l)
the emfs at several temperatures are
T/K 293 298 303
emf/V 0.066 3 0.068 39 0.070 48
(a) Write the cell reaction for the passage of two-faraday of charge.
(b) Calculate G, H and S at 298 K.
Solution First of all a graph between E and T was drawn and its slope was determined to yield the
value of ( E/ T)p as shown in Fig. 8.18.1. The value was found to be 0.000 42 V K–1
(a) The cell reaction may be determined as follows:

Electrode Reduction reaction

Right Hg2Br2(s) + 2e– 2Hg(l) + 2Br(aq) (i)
Left 2AgBr(s) + 2e– 2Ag(s) + 2Br–(aq) (ii)
 Electrochemical Cells 475

Fig. 8.18.1 The graph of

E versus T

Subtracting Eq. (ii) from Eq. (i), we get

Hg2Br2(s) + 2Ag(s) 2Hg(1) + 2AgBr(s)
(b) Now

DG = - nFE = - 2(96 500 C mol -1 ) (0.068 39 V) = - 13 199.3 J mol -1

È Ê ∂E ˆ ˘
DH = - nF Í E - T Á ˜ ˙
Î Ë ∂T ¯ p ˚

= - 2(96 500 C mol -1 ) [(0.068 39 V) - (298 K) (0.000 42 V K -1 )]

= 10 956.6 J mol -1
Ê ∂E ˆ
DS = nF Á ˜
Ë ∂T ¯ p

= 2(96 500 C mol -1 ) (0.000 42 V K -1 ) = 81.06 J K -1 mol -1

Example 8.18.4 For the following cell

Pb | PbCl2(s) | PbCl2(soln.) | AgCl(s) | Ag
the potential at 298 K is 0.490 V and the variation of emf with temperature is given by
E = a – (1.86 × 10–4 V K–1) (T – 25 K)
Write the equation for the cell reaction and calculate G, H and S for the reaction at
298 K.
Solution For the given cell, we have

Electrode Reduction reaction

Right 2AgCl(s) + 2e– 2Ag(s) + 2Cl–(aq) (i)
Left PbCl2(s) + 2e– Pb(s) + 2Cl–(aq) (ii)
476 A Textbook of Physical Chemistry

Subtracting Eq. (ii) from Eq. (i), we get

2AgCl(s) + Pb(s) 2Ag(s) + PbCl2(s)
–4
Now since E = a – (1.86 × 10 V K–1) (T – 25 K), therefore

Ê ∂E ˆ -4 -1
ÁË ˜¯ = - 1.86 ¥ 10 V K
∂T p

Hence DG = - nFE = - 2(96 500 C mol -1 ) (0.490 V)

= - 94 570 J mol -1
È Ê ∂E ˆ ˘
DH = - nF Í E - T Á ˜ ˙
Î Ë ∂T ¯ p ˚

= - 2(96 500 C mol -1 ) [(0.490 V) - (298 K) (- 1.86 ¥ 10 -4 V K -1 )]

= - 105 267.6 J mol -1
Ê ∂E ˆ
DS = nF Á ˜ = 2(96 500 C mol -1 ) (- 1.86 ¥ 10 -4 V K -1 )
Ë ∂T ¯ p

= - 35.9 J K -1 mol -1

Example 8.18.5 At 273 K, the calorimetric determination of H for the reaction

Zn(s) + 2AgCl(s) ZnCl2(aq) + Ag(s)

yielded – 217.78 kJ mol–1, while the emf of the corresponding cell was 1.015 V. What
was ( E/ T)p of the cell?

Solution From the expression

È Ê ∂E ˆ ˘
DH = - nF Í E - T Á ˜ ˙
Î Ë ∂T ¯ p ˚

Ê ∂E ˆ 1È DH ˘
we get ÁË ˜¯ = Í E +
∂T p T Î nF ˙˚

Substituting the given data, we get

Ê ∂E ˆ 1 È (- 217 780 J mol -1 ) ˘

ÁË ˜¯ = Í(1.015 V) + ˙
∂T p (273 K) Î 2(96 500 C mol -1 ) ˚
= - 4.154 ¥ 10 -4 V K -1

Example 8.18.6 (a) At 298 K the standard free energy of formation of H2O(1) is – 237.23 kJ mol–1,
while that of its ionization to hydrogen and hydroxyl ions is 79.71 kJ mol–1. What will
be the reversible emf at 298 K of the cell
 Electrochemical Cells 477

Pt | H2(g, 1 bar) | H+(l M) OH–(l M) | O2(g, 1 bar) | Pt

(b) The enthalpy of formation at 298 K of H2O(1) is – 285.85 kJ mol–1, while its enthalpy
of ionization is 56.90 kJ mol–1. Calculate the temperature coefficient of the standard emf
at 298 K for the cell given in part (a).

Solution (a) The given data are

H2(g) + 1
2
O2(g) H2O(l); ∞
D f G298K = - 237.23 kJ mol -1 (i)

H2O(l) H+(aq) + OH–(aq); ∞

DG298K = 79.71 kJ mol -1 (ii)

Pt | H2(g, 1 bar) | H+(l M) OH–(1 M) | O2(g, 1 bar) | Pt; º K=?

E 298
The cell reaction may be obtained as follows:

Electrode Reduction reaction

Right H2O(1) + 1
2
O2(g) + 2e– 2OH–(aq) (iii)
+ –
Left 2H (aq) + 2e H2(g) (iv)

Subtracting Eq. (iv) from Eq. (iii), we get

H2O(l) + 1
2
O2(g) + H2(g) 2H+(aq) + 2OH–(aq)

The above cell reaction can be obtained from the given reactions (i) and (ii) as follows.
1
H2(g) + 2
O2(g) H2O(l)

2 × [H2O(1) H+(aq) + OH–(aq)]

Adding, we get H2O(1) + 1

2
O2(g) + H2(g) 2H+(aq) + 2OH–(aq)

Hence, Gº of the cell reaction is given by

DG∞ = - 237.23 kJ mol -1 + 2(79.71 kJ mol -1 ) = - 77.81 kJ mol -1

Since DG ∞ = - nFE ∞, it follows that

DG ∞ (- 77 810 J mol -1 )
E∞ = - =- = 0.403 J C-1 = 0.403 V
nF 2(96 500 C mol -1 )
(b) The given data are
(v) H2(g) + 1
2
O2(g) H2O(1); ∞
D f H 298K = - 285.85 kJ mol -1

(vi) H2O(1) H+(aq) + OH– (aq); ∞

DH 298K = 56.9 kJ mol -1
The H º of the cell reaction is
∞
DH 298K = - 285.85 kJ mol -1 + 2(56.9 kJ mol -1 ) = - 172.05 kJ mol -1
Now since

È Ê ∂E ∞ ˆ ˘ Ê ∂E ∞ ˆ
DH ∞ = - nF Í E ∞ - T Á ˜¯ ˙ = DG ∞ + nFT ÁË ˜
Î Ë ∂ T p˚ ∂T ¯ p
478 A Textbook of Physical Chemistry

therefore

Ê ∂E ∞ ˆ DH ∞ - DG ∞
ÁË ˜ =
∂T ¯ p nFT

Substituting the data, we get

Ê ∂E ∞ ˆ - 172 050 J mol -1 - (-77 810 J mol -1 )

ÁË ˜¯ =
∂T p 2(96 500 C mol -1 )(298 K)
= - 0.001 64 V K -1

2. DETERMINATION OF EQUILIBRIUM CONSTANT FROM STANDARD CELL

POTENTIAL
Derivation of the The standard equilibrium constant of a reaction is related to the standard free
Expression energy of the reaction by the relation

∞
DG∞ = - RT ln Keq

Now since Gº = – nFE cell

º , it follows that

∞ = - RT ln Keq
- nFEcell ∞

RT 2.303 RT
or ∞ =
Ecell ∞ =
ln Keq ∞
log Keq (8.18.7)
nF nF
At 298 K, the above expression becomes

∞ = ÊÁ
0.059 13 V ˆ
Ecell ∞
˜¯ log Keq (8.18.8)
Ë n

For a given chemical reaction, we can construct the appropriate cell and
then determine its E º value from the tabulated values of standard half-cell
potentials. The obtained value of Eº can be substituted in Eq. (8.18.8) to give
the value of the standard equilibrium constant K eqº . The following problems
illustrate the procedure.

Example 8.18.7 Determine the standard equilibrium constant of the following reaction at 298 K.
2Fe3+ + Sn2+ 2Fe2+ + Sn4+

Solution In the given reaction, Fe3+ is reduced to Fe2+ (and hence constitutes right half-cell) and
Sn2+ is oxidized to Sn4+ (constitutes left half-cell). Hence the cell producing the given
reaction is
Pt | Sn2+, Sn4+ Fe3+, Fe2+ | Pt
Its standard potential is

∞ = E ∞ 3+ 2+
Ecell ∞ 4+ 2+
- ESn = 0.771 V - 0.150 V = 0.621 V
Fe , Fe | Pt , Sn | Pt
 Electrochemical Cells 479

∞
nFEcell 2(96 500 C mol -1 ) (0.621 V)
∞ =
Therefore log Keq =
2.303 RT 2.303 (8.314 J K -1 mol -1 ) (298 K)
= 21.005
Hence K ºeq = 1.0 × 1021
The above calculations show that the equilibrium constant of the given reaction
has a very large value. It implies that Sn2+ can reduce Fe3+ quantitatively.

Example 8.18.8 Determine the standard equilibrium constant of the following reaction at 298 K.

2MnO–4 + 6H+ + 5H2C2O4 2Mn2+ + 8H2O + 10CO2

Solution In the given reaction, MnO4– is reduced to Mn2+ (and hence constitutes the right
half-cell) and H2C2O4 is oxidized to CO2 (left half-cell). Thus, the cell producing the
given reaction is

Pt | CO2(g) | H2C2O4(aq) H+(aq), MnO–4(aq), Mn2+(aq) | Pt

Its standard potential is

∞ = E ∞ - 2+ +
Ecell - EH∞ 2 C2 O4 | CO2 | Pt = 1.51 V - (- 0.49 V)
MnO , Mn , H
4 | Pt

= 2.0 V
Now since n = 10, we have

∞
nFEcell 10 (96 500 C mol -1 ) (2.0 V)
∞ =
log Keq =
2.303 RT 2.303 (8.314 J K -1 mol -1 ) 298 K)
= 331

Hence º = 10331
Keq

Thus, the oxidation of oxalic acid by permanganate occurs quantitatively.

Example 8.18.9 Determine the standard equilibrium constant of the following reaction at 298 K.

Cd2+ + 4NH3 Cd(NH3)42+

Solution The two half-cell reactions of a cell producing the above reaction are

Right half-cell Cd2+ + 2e– Cd

Left half-cell Cd(NH3)42+ + 2e– Cd + 4NH3

Hence the cell is

Cd | Cd(NH3)2+
4 , NH3 Cd2+(aq) | Cd

and its standard potential is

∞ = ER∞ - EL∞ = - 0.40 V - (- 0.61 V)

Ecell
= 0.21 V
480 A Textbook of Physical Chemistry

∞
nFEcell 2 (96 500 C mol -1 )(0.21 V)
Thus ∞ =
log Keq = = 7.10
2.303 RT 2.303 (8.314 J K -1 mol -1 )(298 K)
Hence º = 1.26 × 107
K eq

Example 8.18.10 Determine the standard equilibrium constant of the following reaction at 298 K.
Cu(OH)2 Cu2+(aq) + 2OH–(aq)

Solution The two half-cell reactions of a cell producing the above reaction are:
Right half-cell Cu(OH)2 + 2e– Cu + 2OH–(aq)
Left half-cell Cu2+(aq) + 2e– Cu
Hence, the cell is
Cu | Cu2+(aq) OH–(aq) | Cu(OH)2(s) | Cu

with ∞ = ER∞ - EL∞ = - 0.224 V - (0.337 V)

Ecell
= - 0.561 V

∞
nFEcell 2 (96 500 C mol -1 )(- 0.561 V)
Thus ∞ =
log Keq = = - 18.97
2.303 RT 2.303 (8.314 J K -1 mol)(298 K)

Hence º = 1.1 × 10–19

K eq

Example 8.18.11 How would you use the arrangement

Ag | AgI(sat. soln.) | AgI(s) | Ag
to measure the solubility product of silver iodide at 298 K?
Solution The half-cell reactions are
Right half-cell (Reduction) AgI + e– Ag + I–(aq)
Left half-cell (Oxidation) Ag Ag+(aq) + e–
The cell reaction is
AgI Ag+(aq) + I–(aq)
The cell potential is given as
RT RT
∞ -
Ecell = Ecell ∞ -
ln (aAg+ )(aI - ) = Ecell ln Ks∞ (AgI)
F F
At equilibrium, we will have
RT
ln Ks∞ (AgI) = Ecell
∞
F
At 298 K, we have
∞
Ecell (- 0.151 V) - (0.799 V) - 0.950 V
log Ks∞ (AgI) = = =
(2.303 RT/F ) 0.059 13 V 0.059 13 V
= - 16.07
Thus K sº (AgI) = 8.58 × 10–17
 Electrochemical Cells 481

Example 8.18.12 An excess of solid AgCl is added to a 0.1 mol dm–3 solution of Br– ions. Assuming
activity equal to ionic concentration, calculate the concentration of Cl– and Br– ions at
equilibrium.

Solution When AgCl is added to a solution containing Br– ions, the possible reaction that can
take place is
AgCl(s) + Br–(aq) AgBr(s) + Cl–(aq)
The two partial half-cell reactions of the above reaction are
Reduction AgCl + e– Ag + Cl–
Oxidation Ag + Br– AgBr + e–
Hence the above reaction will be produced by the cell
Ag | AgBr | Br–(aq) Cl–(aq) | AgCl | Ag
Its standard emf would be

∞ = E∞ -
Ecell ∞-
- EBr
Cl | AgCl | Ag | AgBr | Ag

Consulting the emfs table, we get

∞ = 0.222 V - 0.095 V = 0.127 V

Ecell

∞ = - RT ln Keq
Now since DG ∞ = - nFEcell ∞ , we get

∞
nFEcell
∞ =
log Keq
2.303 RT

Substituting the data, we get

(1)(96 500 C mol -1 )(0.127 V)

∞ =
log Keq = 2.148
(2.303) (8.134 J K -11 mol -1 ) (298 K)

Hence º = 140.6
K eq
Let x be the concentration of Br– that has converted to Cl– at equilibrium. Thus, we
will have
aCl- [Cl - ] x
Keq = = = = 140.6
aBr - [Br - ] (0.1 mol dm -3 ) - x

Solving for x, we get

x = 0.009 928 mol dm -3

Hence at equilibrium, we have

[Cl - ] = 0.009 928 mol dm -3

[Br - ] = 0.1 mol dm -3 - 0.009 928 mol dm -3 = 0.090 072 mol dm -3

482 A Textbook of Physical Chemistry

Alternative Method of If no electrons flow when a cell is short-circuited, then its emf is zero. At this
Computing Equili- stage, the cell reaction is said to be at equilibrium. The emf of a cell can be zero
brium Constant only when the electrode potentials of the two electrodes are equal. Thus for a
cell reaction at equilibrium, we have
ER = EL (8.18.9)
From the above equality, the value of Kºeq may be computed. The following
example illustrates the procedure.

Example 8.18.13 Compute the equilibrium constant of the following reaction at 298 K:
Zn + Cu2+ Zn 2+ + Cu

Solution The two half-cell reduction reactions are

Right half-cell Cu2+ + 2e– Cu
2+ –
Left half-cell Zn + 2e Zn
and the half-cell potentials are given as

RT 1
ECu2+ ∞ 2+
= ECu - ln
| Cu | Cu
2F aCu2+
RT 1
EZn2+ ∞ 2+
= EZn - ln
| Zn | Zn
2F aZn2+

To start with, let aCu2+ > (aCu2+ )eq and aZn2+ < (aZn 2+ )eq where the subscript eq
represents the activity prevailing at equilibrium. At this stage, the emf of the cell is
positive indicating that ECu2+ | Cu > EZn2+ | Zn. If the cell is allowed to operate reversibly,
aCu2+ decreases whereas aZn2+ is increased. Consequently, ECu2+ | Cu decreases whereas
EZn2+ | Zn is increased. Eventually a stage will be reached where ECu2+ | Cu becomes equal
to EZn2+ | Zn and the cell stops working. The cell reaction at this stage is at equilibrium.
Hence equating the two reduction potentials, we get

RT 1 RT 1
∞ 2+
ECu - ln ∞ 2+
= EZn - ln
| Cu | Zn
2F (aCu2+ )eq 2F (aZn 2+ )eq

On rearranging the above equation, we get

RT (a 2+ )eq
ln Zn ∞ 2+
= ECu ∞ 2+
- EZn
| Cu | Zn
2F (aCu2+ )eq

2F
or log K ∞ = ∞
Ecell
2.303 RT

where Kº is the required standard equilibrium constant and is given as

Ê a 2+ ˆ
K ∞ = Á Zn ˜
Ë aCu2+ ¯ eq
 Electrochemical Cells 483

∞ 2+
Substituting ECu ∞ 2+
and EZn , we get
| Cu | Zn

2 ¥ (96 500 C mol -1 )(0.337 V - (- 0.763 V)]

log K∞ = = 37.207
2.303 ¥ (8.314 J K -1 mol -1 )(298 K)

Hence Kº = 1.6 × 1037

3. DETERMINATION OF ACCURATE VALUE OF DISSOCIATION CONSTANT OF A

WEAK ACID
The accurate value of the dissociation constant of a weak acid HA can be
determined by using the cell

Pt | H 2 (1 bar) | HA(m1 ), NaA(m2 ), NaCl(m3 ) | AgCl(s) | Ag (8.18.10)

where NaA is a salt formed from the given acid HA and the strong base NaOH. In
addition to NaA, the electrolytic solution also contains a salt which contains same
cation as the salt NaA and anion common with that of the electrode anion. In this
particular case, the chosen salt is NaCl. The emf of the above cell is given by
Ecell = ECl - | AgCl | Ag
- EH + | H2 | Pt

RT RT 1
or ∞-
Ecell = ECl - ln aCl - + ln
| AgCl | Ag
F F aH+
RT
∞-
= ECl - ln (aH+ )(aCl - )
| AgCl | Ag F
Replacing the activities in terms of molalities and activity coefficients, we get
RT
∞-
Ecell = ECl - ln (mH¢ + mCl
¢ - )(g H+ g Cl - )
| AgCl | Ag
F
which on rearranging gives

∞-
F (Ecell - ECl )
| AgCl | Ag
= - ln mH¢ + mCl
¢ - - ln g H+ g Cl - (8.18.11)
RT
(aH+ )(aA - ) (mH¢ + g H+ )(mA¢ - g A - )
Now Ka∞ = =
aHA ¢ g HA )
(mHA
Taking logarithm, we get
mH¢ + mA¢ - g H+ g A -
ln Ka∞ = ln + ln (8.18.12)
¢
mHA g HA
Substituting Eq. (8.18.12) in Eq. (8.18.11), we get

∞-
F (Ecell - ECl ) ¢ mCl
mHA ¢- g HA g Cl -
- ln Ka∞
| AgCl | Ag
= - ln - ln
RT mA¢ - g A-
484 A Textbook of Physical Chemistry

∞-
F (Ecell - ECl ) ¢ mCl
mHA ¢- g HA g Cl -
- ln Ka∞
| AgCl | Ag
or + ln = - ln
RT mA¢ - g A-
(8.18.13)
The emf of the cell is measured at various values of mHA, mCl– and mA–.
The left side of Eq. (8.18.13) is evaluated and plotted as a function of the
ionic-strength μ of the solution. The latter can be calculated from the expression

1
m=
2
 ci zi2
i

where the summation is to be carried over all ions in the solution. The graph
obtained is extrapolated to zero ionic strength. As μ approaches zero, all activity
coefficients approach unity. Now according to Eq. (8.18.13), the extrapolated
value (or intercept) is equal to – ln K ºa and hence K ºa can be determined.

4. DETERMINATION OF ACCURATE VALUE OF IONIC PRODUCT OF WATER

The accurate value of ionic product of water can be determined by using the
cell
Pt | H 2 (1 bar) | MOH(m1 ), MCl(m2 ) | AgCl(s) | Ag (8.18.14)

The two half-cell reduction reactions are

Right electrode AgCl + e– Ag + Cl–

Left electrode H+ + e– 1
2
H2

and thus the cell reaction is

AgCl + 1
2
H2 Ag + H+ + Cl–

The emf of the cell is given by

RT
E = E∞ - ln (aH+ )(aCl - )
F
Replacing aH+ by Kwº /aOH–, we get

RT RT a -
E = E∞ - ln K w∞ - ln Cl
F F aOH -
RT RT m¢ - RT g -
= E∞ - ln K w∞ - ln Cl - ln Cl
F F ¢ -
mOH F g OH -

E - E∞ m¢ - g -
or + ln Cl = - ln K w∞ - ln Cl (8.18.15)
RT/F ¢ -
mOH g OH -
 Electrochemical Cells 485

If the left side of Eq. (8.18.15) is plotted as a function of ionic strength

(or ionic strength, which gives a rather better plot) and – ln K wº is determined
as the intercept at μ = 0 where γCl–/γOH– = 1. From the value obtained for
– ln K wº , K wº can be determined.

Example 8.18.14 The following emfs refer to the cell at 298 K:

Pt | H2(l bar) | LiOH(0.01 mol dm–3), LiCl(m) | AgCl(s) | Ag
m/mol dm–3 0.01 0.02 0.05 0.10 0.20
E/V 1.049 5 1.031 5 1.007 3 0.988 5 0.969 4
The standard potential of silver-silver chloride half-cell is 0.222 5 V. Determine the ionic
product of water.
Solution The emf of the given cell is

Ecell = ECl - | AgCl | Ag

- EH + | H2 | Pt

RT
∞-
= ECl - ln (aH+ )(aCl - )
| AgCl | Ag
F

Since K w∞ = (aH+ )(aOH - ) , we have

RT RT a -
∞-
Ecell = ECl - ln K w∞ - ln Cl
| AgCl | Ag
F F aOH -

RT RT ¢
mCl RT g -
or ∞-
Ecell = ECl - ln K w∞ - ln - ln Cl
| AgCl | Ag
F F mOH - F g OH -

On rearranging, we get

∞-
Ecell - ECl ¢ -
mCl g Cl -
= - log K w∞ - log
| AgCl | Ag
+ log (8.18.16)
2.303 RT/F ¢ -
mOH g OH -

Thus if the left side of Eq. (8.18.16) is plotted against ionic strength and extrapolated
to zero ionic strength (where γCl– and γOH– approach unity), the extrapolated value will
be equal to – log K wº . Table 8.18.1 includes the values of left side of Eq. (8.18.16) and
the corresponding ionic strengths for the given values of m of LiCl.

Table 8.18.1 Values of m and the left side of Eq. (8.18.16) For the Various
Values of m

∞-
Ecell - ECl | AgCl | Ag Ê m ˆ
m/mol dm–3 μ /mol dm–3 + log Á
0.059 13 V Ë 0.01 mol dm -3 ˜¯

0.01 0.02 13.986 + 0.000 = 13.986

0.02 0.03 13.682 + 0.301 = 13.983
0.05 0.06 13.273 + 0.699 = 13.972
0.10 0.11 12.955 + 1.000 = 13.955
0.20 0.21 12.631 + 1.301 = 13.932
486 A Textbook of Physical Chemistry

The graph between (Ecell – EºCl– | AgCl | Ag)/0.059 13 V + log (m/0.01 mol dm–3) and
μ is shown in Fig. 8.18.2.

Fig. 8.18.2 Graph

between
{(Ecell – EºCl– | AgCl | Ag)/
0.059 13 V} + log (m/0.01
mol dm–3) and μ

From the graph, we observe that

Intercept = - log K w∞ = pK w∞ = 13.994

Hence K w∞ = 1.01 ¥ 10 -14

5. DETERMINATION OF pH OF A SOLUTION
If the half-cell reaction involves either H+ ion or OH– ion, the electrode potential
depends on the activity of H+ ions in the solution. The latter is usually represented
on the pH scale† which is defined as
pH = – log aH+ – log {[H+]/mol dm–3}
Alternatively, if the electrode potential and the activities (or fugacities if
gases are involved) of species other than H+ ions involved in the half-cell reaction
are known, we can calculate the activity of H+ ions or pH of the solution. Among
the electrodes used to measure pH are the hydrogen electrode, the quinhydrone
electrode and the glass electrode. We now describe these electrodes one by one.
Hydrogen Electrode The equilibrium reaction at the electrode is
H+ + e - = 1
H
2 2

†
In potentiometric method, we involve activities (or effective concentrations) rather than
the concentrations. We can extend the definition to pH = – log aH+ in spite of the fact
that the activity of individual ions has no practical significance. For the operational
definition of pH, See Annexure III.
 Electrochemical Cells 487

The potential adopted is given by

RT ( f H2 /f ∞)1/2
E =- ln
F (aH+ )

Assuming H2 gas to be an ideal gas with its pressure equal to 1 bar, the potential
of the electrode becomes

RT 1 2.303 RT
E =- ln =- pH
F aH+ F

At 298 K, we have

E = - (0.059 13 V) pH (8.18.17)

The hydrogen electrode is coupled with a reference electrode to form the cell.
Reference electrode H3O+ (?) | H2 | Pt
and its emf, Ecell, is determined experimentally. At 298 K, we have

Ecell = ER - EL = - (0.059 13 V) pH - Ereference

Ecell + Ereference
Hence pH = - (8.18.18)
(0.059 13 V)

In practice, the use of hydrogen electrode for determination is severely

limited in that it may not be used in solutions containing reducible materials
and is easily poisoned by catalytic poisons. The latter hinders the establishment
of the equilibrium at the surface and the electrode no longer behaves reversibly.
Quinhydrone Quinhydrone is the name given to the molecular crystal formed between quinone
Electrode (Q) and hydroquinone (QH2). When dissolved in water, the crystal decomposes
into its constituent compounds. The reduction reaction at the electrode is

The quinhydrone electrode consists of a spiral of gold wire immersed in the

solution whose pH is to determined. The solution is saturated with quinhydrone.
The reduction potential of the electrode is given by

RT aQH2
EQ, QH +
∞
= EQ, + - ln (8.18.19)
2 , H | Au QH 2 , H | Au 2F (aQ )(aH+ )2

∞
where EQ, has a value of 0.699 6 V.
QH 2, H+ | Au
488 A Textbook of Physical Chemistry

In solution, the activities of Q and QH2 are equal. Thus Eq. (8.18.19)
modifies to
RT 1
EQ, QH +
∞
= EQ, + - ln
2 , H | Au QH 2 , H | Au 2F (aH+ )2

2.303 RT
or EQ, QH +
∞
= EQ, + - pH (8.18.20)
2 , H | Au QH 2 , H | Au F
The quinhydrone electrode can be coupled with a reference electrode to
form a cell:
Reference electrode H3O+ (?), Q, QH2 | Au
and its emf is determined experimentally. We have

Ecell = ER - EL

2.303 RT
or ∞
Ecell = EQ, + - pH - Ereference
QH 2 , H | Au F
∞
EQ, - Ereference - Ecell
QH 2, H+ | Au
Hence pH =
2.303 RT/F
At 298 K, have

∞
EQ, - Ereference - Ecell
QH 2, H+ | Au
pH = (8.18.21)
0.059 13 V

Limitation of using The linear relation between electrode potential and pH of the solution
Eq. (8.18.21) (Eq. 8.18.20) holds good only up to certain pH value ( up to 8.5). Beyond
this pH, the relation is no longer linear as may be seen from the following
considerations.
The hydroquinone is a weak acid and it dissociates in a stepwise manner
as shown below:

[H + ][HQ - ]
H2 Q H + + HQ - K1 = (8.18.22)
[H 2 Q]

[H + ][Q 2 - ]
HQ - H+ + Q2 - K2 = (8.18.23)
[HQ - ]

Mass-balance expression gives

[H 2 Q]0 = [H 2 Q] + [HQ - ] + [Q 2 - ] (8.18.24)

The [HQ–] and [Q2–] are related to [H2Q] through the equilibrium constants
K1 and K2. Thus
 Electrochemical Cells 489

K1[H 2 Q] K1 K2 [H 2 Q]
[H 2 Q]0 = [H 2 Q] + +
+ (8.18.25)
[H ] [H + ]2

[H 2 Q]0 [H 2 Q]0 [H + ]2
or [H 2 Q] = = (8.18.26)
Ê K1 KK ˆ [H + ]2 + K1[H + ] + K1 K2
ÁË 1 + + 1+ 22 ˜
[H ] [H ] ¯
+

Since the solubility of quinhydrone is low, the activities of Q and QH2 may be
replaced by their concentrations, Substituting the concentration of QH2 from
Eq. (8.18.26) into Eq. (8.18.19), we get

RT È [H 2 Q]0 c∞2 ˘
EQ, QH +
∞
= EQ, + - ln Í ˙
2, H | Au QH 2, H | Au
2F + 2 +
Î [Q]0 ([H ] + K1[H ] + K1 K2 ) ˚
(8.18.27)
where cº is the unit concentration. Since [H2Q]0 = [Q]0, therefore
RT
EQ, QH +
∞
= EQ, + + ln ÈÎ{[H + ]2 + K1[H + ] + K1 K2 }/c∞2 ˘˚
2 , H | Au QH 2 , H | Au 2F
(8.18.28)
Applicability of In acid solution, we have
Eq. (8.18.28)
[H + ]2 >> K1 K2 + K1[H]+

and thus Eq. (8.18.28) reduces to

ln {[H + ] /c∞}
RT
EQ, QH ∞
= EQ, +
2, H+ | Au QH 2, H+ | Au
F

2.303 RT
or EQ, QH ∞
= EQ, - pH (8.18.29)
2, H+ | Au QH 2, H+ | Au
F

If K1[H+] >> [H+]2 + K1K2, then Eq. (8.18.28) becomes

RT 2.303 RT
EQ, QH ∞
= EQ, + ln K1∞ - pH (8.18.30)
2, H+ | Au QH 2, H+ | Au 2F 2F
In alkaline solution where

K1K2 >> K1[H+] + [H+]2

we have

RT
EQ, QH ∞
= EQ, + ln K1∞ K2∞ (8.18.31)
2, H+ | Au QH 2, H+ | Au
2F
that is, the potential is independent of pH.
490 A Textbook of Physical Chemistry

Equation (8.18.29) holds for pH < 7; above this pH hydroquinone undergoes

partial ionization and atmospheric oxidation. The quinhydrone electrode is not
useful if the solution contains oxidizing or reducing substances.

Example 8.18.15 Determine at 298 K for the cell

Pt | Q, QH2, H+ 1 M KCl | Hg2Cl2(s) | Hg(1) | Pt
(a) its emf when pH = 5.0,
(b) the pH when Ecell = 0,
(c) the positive electrode when pH = 7.5.

Solution For the given cell, we have

Electrode Reaction Potential

Right (1 M calomel) ∞
Ecalomel = Ecalomel

Left (quinhydrone) 1
Q +H +e = + - 1
QH 2 EQ, QH + ∞
= EQ,
2 2 2, H | Pt QH 2, H + | Pt

RT 1
- ln
F aH+

The emf of the cell is

∞
Ecell = Ecalomel - EQ, QH
2, H + | Pt

RT 1
∞
= (Ecalomel ∞
- EQ, )+ ln
QH 2, H + | Pt
F aH+

At 298 K, we have

∞
Ecell = (Ecalomel ∞
- EQ, ) + (0.059 13 V) pH
QH 2, H + | Pt

= (0.280 V - 0.699 6 V) + (0.059 13 V) pH

= – 0.419 6 V + (0.059 13 V) pH

Thus, we have

(a) Ecell = - 0.419 6 V + (0.059 13 V) ¥ 5 = - 0.123 9 V

1 0.419 6 V
(b) pH = (Ecell + 0.419 6 V) = = 7.1
(0.059 13 V) 0.059 13 V

(c) Ecell = - 0.419 6 V + (0.059 13 V) ¥ 7.5 = 0.023 9 V

Since Ecell is positive, the cell as written would give a spontaneous reaction. Hence
the calomel electrode acts as the positive terminal of the cell.

Glass Electrode The glass electrode consists of a glass tube terminating in a thin-walled bulb A
as shown in Fig. 8.18.3. A special glass of relatively low melting point and high
electrical conductance is used for this purpose. The bulb contains a solution of
constant hydrogen-ion concentration and an electrode of definite potential. Usually
either silver-silver chloride electrode dipped in 0.1 mol dm–3 solution of hydrochloric
 Electrochemical Cells 491

acid or a platinum wire inserted in a pH 4.0 buffer solution containing a small

quantity of quinhydrone is employed. The bulb is inserted in a solution whose pH
is to be determined. The resulting half-cell is combined with a reference electrode
(say, for example, the calomel electrode) through a salt bridge. This entire assembly
constitutes a cell which may be represented as
Solution of Calomel
Ag AgCl(s) 0.1 mol dm–3 KCl Glass unkown pH
electrode
(8.18.32)

Fig. 8.18.3 Determina-

tion of pH of the solution
with the cell containing
galss electrode

The emf of the cell is given by

Ecell = ER - EL (8.18.33)

where ER is the reduction potential of the reference electrode and EL is that of

the rest of unit, i.e.
Ag | AgCl(s) | 0.1 mol dm–3 HCl | Glass | Experimental solution of unknown pH
(8.18.34)
The value of EL is experimentally found to be dependent on the difference
of pH of solutions on either side of glass. Since pH of the solution within the
bulb remains constant, the potential EL depends on pH of the experimental
solution. This dependence is given by
RT
∞ -
Eglass = Eglass ln aH+
F
2.303 RT
∞
= Eglass + pH (8.18.35)
F
where aH+ is the activity of hydrogen-ions in the experimental solution. The
standard reduction potential of the glass electrode is usually determined
experimentally as all glass electrodes do not have the same value. For this, a buffer
solution of known pH is taken and the glass electrode is dipped into this solution
492 A Textbook of Physical Chemistry

and the emf of the cell (Eq. 8.18.32) is determined. From this emf, Eglass can
be determined as follows:
Ecell = Ecalomel - Eglass
2.303 RT
∞ -
= Ecalomel - Eglass pH
F
2.303 RT
Thus ∞ = Ecalomel - Ecell -
Eglass pH
F
After this, the glass electrode is dipped into the solution whose pH is to
be determined and then pH is calculated with E ºglass found above.
Theory Underlying The theory of glass electrode has been explained on the basis of the transfer of
Glass Electrode hydrogen ions through the glass. The potential set up at the glass-solution
interface is analogous to junction potential between two solutions containing
hydrogen ions (Section 8.20), the value of such a potential is given by
RT a
E = (t- - tH+ ) ln 2 (8.18.36)
F a1
where a2 and a1 are the hydrogen-ion activities of outer and inner solutions,
respectively. Since in the glass electrode only hydrogen ions can move across
the boundary, we have
t- = 0 and tH+ = 1 (8.18.37)
Thus, Eq. (8.18.36) reduces to
RT a
E =- ln 2
F a1
Since a1 is constant (inner solution), it follows that
RT
E = constant - ln a2
F
2.303 RT
or E = constant + pH (8.18.38)
F
Equation (8.18.38) is identical in form with the experimentally derived
Eq. (8.18.35).
Limitations of Glass Because of the high internal resistance of the glass electrode, which may amount
Electrode to as much as 100 million ohms, ordinary potentiometers cannot be used to
measure emf of cell. Instead, special vacuum tube potentiometers are employed.
With the glass electrode, it is possible to measure with an accuracy of about
0.000 5 volt or 0.01 pH unit.
The glass electrode can be used up to pH 9. It is unaffected by poisoning
and oxidizing and reducing agents. If the solution pH is greater than 9, particularly
when sodium ions are present, the experimentally obtained pH value is usually
lower than the true value. This is probably due to infiltration of sodium ions into
 Electrochemical Cells 493

the glass lattice. However, new glasses have been developed with which pH range
can be extended up to 13 or 14.

Example 8.18.16 In a cell consisting of glass electrode in solution with pH of 7.0 and a calomel electrode,
the emf of glass electrode at 298 K was 0.062 V. When a solution of unknown pH
replaced the standard buffer, the glass electrode potential was 0.145 V with the glass
electrode negative. Calculate the unknown pH if during caliberation, the glass electrode was
(a) negative, and (b) positive.
Solution (a) Glass electrode as the negative terminal The emf of the glass electrode at 298 K
is given by
∞ + (0.059 13 V) pH
Eglass = Eglass

where Eºglass is a constant. Its value can be determined from the given data that Eglass
= 0.062 V at pH = 7. Thus

∞ = Eglass - (0.059 13 V) pH = 0.062 V - (0.059 13 V) ¥ 7 = - 0.352 V

Eglass

Thus when Eglass = 0.145 V

∞ )
(Eglass - Eglass 0.145 V + 0.352 V
pH = = = 8.4
0.059 13 V 0.059 13 V
(b) Glass electrode as the positive terminal Here
Eglass = - 0.062 V
Therefore

∞ = Eglass - 0.0591 13 V pH = - 0.062 V - (0.059 13 V) ¥ 7

Eglass
= - 0.476 V

∞ )
(Eglass - Eglass 0.145 V + 0.476 V
Hence pH = = = 10.5
0.059 13 V 0.059 13 V

6. POTENTIOMETRIC TITRATIONS
Principle Underlying The potential measurements provide one of the most important analytical
Potentiometric techniques for carrying out acid-base, redox and precipitation titrations.† The
Titrations equivalence point of titrations can be determined accurately without making use
of any visual indicators. The principle underlying the potentiometric titrations
is the Nernst equation according to which the potential of an electrode depends
upon the activities of reduced and oxidized forms of the involved redox couple.
During titration, the activities of these species vary, which in turn, varies the
potential of the electrode. The variation in potential is gradual in the beginning
but becomes faster as the equivalence point is reached. The variation is maximum
at the equivalence point and becomes lesser and lesser beyond the equivalence
point. Thus at the equivalence point, one observes a point of inflexion.

†
See Section 8.19 for the construction of potentiometric titration curves.
494 A Textbook of Physical Chemistry

The potential of the electrode under study (known as indicator electrode)

is determined as usual by combining it with a reference electrode and then
determining the emf of the cell. Calomel electrode is usually employed as the
reference electrode. The equivalence point of titration is determined graphically.
A plot between the potential of the electrode (or the emf of the constructed
cell) and the volume of added titrant is drawn. Figure 8.18.4 displays a typical
variation in the potential of electrode against the volume of added titrant. The
equivalence point of the titration which corresponds to the point of inflexion can
be determined from the graph and the corresponding abscissa gives the volume
of added titrant at the equivalence point.
Location of A more exact method to locate the equivalence point is to construct a graph
Equivalence Point between E/ V and V, where V stands for the volume of titrant added. Figure
8.18.5 displays the typical graph of E/ V versus V. The maximum on the curve
gives the equivalence point of the titration. In addition to the above procedure, a
– – –
graph of 2E/ V2 versus V or ( V/ E)/V versus V, where V is the mean volume
at each point, may be drawn (Figs 8.18.6 and 8.18.7). In the graph of second
derivative, the second derivative has a zero value at the equivalence point and
has different signs before and after the equivalence point. In the graph between
– –
( V/ E)/V and V, two straight lines are observed whose intersection point gives
the equivalence point.

Fig. 8.18.4 A typical potentiometric Fig. 8.18.5 A typical first derivative

titration curve graph

Applicability of Potentiometric titrations constitute the most versatile method of electrochemical

Potentiometric analysis and practically every analytical determination of both inorganic and
Titrations organic systems carried out with classical method could be performed
potentiometrically. The technique offers notable advantages in extending the range
of usefulness of conventional methods. For example, the titration between weak
acid and weak base, titrations in coloured solutions, titrations in non-aqueous
media (where indicators cannot be used), and differential determinations of two
or more than two substances with different solubility products or with different
redox potentials can be carried out by using the potentiometric method.
 Electrochemical Cells 495

Fig. 8.18.6 A typical second derivative Fig. 8.18.7 A typical graph between
– –
graph ( V/ E)/V and V (Gran’s method)

8.19 CONSTRUCTION OF POTENTIOMETRIC TITRATION CURVES

In this section, we describe the procedure for constructing potentiometric titration
curves for (1) acid-base titrations, (2) redox titrations, and (3) precipitation
titrations.
Throughout this section, activity of an ion is replaced by the numerical
value of its concentration.

ACID-BASE TITRATIONS
In acid-base titrations, the hydrogen-ion concentration varies during the course of
titration. The indicator electrode employed in titration is either the quinhydrone
electrode or the glass electrode. The potential of the electrode is given as follows.
Quinhydrone Electrode
2.303 RT
EQ, QH2 , H+ | Pt
∞ QH , H+
= EQ, | Pt - pH (8.19.1)
2
F
Glass Electrode

2.303 RT
∞ +
Eglass = Eglass pH (8.19.2)
F
Saturated calomel electrode is almost universally employed as the reference
electrode. Thus, the assembly used in potentiometric acid-base titration is
Reference electrode Indicator electrode

i.e. Pt | Hg | Hg2Cl2 | Cl– H+, Q, QH2 | Pt

or Pt | Hg | Hg2Cl2 | Cl– H+ | Glass electrode

496 A Textbook of Physical Chemistry

The emf of the cell is measured at different volume V of added titrant

and then graphs of E of indicator electrode versus V and E/ V versus V are
drawn. From these graphs, the equivalence point of the titration is determined.
From Eqs (8.19.1) and (8.19.2), it may be observed that the potential of either of
electrodes depends linearly on pH of the solution. Thus, the general appearance
of graphs of Ecell versus V and pH versus V will be identical and will differ
only in the scaling factor on the y-axis. Since the titration curves of pH versus
V have already been constructed in Chapter 4 of Vol. 1, construction of the
corresponding potentiometric curves can be carried out following Eq. (8.19.1)
or (8.19.2). For illustration, we construct the potentiometric titration curve of
the titration of a strong acid with a strong base.

TITRATION OF HCI VERSUS NAOH

Let 50 cm3 of 0.1 M HCl solution be titrated against 0.1 M NaOH. The pH of
the solution at different stages of titration as calculated in Chapter 4 of Volume 1
are given in Table 8.19.1. It also includes the calculated values of EQ, QH2, H+ | Pt
–
at 25 °C, E/ V, 2E/ V2 and ( V/ E)/V.
Table 8.19.1 Calculated Data of Potentiometric Titration of 50 cm3 of 0.1 M HCl versus 0.1 M NaOH

Total volume of
base added EQ, QH H + | Pt (DE/DV ) ¥ 102 V (D 2 E/DV 2 ) ¥ 102 (DV/DE ) ¥ 103 /V
2,
pH
cm3 V V cm -3 cm 3 V 2 cm -6 V -1
0 1.0 0.699 6 —
0.60 5 33 400
10.0 1.18 0.639 8 —
0.21 15 31 400
20.0 1.37 0.618 6 —
0.14 25 29 400
30.0 1.60 0.605 0 0.007
0.21 35 13 500
40.0 1.95 0.583 9 0.050
0.68 44.5 3 306
49.0 2.99 0.522 7 0.202
6.64 49.45 304.6
49.9 4.00 0.462 9 120
66.00 49.945 30.3
49.99 5.0 0.403 8 11 920
656 49.994 5 3.05
49.999 6.00 0.344 6 918 000
5 200 49.999 45 0.38
49.999 9 6.79 0.297 9 14 400 000
12 400 49.999 95 0.16
50.0 7.0 0.285 5
12 400 50.000 05 0.16
50.000 1 7.21 0.273 1 –14 400 000
5 200 50.000 55 0.38
50.001 8.00 0.226 3 –918 000
656 50.005 5 3.05
50.01 9.00 0.167 2 –11 920
66 50.055 30.3
50.1 10.0 0.108 0 –120
6.5 50.55 304.6
51.0 10.99 0.049 5 –4.9
1.84 51.5 1 055
52.0 11.30 0.031 1 –0.84
1.00 52.5 1 904
53.0 11.47 0.021 1 –0.22
0.78 53.4 2 396
54.0 11.60 0.013 3
 Electrochemical Cells 497

Figure 8.19.1 displays the graphs of E versus V, E/ V versus V and 2E/ V2

versus V. All the three graphs give 50 cm3 of base at the equivalence point of
the titration.

Fig. 8.19.1 Graphs of E

versus V, E/ V versus V
and 2E/ V2 versus V
498 A Textbook of Physical Chemistry

REDOX TITRATIONS
In redox titrations, the addition of titrant changes the concentrations of reduced
and oxidized forms of reactant; the concentration of one of these increases while
that of the other decreases. This results into the change in the potential of the
electrode which can be determined experimentally or theoretically. The platinum
electrode, which is usually employed as the indicator electrode, is dipped into the
solution of reactant. The potential of the electrode relative to a reference electrode
is measured at different stages of titration and then graphs between E versus V,
E/ V versus V, etc., are plotted to determine the equivalence point. The above
curves can also be drawn theoretically following the procedure given below.
At any stage of titration, the two half reactions for the given redox
titration are separately at equilibrium and their reduction potentials are identical.
The potential of the electrode at any point after the start and up to, but not
including, the equivalence point can be conveniently determined by considering
the reduction reaction involving reduced and oxidized forms of reactant. Beyond
the equivalence point, potential can be determined by considering the reduction
reaction involving the two redox species of titrant.
In order to illustrate the procedure for constructing the titration curve, we
describe in detail two typical titrations, namely, (i) ferrous ions versus ceric ions,
and (ii) acidified ferrous ions versus dichromate ions. These two titrations have
been selected with specific objectives in mind. The titration of Fe2+ versus Ce4+
is perhaps the simplest titration for which the potential data can be calculated
easily. The titration of Fe2+ with CrO 2– 7 has been chosen to justify the use of
diphenylamine in the presence of phosphoric acid and N-phenylanthranilic acid
as the common redox indicators in volumetric analysis of ferrous ions. We now
describe these titrations.
Titration of Ferrous Ions versus Ceric Ions
Let 50 cm3 of 0.1 M Fe2+ be titrated against 0.1 M Ce4+ in a medium 0.5 M with
respect to H2SO4. The values of EºCe4+, Ce3+ | Pt and E Fe
º 3+, Fe2+ | Pt, at 25 °C in this
medium can be taken as 1.459 V and 0.700 V, respectively. The redox reaction is

Fe 2+ + Ce 4+ Æ Fe3+ + Ce3+ (8.19.3)

Degree of Before computing the potential of indicator electrode at various stages of titration,
conversion of Fe2+ it is worthwhile to explore the degree of conversion of Fe2+ to Fe3+ at the
to Fe3+ at the equivalence point. This may be done as follows.
Equivalence Point The equilibrium constant of the above redox reaction is given by

[Fe3+ ][Ce3+ ] (E ∞ 4+ - E ∞ 3+ )/0.059 13 V

, Ce3+ |Pt , Fe2+H+ |Pt
Keq = 2+ 4+
= 10 Ce Fe

[Fe ][Ce ]
= 10(1.459 - 0.700)/0.059 13 = 1012.84 = 6.9 ¥ 1012 (8.19.4)

At the equivalence point, we will have

[Fe3+] = [Ce3+] (8.19.5)
2+ 4+
and [Fe ] = [Ce ] (8.19.6)
 Electrochemical Cells 499

With these, Eq. (8.19.4) gives

[Fe3+ ]2 [Fe3+ ]
= 6.9 ¥ 1012 or = 2.6 ¥ 106 (8.19.7)
[Fe 2+ ]2 [Fe 2+ ]
Since the volume of the solution at the equivalence point will be twice as the
original volume of reactant, we will have
0.1 M
[Fe3+ ] + [Fe 2+ ] = = 0.05 M (8.19.8)
2
From Eqs (8.19.7) and (8.19.8), we get
[Fe 2+ ] = 1.9 ¥ 10 -8 M (8.19.9)

Thus, the concentration of Fe2+ is reduced from 0.1 M to 1.9 × 10–8 M

indicating that the conversion is practically complete.
The potential of indicator electrode at various stages of titration may be computed
as follows.
Potential at the Start To start with, the concentration of Fe2+ in solution is given by
of Titration
[Fe2+] = 0.1 M
Since the solution does not contain Fe3+ (or the concentration of Fe3+ which
may have formed due to the aerial oxidation is not known), it is customary to
leave undefined the value of Eelectrode at the start.
Potential Before the The concentration of Fe2+ and Fe3+ ions at any stage of titration before the
Equivalence Point equivalence point may be determined as follows.
The extent to which the reaction has proceeded may be represented in
terms of fraction f given as
v
f = (8.19.10)
V
where v is the volume of 0.1 M solution of Ce4+ that has been added in the
volume V (= 50 cm3) of 0.1 M solution of Fe2+. The total volume of the solution
will become V + v. The concentration of Fe3+ and Fe2+ will be given by
V
[Fe3+ ] = (0.1 M) f (8.19.11)
V +v

V
and [Fe2+ ] = (0.1 M) (1 - f ) (8.19.12)
V +v
The potential of indicator electrode will be given by

RT [Fe 2+ ]
EFe3+ , Fe2+ ∞ 3+ 2+
= EFe - ln (8.19.13)
| Pt , Fe | Pt
F [Fe3+ ]
500 A Textbook of Physical Chemistry

Substituting [Fe3+] and [Fe2+] from Eqs (8.19.11) and (8.19.12), we have
V
(0.1 M) (1 - f )
RT V +v
EFe3+ , Fe2+ ∞ 3+ 2+
= EFe - ln
| Pt , Fe | Pt V
F
(0.1 M) f
V +v
RT 1- f
or EFe3+ , Fe2+ ∞ 3+ 2+
= EFe - ln (8.19.14)
| Pt , Fe | Pt
F f
From Eq. (8.19.14), it follows that the potential of electrode depends on
the fraction of ferrous ion titrated and not on its initial concentration.
Potential at the The two half-cell potentials are given by
Equivalence Point
RT [Fe 2+ ]
EFe3+ , Fe2+ ∞ 3+ 2+
= EFe - ln (8.19.15)
| Pt , Fe | Pt
F [Fe3+ ]
RT [Ce3+ ]
ECe4+ , Ce3+ ∞ 4+ 3+
= ECe - ln (8.19.16)
| Pt , Ce | Pt
F [Ce 4+ ]
Adding Eqs (8.19.15) and (8.19.16), we get

EFe3+ , Fe2+ + ECe 4+ , Ce3+ ∞ 3+ 2+

= EFe ∞ 4+ 3+
+ ECe
| Pt | Pt , Fe | Pt , Ce | Pt
2+ 3+
RT [Fe ][Ce ]
- ln (8.19.17)
F [Fe3+ ][Ce 4+ ]
As indicated earlier, the two half-cell potentials will be identical at any
stage of titration. Thus Eq. (8.21.17) becomes

1 1 RT [Fe 2+ ][Ce3+ ]
Eelectrode = (E ∞ 3+ 2+ ∞ 4+ 3+
+ ECe )- ln
2 Fe , Fe | Pt , Ce | Pt
2 F [Fe3+ ][Ce 4+ ]
(8.19.18)
Now at the equivalence point, Eqs (8.19.5) and (8.19.6) will also hold
good. With these, Eq. (8.19.18) becomes
1
Eequiv. point = [E ∞ 3+ 2+ ∞ 4+ 3+ ]
+ ECe (8.19.19)
2 Fe , Fe | Pt , Ce | Pt

Potential After the The potential of the electrode may be determined from the expression
Equivalence Point
RT [Ce3+ ]
ECe4+ , Ce3+ ∞ 4+ 3+
= ECe - ln (8.19.20)
| Pt , Ce | Pt
F [Ce 4+ ]
Now the concentration of Ce3+ will vary only due to the dilution effect whereas
that of Ce4+ will increase as more and more Ce4+ solution is added. Thus, we
have

Ê V ˆ Ê V ˆ
[Ce3+ ] = [Fe 2+ ]original Ë = (0.1 M) Ë (8.19.21)
2V + v ¯ 2V + v ¯
 Electrochemical Cells 501

Ê v ˆ
and [Ce 4+ ] = (0.1 M) Ë (8.19.22)
2V + v ¯
where v is the volume of Ce4+ solution added after the equivalence point and
V (= 50 cm3) is the initial volume of the reactant. Substituting Eqs (8.19.21)
and (8.19.22) in Eq. (8.19.20), we get
RT V
ECe4+ , Ce3+ ∞ 4+ 3+
= ECe - ln (8.19.23)
| Pt , Ce | Pt
F v
Display of Computed Table 8.19.2 shows the data obtained from Eqs (8.19.14), (8.19.19) and (8.19.23)
Potentials at various stages of titration of Fe2+ versus Ce4+.

Table 8.19.2 Calculated Data of Potentiometric Titration of 50 cm3 of 0.1 M Fe2+

versus 0.1 M Ce4+

EElectrode (DE/DV ) ¥ 102 (D 2 E/DV 2 ) ¥ 102

Volume of f V/cm 3
V V cm -3 V 2 cm -6
Ce4+/cm3
0.0
10.0 0.2 0.66
20.0 0.4 0.69
0.2 25
30.0 0.6 0.71 0.01
0.3 35
40.0 0.8 0.74 0.013
0.4 42.5
45.0 0.9 0.76 0.13
1.0 47.0
49.0 0.98 0.80 1.3
4.0 49.25
49.5 0.99 0.82 13
10 49.7
49.90 0.998 0.86 140
40 49.925
49.95 0.999 0.88 7 200
400 49.975
50.00 1.0 1.08 0
400 50.025
50.05 — 1.28 –7 200
40 50.075
50.10 — 1.30 –140
10 50.3
50.50 — 1.34 –13
4.0 50.75
51.00 — 1.36 –1.3
1.0 53.0
55.00 — 1.40 –0.013
0.4 57.5
60.00 — 1.42
502 A Textbook of Physical Chemistry

Figure 8.19.2 displays the graphs obtained for E versus V, E/ V versus V and
2
E/ V2 versus V. Note that the graph of E versus V is symmetrical around the
equivalence point.

Fig. 8.19.2 Graphs of E

versus, V, E/ V versus V
and 2E/ V2 versus V
 Electrochemical Cells 503

Titration of Ferrous Ions versus Dichromate Ions

Let 50 cm3 of an acid solution (pH = 1.0) of 0.1 M Fe2+ be titrated against
(0.1 M/6), i.e. 0.1 N dichromate solution. The two half-cell reduction reactions are:
Cr2 O27 - + 14H + + 6e - Æ 2Cr 3+ + 7H 2 O
Fe3+ + e - Æ Fe 2+

∞ 3+ 2+
The values of EFe and EC∞ O2- , Cr3+ , H+ | Pt are 0.770 V and 1.330 V,
, Fe | Pt 2 7
respectively.
The potential of the indicator electrode at various stages of titrations may
be computed as follows.
Potential at the Start To start with, the concentration of Fe2+ in solution is given by
of Titration [Fe2+] = 0.1 M
Since the solution does not contain Fe3+ (or the concentration of Fe3+ which
may have formed due to the aerial oxidation is not known), it is customary to
leave undefined the value of Eelectrode at the start.
Potential Before the The concentration of Fe2+ and Fe3+ may be determined as follows.
Equivalence Point The extent to which the reaction has proceeded may be represented in terms
of fraction f given as
v
f =
V
where v is the volume of 0.1 N solution of Cr2O72– that has been added in the
volume V (= 50 cm3) of 0.1 M solution of Fe2+. The total volume of the solution
will become V + v. The concentrations of Fe3+ and Fe2+ will be given by
V
[Fe3+ ] = (0.1 M) f (8.19.24)
V +v
V
[Fe2+ ] = (0.1 M) (1 - f ) (8.19.25)
V +v
The potential of indicator electrode will be given by
RT [Fe 2+ ]
EFe3+ , Fe2+ ∞ 3+ 2+
= EFe - ln (8.19.26)
| Pt , Fe | Pt
F [Fe3+ ]
Substituting [Fe3+] and [Fe2+] from Eqs (8.19.24) and (8.19.25), we have
RT 1- f
∞ 3+ 2+
EFe3+ , Fe2+ | Pt = EFe - ln (8.19.27)
, Fe | Pt
F f
From Eq. (8.19.27), it follows that the potential of electrode depends on
the fraction of ferrous ions titrated and not on its initial concentration.
Potential at the The two half-cell potentials are given by
Equivalence Point
RT [Fe 2+ ]
EFe3+ , Fe2+ ∞ 3+ 2+
= EFe - ln (8.19.28)
| Pt , Fe | Pt
F [Fe3+ ]
504 A Textbook of Physical Chemistry

RT [Cr 3+ ]2 c∞13
ECr O2- , Cr3+ , H+ ∞ 2- 3+ +
= ECr - ln
2 7 | Pt O , Cr , H
2 7 | Pt
6F [Cr2 O72 - ][H + ]14
(8.19.29)
–3
where cº = 1 mol cm .
Multiplying Eq. (8.19.29) by 6 and then adding to it Eq. (8.19.28), we get
EFe3+ , Fe2+ + 6ECr O2- , Cr3+ , H+ ∞ 3+ 2+
= EFe ∞ 2- 3+ +
+ 6ECr
| Pt 2 7 | Pt , Fe | Pt O , Cr , H | Pt
2 7

RT Ê [Fe ][Cr ] c∞ 2+
ˆ 3+ 2 13
- ln Á 3+ (8.19.30)
F Ë [Fe ][Cr2 O7 ][H ] ˜¯
2 - + 14

The two half-cell potentials will be identical at any stage of titration.

Thus, Eq. (8.19.30) becomes
1
Eelectrode = [E ∞ 3+ 2+ ∞ 2- 3+ +
+ 6ECr ]
7 Fe , Fe | Pt 2O , Cr , H
7 | Pt

1 RT Ê [Fe 2+ ][Cr 3+ ]2 c∞13 ˆ

- ln Á 3+ (8.19.31)
7 F Ë [Fe ][Cr2 O27 - ][H + ]14 ¯˜
From the reaction
Cr2O 2–
7 + 6Fe
2+
+ 14H+ Æ 2Cr3+ + 6Fe3+ + 7H2O
it follows that at the equivalence point
[Fe2+ ] = 6[Cr2 O72 - ] and [Fe3+ ] = 3[Cr 3+ ]

Substituting these in Eq. (8.19.31), we get

1
Eequiv. point = [E ∞ 3+ 2+ ∞ 2- 3+ + ]
+ 6ECr (8.19.32)
7 Fe , Fe | Pt 2 O7 , Cr , H | Pt

1 RT 1 RT
+ ln ([H + ]/c∞)14 - ln (2[Cr 3+ ]/c∞)
7 F 7 F
Potential After the The potential of the electrode may be determined from the expression
Equivalence Point
RT [Cr 3+ ]2 c∞13
ECr O2- , Cr3+ , H+ ∞ 2- 3+ +
= ECr - ln
2 7 | Pt O , Cr , H
2 7 | Pt
6F [Cr2 O72 - ][H + ]14
(8.19.33)
Now the concentration of Cr3+ will vary only due to the dilution effect
whereas that of Cr2O72– will increase as more and more Cr2O72– solution is
added. Thus, we have
1 2+ Ê V ˆ Ê 0.1 M ˆ Ê V ˆ
[Cr 3+ ] = [Fe ]original Ë = (8.19.34)
3 2V + v ¯ Ë 3 ¯ Ë 2V + v ¯
Ê 0.1 M ˆ Ê v ˆ
[Cr2 O2-
7 ]= Ë (8.19.35)
6 ¯ Ë 2V + v ¯
where v is the volume of Cr2O72– solution added after the equivalence point and
V(= 50 cm3) is the initial volume of reactant.
 Electrochemical Cells 505

Substituting Eqs (8.19.34) and (8.19.35) in Eq. (8.19.33), we get

Ï
( ) ¸
2
0.1 V
RT Ô
Ô ÔÔ
∞ 2- 3+ + - 3 2V + v

( )
ECr O2- , Cr3+ , H+ | Pt
= ECr O , Cr , H | Pt
ln Ì ˝
6F Ô 0.1 v ([H + ]/c∞)14 Ô
2 7 2 7

ÔÓ 6 2V + v Ô˛
(8.19.36)
Display of Com- Table 8.19.3 shows the data obtained from Eqs (8.19.27), (8.19.32) and (8.19.36)
puted Potentials at various stages of titration of an acid solution of Fe2+ versus Cr2O72–.

Table 8.19.3 Calculated Data of Potentiometric Titration of 50 cm3 of an Acid

Solution (pH = 1.0) of 0.1 M Fe2+ versus (0.1 M/6) Cr2O72–

Volume of
Cr2O27 - Eelectrode (DE/DV ) ¥ 102 V (DE 2 /DV 2 ) ¥ 102
f
cm 3
V V cm -3 cm 3 V 2 cm -6
0.0
10.0 0.2 0.74
15
20.0 0.4 0.76
25
30.0 0.6 0.78
0.20 35
40.0 0.8 0.80 0.053
0.60 42.5
45.0 0.9 0.83 0.088
1.0 47.0
49.0 0.98 0.87 1.3
4.0 49.25
49.5 0.99 0.89 13
10 49.7
49.9 0.998 0.93 130
40 49.925
49.95 0.999 0.95 6 800
380 49.975
50.0 1.0 1.14 –6 040
76 50.025
50.05 — 1.178 –1 400
4.0 50.075
50.10 — 1.18 –20.0
1.75 50.3
50.5 — 1.187 –2.0
0.60 50.75
51.0 — 1.190 –0.19
0.17 53.0
55.0 — 1.197 –0.024
0.06 57.5
60.0 — 1.200

Figure 8.19.3 displays the graphs of E versus V, E/ V versus V and

2
E/ V2 versus V. Note that the graph of E versus V is not symmetrical around
the equivalence point.
506 A Textbook of Physical Chemistry

Fig. 8.19.3 Graphs of E

versus V, E/ V versus V
and 2E/V2 versus V
 Electrochemical Cells 507

Use of Redox In the routine volumetric titration of Fe2+ versus Cr2O72– in laboratories, we
Indicators make use of diphenylamine in the presence of phosphoric acid and
N-phenylanthranilic acid as the internal indicators. It is worthwhile to consider
here the theory underlying the use of internal indicators in the redox titrations.
In general, a redox indicator is an organic compound which can undergo
oxidation-reduction reaction. The colours of oxidized and reduced forms of
the indicator in solution differ significantly. For example, diphenylamine or
diphenylbenzidine (reduced form) is colourless whereas diphenylbenzidine violet
(oxidized form) is violet in colour. In general, we have two types of redox
indicators depending upon whether H3O+ participitates or does not participitate
in the indicator redox reaction. Thus, we have
(i) Inox + ne– Inred
RT ÏÊ In ˆ ¸
∞ red | Pt -
Eox, red | Pt = Eox, ln ÌÁ red ˜ ˝ (8.19.37a)
nF ÓË In ox ¯ ˛
(ii) Inox + nH3O+ + ne– Inred

RT Ï [In red ] c∞n ¸

∞ - ln Ì + n˝
Eox, red, H+ | Pt
= Eox, red, H+ | Pt
(8.19.37b)
nF Ó[In ox ][H3 O ] ˛
The colour of the solution depends on the ratio [Inred]/[Inox]. On an average,
the solution acquires a distinct colour characteristic of Inred if concentration of
the latter is approximately 10 times (or more) greater than that of Inox and vice
versa. Thus at 298 K, we have:
(i) At
(0.059 V)
∞ red | Pt -
Eox, red | Pt = Eox, (8.19.38a)
n
(0.059 V)
or Eox, red, H+ ∞
= Eox, -
+ (0.059 V) log ([H 3 O+ ]/c∞)
| Pt red, H+ n | Pt

(8.19.38b)
the ratio [Inred]/[lnox] in the solution is (10/1). For this potential, the percentage
conversion of reduced form to oxidized form is
[In ox ] 1
= ¥ 100 = 0.91
[In ox ] + [In red ] (1 + 10)
Thus, most of the indicator is present in the reduced form and the solution
gets the colour characteristic of this form. In fact, the value of E as given by
Eq. (8.19.38a) or (8 19.38b) is the maximum potential up to which the solution
has a distinct colour characteristic of the reduced form of the indicator. At
potentials smaller than this potential still more of the indicator is present in the
reduced form. Thus at
(0.59 V)
E1 £ Eox, red | Pt -
n
508 A Textbook of Physical Chemistry

(0.059 V)
or E1 £ Eox, red, H+ | Pt
- + (0.059 V) log ([H3 O+ ] /cc∞)
n
the solution has a colour characterstic of the reduced form of the indicator.
(ii) At
(0.059 V)
∞ red | Pt +
Eox, red | Pt = Eox, (8.19.39a)
n
(0.059 V)
or Eox, red, H+ ∞
= Eox, + + (0.059 V) log ([H 3 O+ ] /c∞)
| Pt red, H+ | Pt
n
(8.19.39b)
the ratio of [Inred]/[Inox] in the solution is (1/10). For this potential, the percentage
conversion of reduced form to oxidized form is
[In ox ] 10
= ¥ 100 91
[In ox ] + [In red ] (10 + 1)
Thus, most of the indicator is present in the oxidized form and the solution
gets the colour characteristic of this form. In fact, the value of E as given by
Eq. (8.19.39a) or (8.19.39b) is the minimum potential up to which the solution
has a distinct colour characteristic of the oxidized form of the indicator. At
potentials greater than this potential, still more of the indicator is present in
the oxidized form. Thus at
(0.059 V)
E2 ≥ Eox, red | Pt +
n
(0.059 V)
or E2 ≥ Eox, red, H+ | Pt
+ (0.059 V) log ([H3 O+ ]/c∞)
+
n
the solution has a colour characteristic of the oxidized form of the indicator.
Indicator Transition The potential range E1 to E2 is known as indicator transition range and has a
Range value of (0.118/n) V. Within this range, transition of colour of the solution takes
place. Since the transition interval is usually very small (it is maximum when n
= 1), it is usually sufficient to know the value of Eox, red | Pt, called the transition
potential, around which the indicator changes colour. A list of indicators is given
in Table 8.19.4, which includes the colours of reduced and oxidized forms of
each indicator.
Selection of At any stage of titration, the potential Ered, ox | Pt will have the same value as that
Indicators of the indicator electrode. This, in turn, will vary the ratio [red]/[ox] in the solution.
We have seen earlier that the solution potential changes very rapidly
near the equivalence point of the titration. The curve is almost steep near the
equivalence point. Consequently, the ratio [red]/[ox] also changes rapidly near
the equivalence point of the titration. It is obvious that if the steep change in
the potential of the solution near the equivalence point covers the transition
potential of the indicator a change of colour of the solution is expected. Thus,
the selection of indicator must satisfy the following requirement.
The transition potential of redox indicator must coincide with the steep
portion of the titration curve.
 Electrochemical Cells 509

Table 8.19.4 Oxidation-Reduction Indicators

Transition
Indicator Colour of potential at
reduced form oxidized form approximately
pH = 0

5-Nitro-l, 10-phenanthroline Red Pale blue 1.25

iron(II) (nitroferroin)
1, 10-Phenanthroline iron(II) ferroin Red Pale blue 1.11
N-phenylanthranilic acid Colourless Pink 1.08
Erioglaucine A Green Red 1.02
2, 2 -Dipyridineiron(II) Red Pale blue 0.97
Sodium diphenylamine sulphonic Colourless Purple 0.85
acid and sodium diphenylbenzidine
sulpnonic acid
Diphenylamine and diphenylbenzidine Colourless Violet 0.76
Methylene blue Colourless Blue 0.53
Nile blue Colourless Blue 0.41
Indigo tetrasulphonic acid Colourless Blue 0.36
Indigo monosulphonic acid Colourless Blue 0.26

Use of Diphenylamine or Diphenylbenzidine in the Volumetric Estimation of Ferrous Ions

Now the use of diphenylamine or diphenylbenzidine in the presence of phosphoric
acid as the common indicator in the redox titration of Fe2+ versus Cr2O 72– may be
explained as follows.
Diphenylamine undergoes the following oxidation reactions in strong
oxidizing media:
510 A Textbook of Physical Chemistry

The reaction transforming diphenylamine (DPA) to diphenylbenzidine

(DPB) is irreversible, so that the use of diphenylbenzidine instead of diphenylamine
eliminates this step and avoids the consumption of additional titrant. The indicator
reaction is the transformation of diphenylbenzidine to diphenylbenzidine violet
(DPVB). The transition potential in a solution of pH = 0 is 0.76 V at 298 K.
The potential of ferric-ferrous system is 0.77 V. Hence, ferric ions can
oxidize diphenylbenzidine to diphenylbenzidine violet and thus result into a
premature end point What we want is a complete transformation of Fe2+ to Fe3+
by Cr2O72– and then a slight excess of the latter should oxidize the indicator.
This is achieved by adding phosphoric acid in the reactant solution. The ferric
ion forms complex Fe(H2PO4)2+ and thus its concentration in solution is very
much diminished. This, in turn, lowers the potential of ferric-ferrous system as
may be seen from the potential expression

RT [Fe 2+ ]
EFe3+ , Fe2+ ∞ 3+ 2+
= EFe - ln
| Pt , Fe | Pt
F [Fe3+ ]
Thus, the ability of ferric ions to oxidize diphenylamine benzidine indicator
is completely lost. When Fe2+ is completely oxidized to Fe3+ and a slight excess
of Cr2O72– is present, the potential of the solution suffers a steep change which
encompasses the transition potential of the indicator, and hence a change of
colour of the solution takes place.

PRECIPITATION TITRATIONS
In precipitation titrations, the concentration of reactant decreases as a result of
formation of a precipitate with the titrant. If an electrode reversible with the
reactant is dipped into the solution, its potential will vary during the course of
titration. Hence precipitation titration can be carried out potentiometrically. In
order to illustrate the procedure for constructing the titration curve, we describe
below the precipitation titration involving chloride and silver ions.
Titration of Chloride Ions Versus Silver Ions
Let 50 cm3 of 0.1 M Cl– be titrated against 0.1 M Ag+. The silver-silver chloride
electrode can be employed as the indicator electrode. This electrode is reversible
with chloride ions according to the following reaction.
AgCl(s) + e– Ag(s) + Cl–
Its potential is given by the expression
RT
ECl - | AgCl | Ag
∞-
= ECl | AgCl | Ag
- ln ([Cl - ]/c∞) (8.19.40)
F
with ∞-
ECl = 0.222 V
| AgCl | Ag
The potential of the electrode at various stages of titrations may be
computed as follows.
Potential at the Start To Start with, the concentration of Cl– in solution is given by
of Titration [Cl–] = 0.1 M
 Electrochemical Cells 511

Thus, the potential of electrode at 298 K as given by Eq. (8.19.40) is

ECl - | AgCl | Ag
= 0.222 V - (0.059 V) ¥ log (0.1)
= 0.281 V
Potential Before the During titration, the concentration of Cl– decreases. The progress of titration can
Equivalence Point be described by the fraction f which is given as
v
f =
V
where v is the volume of 0.1 M solution of Ag+ that has been added in
V(= 0.50 cm3) of 0.1 M solution of Cl–. The total volume of the solution will become
V + v. The concentration of Cl– during the course of titration will be given as
Ê V ˆ
[Cl - ] = (0.1 M) Ë (1 - f )
V + v¯
The potential of the electrode will be given by

ECl - | AgCl | Ag
∞-
= ECl | AgCl | Ag
-
RT
F
ln {
(0.1) V
V +v }
(1 - f )

Potential at the The concentration of Cl– ions at the equivalence point may be calculated from
Equivalence Point the solubility product of silver chloride. At 25 °C, the latter has a value of
1.56 × 10–10 (mol dm–3)2. Since at equivalence point, the [Cl–] is identical to
[Ag+] it is obvious that

[Cl - ]equiv. point = Ks (AgCl) = 1.56 ¥ 10 -10 M2

= 1.24 ¥ 10 -5 M
The above concentration can be substituted in Eq. (8.19.40) to get the
potential value at the equivalence point.
Potential Beyond Beyond the equivalence point, the concentration of Cl– ions can again be
the Equivalence determined through the solubility product of silver chloride and is given by
Point
Ks 1.56 ¥ 10 -10 M2
[Cl - ] = = (8.19.41)
[Ag+ ] [Ag+ ]
The concentration of Ag+ will be given by
Ê v ˆ
[Ag+ ] = (0.1 M) Ë (8.19.42)
2V + v ¯
where v is the volume of Ag+ solution added after the equivalence point and V
(= 0.50 cm3) is the initial volume of reactant.
Alternatively, the potential of the electrode may be computed from the
expression:

∞ +
RT Ê 1 ˆ
EAg+ = EAg - ln Á (8.19.43)
| Ag | Ag
F Ë ([Ag+ ]/c∞) ˜¯

where ∞ +
EAg = 0.799 V
| Ag
512 A Textbook of Physical Chemistry

Table 8.19.5 shows the data obtained from Eq. (8.19.40) at various stages
of titration of 0.1 M Cl– versus 0.1 M Ag+.
Table 8.19.5 The Calculated Data of Potentiometric Titration of 50 cm3
of 0.1 M Cl– versus 0.1 M Ag+

Volume of
Eelectrode (DE/DV ) ¥ 102 V (D 2 E/DV 2 ) ¥ 10 4
Ag+/cm3 f
V V cm -3 cm 3 V 2 cm -6
0.0 0 0.282
0.10 5.0
10.0 0.2 0.292 0.10
0.11 15.0
20.0 0.4 0.303 0.30
0.14 25.0
30.0 0.6 0.317 0.7
0.21 35.0
40.0 0.8 0.338 2.3
0.38 42.5
45.0 0.9 0.357 10.5
0.80 46.5
48.0 0.96 0.381 50
1.8 48.5
49.0 0.98 0.399 240
3.6 49.25
49.5 0.99 0.417 1 100
8.0 49.65
49.8 0.996 0.441 4 500
17.0 49.85
49.9 0.998 0.458 37 000
54.0 49.95
50.0 1.0 0.512 0.0
54.0 50.05
50.10 — 0.566 –37 000
17.0 50.15
50.20 — 0.583 –4 500
8.0 50.35
50.50 — 0.607 –1 100
3.6 50.75
51.0 — 0.625 –240
1.8 51.5
52.0 — 0.643

Figure 8.19.4 displays the graphs of E versus V, ( E/ V) versus V and ( 2E/ V2)
versus V.
Titration Involving It is possible to titrate a solution containing two (or more) reductants with a
Multiple Redox- standard solution of a suitable oxidant. The curve of Eelectrode versus volume of
System titrant will show two (or more) distinct breaks, one at each equivalence point,
provided that the separation of the E red, º ox | Pt values for the two reductants
is large enough and that the E red, º ox | Pt values for the oxidant is sufficiently
higher than the larger E red,
º ox | Pt value of the reductant system. For example, an
acid solution of Ti3+ and Fe2+ can be titrated against a standard solution of Ce4+.
The values of ETiO∞ 2+ 3+ E∞ and ECe∞ 4+ 3+ at 25 °C in 2 M
, Ti | Pt, Fe3+ , Fe2+ | Pt
2 , Ce | Pt
H2SO4 are 0.10, 0.70 and 1.459 V, respectively.
Thus, first of all, Ti3+ is oxidized to TiO22+ and when it is completely
oxidized, Fe2+ starts oxidizing to Fe3+. The entire potentiometric curve can be
calculated following the procedure given above.
Similarly, multiple acid-base and precipitation titrations can be carried
out potentiometrically. For example, a solution containing Cl– and I– ions
can be titrated against a standard solution of silver nitrate. Two breaks in the
potentiometric curve will be observed; the first break corresponds to the complete
precipitation of I– and the second one to that of Cl–.
 Electrochemical Cells 513

Fig. 8.19.4 Graphs of E

versus V, E/ V versus V
and 2E/ V2 versus V
514 A Textbook of Physical Chemistry

8.20 CONCENTRATION CELLS WITHOUT LIQUID JUNCTION POTENTIAL

Concentration cells are made up of two half-cells which are similar chemically
but differ in the activity of some common component. The common component
may be the electrode or the electrolytic solution. The emf of the cell is due to
the difference in activity of the common component. We describe below three
categories of concentration cells without liquid junction.
Cells with Amalgam Such a cell is formed by two metal amalgam electrodes of different metal activity
Electrodes dipping into a common solution of a soluble salt of the metal. For example, the cell
Pb(Hg)(aPb = a1) | Pb2+(aPb2+) | Pb(Hg)(aPb = a2) (8.20.1)
includes two lead amalgams with activities of lead equal to a1 and a2 immersed
in a solution of lead ions of activity aPb2+. For this cell, we have

Electrode Reduction reaction Reduction potential

RT a
Right Pb2+ + 2e– Pb(Hg)(a2) ER = E ∞ - ln 2 (i)
2F aPb2+
RT a
Left Pb2+ + 2e– Pb(Hg)(a1) EL = E ∞ - ln 1 (ii)
2F aPb2+

Subtracting Eq. (ii) from Eq. (i), we get

Pb(Hg)(a1) Pb(Hg)(a2) (8.20.2)
RT a
and Ecell = ln 1 (8.20.3)
2F a2

Cells with Gas Consider a cell consisting of two hydrogen electrodes operating at different
Electrodes pressures dipping into a common solution of hydrochloric acid:
Operating at
Different Pressures
Pt | H2(p1) | H+(aH+) | H2(p2) | Pt (8.20.4)
We have

Electrode Reduction reaction Reduction potential

RT ( p /p∞ )
Right 2H+ + 2e– H2( p2) ER = - ln 22 (i)
2F aH+

RT ( p /p ∞ )
Left 2H+ + 2e– H2( p1) EL = - ln 12 (ii)
2F aH+

Subtracting Eq. (ii) from Eq. (i), we get

H 2 ( p1 ) Æ H 2 ( p2 ) (8.20.5)

RT p
and Ecell = ln 1 (8.20.6)
2F p2
 Electrochemical Cells 515

Cells with Different This type of cells can be formed by making a composite cell out of two cells
Electrolytic differing only in the activity of the electrolytic solution. For example, the cell
Activities
Pt | H2( p) | H+Cl–(a±)1 | AgCl | Ag (8.20.7)
may be combined with a cell
Pt | H2(p) | H+Cl–(a±)2 | AgCl | Ag (8.20.8)
to give the following composite cell.
Pt | H2( p) | H+Cl–(a±)1 | AgCl(s) | Ag – Ag | AgCl | H+Cl–(a±)2 | H2(p) | Pt
(8.20.9)
The emf of the above cell is the sum of the emfs of two cells separately,
i.e. the emf of the left cell (L) plus the emf of the right cell (R). Thus
Ecell = EL + ER (8.20.10)

= (ECl - | AgCl | Ag
- EH + )
| H2 | Pt L
+ (EH+ , H | Pt
- ECl - )
| AgCl | Ag R
(8.20.11)
2

Writing the Nernst equation for each potential, we obtain

È RT RT ( p/p∞)1/2 ˘
∞-
Ecell = Í ECl - ln (aCl - )1 + ln ˙
| AgCl | Ag
Î F F (aH+ )1 ˚
È RT (p/p∞)1/2 RT ˘
+ Í- ln - ECl∞- + ln (aCl - )2 ˙
| AgCl | Ag
Î F (aH+ )2 F ˚

RT (a + )2 (aCl - )2 2RT (a )
or Ecell = ln H = ln ± 2 (8.20.12)
F (aH+ )1 (aCl - )1 F (a± )1

The net cell reaction is obtained by adding the individual cell reactions.
Thus, we have

Cell Cell reaction

Left AgCl + 1
2
H2 Ag + H+(a1) + Cl–(a1) (i)
Right Ag + H+(a2) + Cl–(a2) AgCl + 1
2
H2 (ii)

Adding Eqs (i) and (ii), we get

H+(a2) + Cl–(a2) H+(a1) + Cl–(a1) (8.20.13)
Note that the emf of the cell (Eq. 8.20.12) may be derived directly from the
cell reaction (Eq. 8.20.13).
If one faraday of electricity is withdrawn from the cell, the net result that is
produced is the transfer of 1 mol of each of hydrogen and chloride ions from the
right-side cell to the left-side cell (Eq. 8.20.13). A cell of this type is called a
concentration cell without transference. The operation of cell is not accompanied
by the direct transfer of electrolyte from one solution to the other. The transference
516 A Textbook of Physical Chemistry

occurs indirectly as the result of chemical reactions at the electrodes. A comparison

of the concentration cell with transference (Section 8.21) with that for the same
solutions without transference shows that the change of type is achieved by
introducing an intermediate electrode AgCl(s) | Ag | AgCl(s) between the two
solutions. In general, a concentration cell with transference, in which the electrodes
are reversible with respect to the cation, can be converted into one without
transference by separating the two solutions by means of an electrode that is
reversible with the anion of the electrolyte. If the end electrodes were the anion
electrodes, then a cell without transference would be obtained by using a suitable
cation electrode to separate the two solutions. One such example is
Ag | AgCl(s) | ZnCl2(a1) | Zn – Zn | ZnCl2(a2) | AgCl(s) | Ag

Example 8.20.1 Find the cell reaction and calculate the potential of the following cell at 298 K.
Cd(s) | CdSO4(0.01 mol kg–1, γ = 0.383), PbSO4(s) | Pb – Pb | PbSO4(s),
CdSO4(1.00 mol kg–1, γ = 0.042) | Cd(s)
Solution The cell reaction can be obtained by adding individual cell reactions.
Cell reaction of left cell We have

Electrode Reduction reaction

Right PbSO4(s) + 2e– Pb(s) + (SO2–
4 )L (i)
Left (Cd2+)L + 2e– Cd(s) (ii)

Subtracting Eq. (ii) from Eq. (i), we get

PbSO4(s) + Cd(s) Pb(s) + (Cd2+)L + (SO42–)L (iii)
Cell reaction of right cell We have

Electrode Reduction reaction

Right (Cd2+)R + 2e– Cd(s) (iv)
–
Left PbSO4(s) + 2e Pb(s) + (SO42–)R (v)

Subtracting Eq. (v) from Eq. (iv), we get

Pb(s) + (Cd2+)R + (SO42–)R PbSO4(s) + Cd(s) (vi)
Adding Eqs (iii) and (vi), we get the overall reaction as given below.
(Cd2+)R + (SO42–)R (Cd2+)L + (SO42–)L
The cell potential is given by

RT ÏÔ (aCd2+ )L (aSO2- )L ¸Ô
Ecell = - ln Ì 4
˝
2F (a ) (a )
ÓÔ Cd2+ R SO24- R ˛Ô

RT (a± )L RT (m± )L (g ± )L
=- ln =- ln
F (a± )R F (m± )R (g ± )R
 Electrochemical Cells 517

Substituting the given data, we get

Ï (0.01)(0.383) ¸
Ecell = - (0.059 13 V) log Ì ˝ = 0.061 5 V
Ó (1.0)(0.042) ˛

Example 8.20.2 Show that the emf of the cell

M(s) | MxXy(a±1) | AxXn(s) | A – A | AxXn(s) | MxXy(a±2) | M(s)
is given by

Ê x + y ˆ RT Ê a±1 ˆ
E =-Ë ln Á
x ¯ yF Ë a±2 ˜¯

Solution The cell reaction can be obtained by adding the individual cell reactions.
Cell reaction of left cell We have

Cell Cell reaction

1 1 1
Right A x X n + e - Æ A + (X x - )L (i)
xn n x
1 1
Left (M y + )L + e - Æ M (ii)
y y

Subtracting Eq. (ii) from Eq. (i), we get the cell reaction

1 1 1 1 1
A x X n + M Æ A + (M y + )L + (X x - )L
xn y n y x

Cell reaction of right cell Here, the cell reaction will be just reverse of the above cell
reaction, i.e.

1 1 1 1 1
A + (M y + )R + (X x - )R Æ A x X n + M
n y x xn y

Adding the two cell reactions, we get

1 1 1 1
(M y + )R + (X x - )R Æ (M y + )L + (X x - )L
y x y x
The cell potential will be given by

RT (a y + )1/L y (a x - )1/L x
E =- ln M 1/y X 1/x
F (aM y + )R (aX x - )R

Multiplying and dividing the right side of the above expression by xy, we get

1 RT (a y + )Lx (a x - )Ly
E =- ln M x X y
x yF (aM y + )R (aX x - )R

Now making use of the expression

518 A Textbook of Physical Chemistry

a±x +y (M x X y ) = (aM y + ) x (aX x - ) y

Ê x + y ˆ RT Êa ˆ
we get E =-Ë ln Á ±1 ˜
x ¯ yF Ë a±2 ¯

Example 8.20.3 Calculate the potential at 298 K of the following cell.

Zn | ZnCl2(m = 0.01 mol kg–1, γ± = 0.708) | AgCl | Ag | AgCl |
ZnCl2(m = 0.10 mol kg–1, γ± = 0.502) | Zn
Solution The cell reaction can be obtained by adding the individual cell reactions.
Cell reaction of left cell We have

Electrode Reduction reaction

Right 2AgCl(s) + 2e– 2Ag(s) + 2(Cl–)L (i)
2+ –
Left (Zn )L + 2e Zn(s) (ii)

Subtracting Eq. (ii) from Eq. (i), we get

2AgCl(s) + Zn(s) 2Ag(s) + (Zn2+)L + 2(Cl–)L (iii)

Cell reaction of right cell We have

Electrode Reduction reaction

Right (Zn2+)R + 2e– Zn(s) (iv)
– –
Left 2AgCl(s) + 2e 2Ag(s) + 2(Cl )R (v)

Subtracting Eq. (v) from Eq. (iv), we get

(Zn2+)R + 2(Cl–)R + 2Ag(s) Zn(s) + 2AgCl(s) (vi)
Adding Eqs (iii) and (vi), we get the overall cell reaction:
(Zn2+)R + 2(Cl–)R (Zn2+)L + 2(Cl–)L
The cell potential is given by

RT ÏÔ (a 2+ )L (aCl 2
- )L ¸Ô RT Ï (a )3 ¸
Ecell = - ln Ì Zn 2 ˝ =- ln Ì ± 3L ˝
2F ÔÓ (aZn 2+ )R (aCl - )R Ô˛ 2F Ó (a± )R ˛
RT ÏÔ (4m¢3 ) (g )3 ¸Ô 3RT Ï (m¢ )L (g ± )L ¸
L ± L
=- ln Ì ˝ =- ln Ì ˝
2F ÓÔ (4m¢ )R (g ± )R ˛Ô
3 3 2F Ó (m¢ )R (g ± )R ˛

where m = m /m°. Substituting the given data, we get

3 Ï (0.01)(0.708) ¸
Ecell = - ¥ (0.059 13 V) ¥ log Ì ˝
2 Ó (0.10)(0.502) ˛
= 0.075 5 V
 Electrochemical Cells 519

8.21 CONCENTRATION CELLS WITH LIQUID JUNCTION POTENTIAL

Development of In a cell if two electrolytic solutions of different concentrations are in contact
Liquid Junction with each other, a potential difference develops across the boundary of the two
Potential solutions. This potential difference is called the liquid junction potential or the
diffusion potential. It arises because of the difference in the rates of diffusion of
positive and negative ions from more concentrated solution to less concentrated
solution. The rate of diffusion of an ion is determined by its transference
number. To illustrate how the liquid junction potential arises, we consider two
hydrochloric acid solutions of different concentrations separated from each
other by a boundary. If the boundary between the two solutions is an open
one, then H+ and Cl– ions will diffuse from more concentrated solution to less
concentrated solution. Since H+ ions can diffuse more rapidly than Cl– ions, an
electrical double layer is formed at the boundary. This gives rise to the liquid
junction potential. Once the electrical double layer is formed, it has an effect
of decreasing the speed of faster moving ion and increasing the speed of slower
moving ion. A steady state is established where both the ions migrate with the
same speed; the ion which moved faster initially leads the march.
Computation of Cell The emf Ecell(wlj) of a cell with liquid junction potential may be computed from
Potential the changes that take place in the cell when one faraday of electricity is
withdrawn from the cell. We can determine the sum of the free-energy
changes of various processes that take place in the cell and then equate it to
– FEcell(wlj), such that

- FEcell(wlj) = Â DGi (8.21.1)

i

Computation of The liquid junction potential may be determined as follows.

Liquid Junction The given cell with liquid junction potential is converted into a cell without
Potential liquid junction by connecting the two electrolytic solutions through a salt
bridge. The emf Ecell(wolj) of the resultant cell without liquid junction potential
is determined. The difference of Ecell(wlj) and Ecell(wolj) gives the value of liquid
junction potential Elj, i.e.
Elj = Ecell(wlj) - Ecell(wolj) (8.21.2)

We now consider the following two types of cells with liquid junction
and derive the expressions of Ecell(wlj), Ecell(wolj) and Elj.

1. CELL IN WHICH ELECTRODES ARE REVERSIBLE WITH RESPECT TO CATION

A Typical Example Consider the cell
Pt | H2(l bar) | HCl(a1) HCl (a2) | H2(l bar) | Pt
The above cell is also shown in Fig. 8.21.1.
Working of the Cell We know that electrons are given out from the left electrode and are fed back
at the right electrode, i.e. electrons flow externally from left to right. Inside the
electrochemical cell, the current is carried by ions. In order to have a complete
520 A Textbook of Physical Chemistry

Fig. 8.21.1 Cell in which

electrodes are reversible
with respect to cations

circuit of flow of electrons, it is obvious that negative ions (which carry the
surplus electrons) will move from right to left and positive ions will move from
left to right. Let t+ and t_ be the transference numbers of positive and negative
ions, respectively. If one faraday of electricity is withdrawn, it is obvious that t+
mole of positive ions will migrate across the liquid junction from left to right
and t_ mole of negative ions from right to left. The changes that take place when
one faraday of electricity is withdrawn from the cell given in Fig. 8.21.1 are
described below.

(i) Electrode reaction at anode 1

H (1
2 2
bar) Æ H + (a1 ) + e -
(ii) Electrode reaction at cathode H + (a2 ) + e - Æ 1
2
H 2 (1 bar)
(iii) Transfer of t+ mole of
H+ from left to right t+H+(a1) t+H+(a2)
(iv) Transfer of t_ mole of Cl– from
right to left t–Cl–(a2) t–Cl–(a1)
The net change in the cell is obtained by adding the above four changes. Thus,
we have
1 H (1
2 2
bar) + H + (a2 ) + t+ H + (a1 ) + t- Cl - (a2 ) Æ H + (a1 ) + 1 H (1 bar)
2 2

+ t+ H + (a2 ) + t- Cl - (a1 )
Cancelling the common term, we get
H+(a2) + t+H+(a1) + t_Cl–(a2) H+(a1) + t+H+(a2) + t_Cl–(a1)
which on rearranging gives
H + (a2 ) - t+ H + (a2 ) + t- Cl - (a2 ) Æ H + (a1 ) - t+ H + (a1 ) + t- Cl - (a1 )

or (1 - t+ )H + (a2 ) + t- Cl - (a2 ) Æ (1 - t+ )H + (a1 ) + t- Cl - (a1 )

or t– H + (a2 ) + t– Cl – (a2 ) Æ t– H + (a1 ) + t– Cl – (a1 )

 Electrochemical Cells 521

Thus, the net cell reaction is to transfer t– mole of HCl from the solution
of activity a2 to that of activity a1.
Free-Energy of Cell The total free energy change of the net cell reaction is
Reaction
DG = t- [ mH+ (a ) + mCl - (a ) - mH+ (a ) - mCl - (a ) ]
1 1 2 2

= t- [{mH∞ + + RT ln (a1 )H+ } + {mCl

∞ - + RT ln (a1 ) - }
Cl

- {mH∞ + + RT ln (a2 )H+ } - {mCl

∞ - + RT ln (a2 ) - }]
Cl

ÔÏ (a1 )H+ (a1 )Cl - Ô¸

= t- RT ln Ì ˝
ÔÓ (a2 )H+ (a2 )Cl - Ô˛
(a )
= 2t- RT ln ±1 HCl (8.21.3)
(a±2 )HCl

Substituting Eq. (8.21.3) in Eq. (8.21.1), we get

RT (a )
Ecell(wlj) = - 2t- ln ±1 HCl (8.21.4)
F (a±2 )HCl

Cell Without Liquid Now if the two solutions of the cell given in Fig. 8.21.1 are connected through
Junction Potential a salt bridge, the liquid junction potential is eliminated. If now one faraday of
electricity is withdrawn, the changes in the two half-cells will only be due to
the electrode reactions. Thus, we have

Electrode reaction at anode 1

H (1
2 2
bar) Æ H + (a1 ) + e -

Electrode reaction at cathode H + (a2 ) + e - Æ 1

2
H 2 (1 bar)

The net cell reaction is

H+(a2) H+(a1)
and the cell potential is

RT (a1 )H+ RT (a )
Ecell(wolj) = - ln =- ln ±1 HCl (8.21.5)
F (a2 )H+ F (a±2 )HCl

where aH+ has been replaced by the mean ionic activity a±.
Expression of Liquid Making use of Eq. (8.21.2), we get
Junction Potential
Elj = Ecell(wlj) - Ecell(wolj)
RT (a ) RT (a )
= - 2t - ln ±1 HCl + ln ±1 HCl
F (a±2 )HCl F (a±2 )HCl
522 A Textbook of Physical Chemistry

RT (a )
= (1 - 2t- ) ln ±1 HCl (8.21.6)
F (a±2 )HCl

Since t+ + t– = 1, Eq. (8.21.6) may be written as

RT (a )
Elj = (t+ - t- ) ln ±1 HCl (8.21.7)
F (a±2 )HCl

Comparing Eqs (8.21.4) and (8.21.5), we get

Ecell(wlj) = 2t- Ecell(wolj) (8.21.8)

If the cell without liquid junction is to function spontaneously, we must

have

(a±2)HCl > (a±1)HCl

since only then Ecell(wolj) as given by Eq. (8.21.5) will have a positive value.
Since tH+ is greater than tCl–, it follows from Eq. (8.21.7) that the liquid junction
potential Elj will have a negative value.

Comment on Liquid In general, the sign and magnitude of the liquid junction potential depends on
Junction Potential the transport numbers of the involved cations and anions. In a cell with
(a±2)HCl > (a±1)HCl, we will have

Elj positive if t– > t+

Elj negative if t– < t+

and Elj zero if t– = t+ (8.21.9)

From Eq. (8.21.8), we get

Ecell(wlj) > Ecell(wolj) if t– > t+

Ecell(wlj) < Ecell(wolj) if t– < t+

and Ecell(wlj) = Ecell(wolj) if t– = t+ (8.21.10)

The results of Eq. (8.21.10) also follow from Fig. 8.21.2 where the separation
of charges across the boundary of the two solutions is shown. The separation
of charges results from the diffusion of ions from a more concentrated solution
(right electrode) to a less concentrated solution (left electrode). When t_ > t+,
the separation of charges across the boundary matches with that of the electrodes
and thus the two potentials, viz., liquid junction Elj and cell potential Ecell(wolj)
have the same sign. Thus on adding the two potentials, we get Ecell(wlj) which is
greater than Ecell(wolj). On the other hand, when t_ < t+, the separation charges
across the boundary is opposite to that of electrodes and thus the two potentials
have different signs which on adding gives Ecell(wlj) < Ecell(wolj).
 Electrochemical Cells 523

Fig. 8.21.2 Correlation of

the sign of liquid junction
potential with the
separation of charges at the
boundary;
(i) t– > t+, Elj is positive and
Ecell(wlj) > Ecell(wolj) and
(ii) t– < t+, Elj is negative
and Ecell(wlj) < Ecell(wolj)

2. CELL IN WHICH ELECTRODES ARE REVERSIBLE WITH RESPECT TO ANIONS

A Typical Example Consider the cell
Ag | AgCl | HCl(a1) HCl(a2) | AgCl | Ag
The above call is also shown in Fig. 8.21.3.

Fig. 8.21.3 A cell in

which electrodes are
reversible with respect to
anions

Working of the Cell The changes that take place when one faraday of electricity is withdrawn from
the cell are shown below:
(i) Electrode reaction at anode Ag(s) + Cl–(a1) AgCl(s) + e–
–
(ii) Electrode reaction at cathode AgCl(s) + e Ag(s) + Cl–(a2)
(iii) Migration of H+ ions +
t+H (a1) +
t+H (a2)
(iv) Migration of Cl– ions t–Cl–(a2) t–Cl–(a1)
The net effect is obtained by adding the above four changes, which gives
Cl - (a1 ) + t+ H + (a1 ) + t- Cl - (a2 ) Æ Cl - (a2 ) + t+ H + (a2 ) + t- Cl - (a1 )

or t+ H + (a1 ) + Cl - (a1 ) - t- Cl - (a1 ) Æ t+ H + (a2 ) + Cl - (a2 ) - t- Cl - (a2 )

t+ H + (a1 ) + t+ Cl - (a1 ) Æ t+ H + (a2 ) + t+ Cl - (a2 )

Thus, the net cell reaction is to transfer t+ mole of HCl from the solution
of activity a1 to that of activity a2.
524 A Textbook of Physical Chemistry

The free energy change of the net cell reaction is

(a2 )H+ (a2 )Cl - (a±2 )HCl
DG = t+ RT ln = 2t+ RT ln
(a1 )H+ (a1 )Cl - (a±1 )HCl

DG RT (a )
Hence Ecell(wlj) = - = - 2t + ln ±2 HCl (8.21.11)
F F (a±1 )HCl

Cell Without Liquid If the cell given by Fig. 8.21.3 functions without liquid junction potential, its
Junction Potential cell reaction would be
Cl–(a1) Cl–(a2)
The cell potential would be

RT (a2 )Cl - RT (a )
Ecell(wolj) = - ln =- ln ±2 HCl (8.21.12)
F (a1 )Cl - F (a±1 )HCl

where aCl– has been replaced by the mean ionic activity a±.

Expression of Liquid Now since

Junction Potential
Elj = Ecell(wlj) – Ecell(wolj)
we get

RT (a ) RT (a )
Elj = - 2t+ ln ±2 HCl + ln ±2 HCl
F (a±1 )HCl F (a±1 )HCl

RT (a )
or Elj = (1 - 2t+ ) ln ±2 HCl (8.21.13)
F (a±1 )HCl

RT (a )
or Elj = (t- - t+ ) ln ±2 HCl (8.21.14)
F (a±1 )HCl

Combining Eqs (8.20.11) and (8.20.12), we get

Ecell(wlj) = 2t+ Ecell(wolj) (8.21.15)
If the cell without liquid junction is to function spontaneously, we must have
(a±1)HCl > (a±2)HCl
since only then Ecell(wolj) as given by Eq. (8.21.12) will have a positive value.
Since tH+ is greater than tCl–, it follows from Eq. (8.21.14) that the liquid
junction potential Elj will have a positive value.
Comment on Liquid In general, the sign and magnitude of the liquid function potential depends on
Junction Potential the transference numbers of involved cations and anions. In a cell with
(a±1)HCl > (a±2)HCl, we will have
 Electrochemical Cells 525

Elj positive if t+ > t–

Elj negative if t+ < t–
and Elj zero if t+ = t– (8.21.16)
From Eq. (8.21.15) we get
Ecell(wlj) > Ecell(wolj) if t+ > t–
Ecell(wlj) < Ecell(wolj) if t+ < t–
and Ecell(wlj) = Ecell(wolj) if t+ = t– (8.21.17)
The results of Eq. (8.21.17) also follows from Fig. 8.21.4 where the
separation of charges across the boundary of the two solutions is shown as a
result of migration ions.

Fig. 8.21.4 Correlation

of the sign of liquid
junction potential with
the separation of charges
at the boundary;
(i) t+ > t–, Elj is positive and
Ecell(wlj) > Ecell(wolj) and
(ii) t+ < t–, Elj is negative
and Ecell(wlj) < Ecell(wolj)

Generalization of From Eqs (8.21.4) and (8.21.11), it may be observed that the transference number
Results which appears in expression of Ecell(wlj) is that of the ionic species with respect
to which the electrodes are not reversible. Expressions of Ecell(wlj), Ecell(wolj) and
Elj of both types of cells discussed above may be written together as shown
below:

RT (a )
Ecell(wlj) = ± 2t ln ±2 HCl (8.21.18)
F (a±1 )HCl

RT (a )
Ecell(wolj) = ± ln ±2 HCl (8.21.19)
F (a±1 )HCl

Ecell(wlj) = 2t Ecell(wolj) (8.21.20)

RT (a )
Elj = (1 - 2t ) ln ±2 HCl
F (a±1 )HCl
RT (a )
= (t- - t+ ) ln ±2 HCl (8.21.21)
F (a±1 )HCl

where the upper and lower signs are meant for cells involving electrodes reversible
with respect to cations and anions, respectively.
526 A Textbook of Physical Chemistry

Use of KCI (or From Eqs (8.21.9) and (8.21.16), it may be observed that Elj is zero if t+ = t–.
NH4NO3) in Salt This fact forms the basis of using potassium chloride (or ammonium nitrate) as
Bridge a bridge in cell measurements involving liquid junction, since the two transport
numbers are very nearly identical in this electrolyte.

Example 8.21.1 Show that the emf of cell

M(s) | MxXy(a±1) MxXy(a±2) | M(s)
is given by

Ê x + y ˆ RT Ê a±1 ˆ
E = - t- Ë ln Á
x ¯ yF Ë a±2 ˜¯

Solution Since the electrode reactions are reversible with respect to cation of charge number y
we write, for the sake of simplicity, the cell reaction for the withdrawal of y faraday of
electricity. The various reactions are:
(i) Reaction at left cell
M (My+)L + ye– (1)
(ii) Reaction at right cell
(My+)R + ye– M (2)
(iii) Transfer of cations from the left to right cell
yt+ equivalent of (My+)L yt+ equivalent of (My+)R
or t+ mole of (My+)L t+ mole of (My+)R i.e. t+(My+)L t+(My+)R (3)
(iv) Transfer of anions from the right to left cell
yt_ equivalent of (Xx–)R yt_ equivalent of (Xx–)L

yt- yt Ê yt ˆ Ê yt ˆ
or mole of (X x - )R Æ - mole of (X x - )L i.e. Ë - ¯ (X x - )R Æ Ë - ¯ (X x - )L (4)
x x x x

Adding Eqs (1) to (4) and rearranging, we get

Ê yt ˆ Ê yt ˆ
t- (M y + )R + Ë - ¯ (X x - )R Æ t- (M y + )L + Ë - ¯ (X x - )L
x x

The free energy change is given by

{ Ê yt ˆ
x }{ Ê yt ˆ
DG = t- (m M y + )L + Ë - ¯ (m X x - )L - t- (m M y + )R + Ë - ¯ (m X x - )R
x }
Writing μ in terms of μ° and activity and cancelling the μº terms, we get

(aM y + )L yt- (a x - )L
DG = t- RT ln + RT ln X
(aM y + )R x (aX x - )R
 Electrochemical Cells 527

Multiplying and dividing the first term by x and merging both the terms, we have

t- (a y + )Lx (a x - )Ly
DG = RT ln M x X y
x (aM y + )R (aX x - )R

Making use of the expression

x +y x y
(a± )M M = (aM y + ) (aX x - )
x y

Ê x + yˆ a
we get DG = t- Ë RT ln ±1
x ¯ a±2

Since y faraday of electricity has been withdrawn, we have

G = – yFE
and thus

Ê x + y ˆ RT Ê a±1 ˆ
E = - t- Ë ln Á
x ¯ yF Ë a±2 ˜¯

Example 8.21.2 Find the cell reaction and calculate the potential of following cell with transference at
298 K.
Pb(s) | PbSO4(s), CuSO4(0.2 mol kg–1, γ = 0.110) CuSO4(0.02 mol kg–1,
γ = 0.320), PbSO4(s) | Pb
2+
The transport number of Cu is 0.370. Is the cell reaction spontaneous, as written?
What would be the cell potential if the above cell is converted into one without liquid
junction potential?

Solution The cell reaction can be obtained by adding various reactions that take place when one
faraday of electricity is withdrawn from the cell. The various reactions are:
(i) Reaction at left electrode (anode)
1
2
Pb(s) + 1
2
(SO24 - )L Æ 1
2
PbSO4 (s) + e- (i)

(ii) Reaction at right electrode (cathode)

1
2
PbSO4 (s) + e- Æ 1
2
Pb(s) + 1
2
(SO24 - )R (ii)

(iii) Transference of cations

t+ equivalent of (Cu2+)L t+ equivalent of (Cu2+)R
or (t+/2) mole of (Cu2+)L (t+/2) mole of (Cu2+)R (iii)
(iv) Transference of anions
t– equivalent of (SO42–)R t– equivalent of (SO42–)L
or (t–/2) mole of (SO42–)R (t–/2) mole of (SO42–)L (iv)
528 A Textbook of Physical Chemistry

Adding Eqs (i) to (iv) and rearranging, we get

t+ t t t
(Cu2+ )L + + (SO24 - )L Æ + (Cu2+ )R + + (SO24 - )R
2 2 2 2
The cell potential is given by

t+ RT ÏÔ (aCu2+ )R (aSO2- )R ¸Ô RT Ï (a ) ¸
Ecell(wlj) = - ln Ì 4
˝ = - t+ ln Ì ± R ˝
2 F (a ) (a
ÓÔ Cu L SO4 L ˛Ô
2+ 2 - ) F Ó (a± )L ˛
RT Ï (m¢ ) (g ) ¸ RT Ï (m¢ )R (g ± )R ¸
= - t+ ln Ì ± R ± R ˝ = - t+ ln Ì ˝
F Ó (m±¢ )L (g ± )L ˛ F Ó (m¢ )L (g ± )L ˛

where m = m /m°. Substituting the given data, we get

Ï (0.02)(0.320) ¸
Ecell(wlj) = - (0.370) (0.059 13 V) log Ì ˝
Ó (0.2)(0.110) ˛
= 0.011 7 V
Since Ecell(wlj) positive, the cell reaction will be spontaneous. Now since

Ecell(wlj) = 2t+ Ecell(wolj)

if follows that

Ecell(wlj) 0.011 7 V
Ecell(wolj) = = = 0.015 81 V
2t+ 2 ¥ 0.370

8.22 COMMERCIAL CELLS

In this section, we describe some of the electrochemical cells which are commonly
employed as sources of electrical energy. The electrochemical cells may be
broadly classified into two categories as described below.

THE PRIMARY CELLS

Such types of cells can be used only so long the active materials are present.
Once these are consumed, the cell cannot be recharged by passage of current
through it, and hence it has to be discarded.
Leclanche or Dry One of the examples is the Leclanche or dry cell represented as
Cell
Zn | NH4Cl(20%), ZnCl2 | MnO2 | C
The reactions involved are:
Anode Zn(s) Zn2+ + 2e–
Cathode 2MnO2(s) + H2O(1) + 2e– Mn2O3(s) + 2OH–
Overall Zn(s) + 2MnO2(s) + H2O(1) Zn2+ + 2OH– + Mn2O3(s)
 Electrochemical Cells 529

The OH– generated in the above electrochemical reaction causes the

following secondary reactions:
NH4Cl + OH– NH3 + Cl– + H2O
Zn2+ + 2NH3 + 2C1– Zn(NH3)2Cl2
Since these reactions are not involved directly in the electrode reactions,
they do not contribute anything towards the cell emf of 1.5 V. Since the cathode
potential is a function of pH, the cell potential falls rapidly on continuous
discharge.
Ruben-Mallory Cell Another example of the primary cell which provides more constant voltage is
the Ruben-Mallory cell. Here the use of a large excess of hydroxyl ions makes
the cell less sensitive to pH change. The cell is represented as
Hg | HgO | KOH | Zn(OH)2 | Zn
The reactions involved are:
Anode Hg(l) + 2OH–(aq) HgO(s) + H2O(1) + 2e–
Cathode Zn(OH)2(s) + 2e– Zn(s) + 2OH–(aq)
Overall Hg(l) + Zn(OH)2(s) HgO(s) + Zn(s) + H2O(1)

THE SECONDARY CELLS

Such types of cells can be used again and again by recharging the cell.
Load Storage Cell One of the examples is the lead storage cell where lead acts as anode and lead
impregnated with lead dioxide acts as cathode. The electrolyte is a solution of
approximately 20 per cent sulphuric acid with a specific gravity of about 1.15
at room temperature. The reactions involved are:
Anode Pb(s) + SO42–(aq) PbSO4(s) + 2e–
Cathode PbO2(s) + 4H+(aq) + SO42–(aq) + 2e– PbSO4(s) + 2H2O(1)
Overall Pb(s) + PbO2(s) + 2H2SO4(aq) 2PbSO4(s) + 2H2O(1)
The emf of the cell depends on the activity of sulphuric acid in solution.
At 25 °C, some of the values are 1.90 V at 7.4 per cent H2SO4, 2.0 V at 21.4
per cent H2SO4, and 2.14 V at 39.2 per cent H2SO4.
To recharge the cell, it is connected with a cell of potential higher than that
of the cell in such a way that the lead storage cell now acts as an electrolytic
cell where lead is deposited on the cathode, lead dioxide is formed at the anode
and H2SO4 is regenerated. The specific gravity of the solution rises due to the
increase in H2SO4 concentration. The recharging is carried out only up to a
certain specific gravity value.
Nicad Cell Another example of the secondary cell is the ‘nicad’ or nickel-cadmium battery.
The anode and cathode are Cd and NiO2, respectively, and the electrolytic
solution is KOH. The reactions are:
530 A Textbook of Physical Chemistry

Anode Cd(s) + 2OH–(aq) Cd(OH2(s) + 2e–

Cathode NiO2(s) + 2H2O(1) + 2e– Ni(OH)2(s) + 2OH–(aq)
Overall Cd(s) + NiO2(s) + 2H2O(1) Cd(OH)2(s) + Ni(OH)2(s)
The emf of the cell is 1.4 V. This cell has comparatively longer life than
a lead storage cell and can be packed in a sealed unit. This cell find its much
applications in electronic calculators and electronic flash.
A Few More A few other examples of secondary cells are:
Examples
1. Edison cell (anode—iron, cathode—nickel oxide, electrolyte—KOH
solution).
2. Silver-Zinc cell (anode—zinc, cathode—silver oxide, electrolyte—KOH
solution).
3. Silver-Cadmium cell (anode—cadmium, cathode—silver oxide,
electrolyte—KOH solution).
The term battery is used wherever a number of cells are connected in
series or in series-parallel.
Fuel Cell Fuel cells are another means by which chemical energy may be converted into
electrical energy. Here the cathode and anode constituents are continually supplied
and thus energy can be withdrawn indefinitely from a fuel cell as long as the
outside supply of fuel is maintained. One of the examples is the hydrogen-oxygen
fuel cell. The cell consists of three compartments separated from one another by
porous electrodes. The hydrogen gas is fed into one compartment and the oxygen
gas is fed into another compartment. These gases then diffuse slowly through the
electrodes and react with an electrolyte that is in the central compartment. The
electrodes are made of a conducting material, such as graphite, with a sprinkling
of platinum to act as a catalyst, and the electrolyte is an aqueous solution of a
base. The reactions are:
Anode H2(g) + 2OH–(aq) 2H2O(1) + 2e–
Cathode O2(g) + 2H2O(1) + 4e– 4OH–(aq)
Overall 2H2(g) + O2(g) 2H2O(1)
One of the advantages of the fuel cells is that the energy is extracted from
the reactants under more nearly reversible conditions. This type of cell finds
great importance in space vehicles.

8.23 SOLVED PROBLEMS

1. A half-cell A consisting of a strip of cobalt dipped into a 1 M solution of Co2+ and
a half-cell B consisting of a strip of chromium dipped into a 1 M solution of Cr3. The
magnitudes of the individual half-cell potentials were then determined as
Co2+ + 2e– Co; | Eº | = 0.277 V
3+ –
Cr + 3e Cr; | E° | = 0.744 V
Answer the following:
(a) When both half-cells were connected separately with the standard hydrogen half-cell,
the metallic electrode was found to be negative. What are the correct signs of the electrode
potentials?
 Electrochemical Cells 531

(b) Will a reaction occur when metallic cobalt is placed in a 1 M solution of Cr3+ and
when metallic chromium is dipped into a 1 M solution of Co2+?
(c) Of the substances, Co, Co2+, Cr and Cr3+, which one is the strongest oxidant and the
strongest reductant?
(d) Cobaltous ion forms complex with ammonia [Co(NH3)6]2+. If ammonium hydroxide
were added to half-cell A, would its electrode potential become more positive, less
positive or be unaffected?
(e) If the half-cells A and B were connected together, which electrode would be negative?
What would be the cell voltage? Suppose the above cell is connected with an external battery
of voltage 1.0 V with (i) negative terminal of the cell attached to the negative terminal of
the external battery, and (ii) negative terminal of the cell attached to the positive terminal
of the external battery. What would be the cell reaction in the two cases?
Solution (a) Since the metallic electrode was found to be negative, we may write the cell as

Co | Co2+ H+ | H2 | Pt (i)

Cr | Cr3+ H+ | H2 | Pt (ii)
The emfs of the above two cells will be positive and are given by

∞
Ecell(i) = EH∞ + ∞ 2+
- ECo ∞ 2+
= - ECo
| H 2 | Pt | Co | Co

∞
Ecell(ii) = EH∞ + ∞ 3+
- ECr ∞ 3+
= - ECr
| H 2 | Pt | Cr | Cr

∞ 2+
Since Eºcells are positive, it is obvious that the potentials ECo ∞ 3+
and ECr must be
| Co | Cr
negative. Hence the values of these potentials are

∞ 2+
ECo = - 0.277 V
| Co

∞ 3+
ECr = - 0.744 V
| Cr

(b) The expected reactions would be

(i) 3Co + 2Cr3+ 3Co2+ + 2Cr
and (ii) 2Cr + 3Co2+ 3Co + 2Cr3+
The cells giving these reactions would be
(i) Co | Co2+ Cr3+ | Cr
(ii) Cr | Cr3+ Co2+ | Co
and the cell potentials would be

∞
Ecell(i) ∞ 3+
= ECr ∞ 2+
- ECo
| Cr | Co
= - 0.744 V - (- 0.277 V) = - 0.467 V
∞
Ecell(ii) ∞ 2+
= ECo ∞ 3+
- ECr
| Co | Cr
= - 0.277 V - (- 0.744 V) = 0.467 V
532 A Textbook of Physical Chemistry

Since E ºcell(ii) is positive, it is obvious that Cr can react with Co2+ whereas Co
cannot react with Cr3+.

∞ 2+
(c) Of the two potentials, ECo is more positive and thus Co2+ ions are more easily
| Co
reducible than Cr ions. Hence Co2+ ions act as a more powerful oxidizing agent
3+

(strongest oxidant). On the other hand, Cr will act as a more powerful reducing agent
(strongest reductant).
(d) The reaction of Co2+ with NH3 is
Co2+ + 6NH3 [Co(NH3)6]2+
which reduces the concentration of free Co2+ ions in solution. The Nernst equation for
the reaction
Co2+ + 2e– Co
RT 1
is given by ECo2+ ∞ 2+
= ECo - ln
| Co | Co
2F a(Co2+ )

Thus, on decreasing the activity of Co2+ ions, the potential ECo2+ | Co will become less
positive.
(e) If the half-cells A and B are connected to give a galvanic cell, then the more negative
electrode will serve as the negative electrode, i.e. the chromium electrode. The potential
would be

∞ = E ∞ 2+
Ecell ∞ 3+
- ECr = - 0.277 V - (- 0.744 V) = 0.467 V
Co | Co | Cr

If this cell is connected with an external battery of 1.0 V in the two given ways, we
would have:
(i) Negative terminal of the cell connected to the negative terminal of the external battery:
Since the potential of the external battery is larger than the emf of the cell, the electrons
will flow from the external battery into the cell. Thus, the given cell will become an
electrolytic cell with the following cell reaction:
At cathode Cr3+ + 3e– Cr (i)
(negative terminal)
At anode Co Co2+ + 2e– (ii)
(positive terminal)
Multiplying Eq. (i) by 2 and Eq. (ii) by 3, then adding we get
2Cr3+ + 3Co 2Cr + 3Co2+
(ii) Negative terminal of the cell connected to the positive terminal of the external battery:
In this case, the electrons flow from the negative terminal of the cell to its positive
terminal through the external battery, i.e. the cell continues to serve as the galvanic cell
with the cell reaction:
2Cr + 3Co2+ 2Cr3+ + 3Co

2. (a) The standard potentials of the two reactions

Mn+ + ne– = M
Mm+ + me– = M
are EM∞ n+ ∞ m + , respectively. Assuming n to be greater than m, show that the
and EM
|M |M
standard potential of the reaction
 Electrochemical Cells 533

Mn+ + (n – m)e– Mm+

is given by
∞ n+
nEM ∞ m+
- mEM
∞ n+ m+
EM = |M |M
,M | Pt
n-m
(b) From the data
(i) Cr3+ + 3e– Cr ∞ 3+
ECr = - 0.74 V
| Cr

(ii) Cr3+ + e– Cr2+ ∞ 3+ 2+

ECr = - 0.40 V
, Cr | Pt

Compute E° for the reaction

(iii) Cr2+ + 2e– Cr
(c) A cell is to be constructed to give a reaction
Cr + 2Cr3+ 3Cr2+
show how it can be constructed by combining the half-cells Cr 3+ | Cr and
Cr3+, Cr2+ | Pt; Cr3+ | Cr and Cr2+ | Cr; and Cr3+, Cr2+ | Pt and Cr2+ | Cr. Do you expect
the same E° value in each case? If not, explain why. Calculate the equilibrium constant
for the above reaction at 298 K.

Solution (a) We have

Electrode Electrode Free energy

reaction potential change

(i) Mn+ + ne– M ∞ n+

EM ∞ n+
DG1 = - nFEM
|M |M

(ii) M m+
+ me–
M E ∞ m+
M |M
∞ m+
DG2 = - mFEM |M

(iii) M n+
+ (n – m)e –
M m+
E ∞ n+
M , M m + | Pt
∞ n+ m+
DG3 = - (n - m) FEM ,M | Pt

Now reaction (iii) can be obtained by subtracting reaction (ii) from reaction (i). Hence,
we must have

DG3∞ = DG1∞ - DG2∞

∞ n+ m+
- (n - m)FEM ∞ n+
= - nFEM ∞ m+
- (- mFEM )
,M | Pt |M |M

∞ n+
nEM ∞ m+
- mEM
Thus ∞ n+ m+
EM = |M |M
,M | Pt
(n - m)
(b) We have:

Electrode Electrode Free energy

reaction potential change

(i) Cr3+ + 3e– Cr ∞ 3+

ECr = - 0.74 V DG1∞ = - 3F (- 0.74 V)
| Cr

(ii) Cr3+ + e– Cr2+ ∞ 3+ 2+

ECr = - 0.40 V DG2∞ = - F (- 0.40 V)
, Cr | Pt

(iii) Cr2+ + 2e– Cr ∞ 2+

ECr =? DG3∞ = - 2FECr
∞ 2+
| Cr | Cr
534 A Textbook of Physical Chemistry

The reaction (iii) can be obtained by subtracting reaction (ii) from reaction (i) Hence,
we must have.

DG3∞ = DG1∞ - DG2∞

∞ 2+
- 2FECr = 3F (0.74 V) - F (0.40 V)
| Cr

2.22 V - 0.40 V 1.82 V

Thus ∞ 2+
ECr =- =- = - 0.91 V
| Cr
2 2

(c) The given cell reaction is

Cr + 2Cr3+ 3Cr2+
The cell giving the above reaction may be constructed as follows.
(i) Using half-cells Cr3+ | Cr and Cr3+, Cr2+ | Pt.
The given reaction may be split into the following half-cell reactions:
Right electrode, Reduction Cr3+ + e– Cr2+
Left electrode, Oxidation Cr Cr3+ + 3e–
Multiplying the former reaction by 3 and then adding it to the latter reaction, we get the
given cell reaction. Thus, the cell would be
Cr | Cr3+ Cr3+, Cr2+ | Pt

with ∞ = E ∞ 3+ 2+
Ecell ∞ 3+
- ECr = - 0.40 V - (- 0.74 V) = 0.34 V
Cr , Cr | Pt | Cr

and Gº = – nFE ºcell = – 3F(0.34 V) = – F (1.02 V)

(ii) Using half-cells Cr3+ | Cr and Cr2+ | Cr.
In this, case, we will have
Right electrode, Reduction Cr3+ + 3e– Cr
2+
Lift electrode, Oxidation Cr Cr + 2e–
Multiplying the former reaction by 2 and the latter reaction by 3 and then on adding,
we get the given cell reaction. Hence, the cell would be
Cr | Cr2+ Cr3+ | Cr

with ∞ = E ∞ 3+
Ecell ∞ 2+
- ECr = - 0.74 V - (- 0.91 V) = 0.17 V
Cr | Cr | Cr

and Gº = – nFE ºcell = – 6F(0.17 V) = – F (1.02 V)

(iii) Using half-cells Cr3+, Cr2+ | Pt and Cr2+ | Cr.
In this case, we have
Right electrode, Reduction Cr3+ + e– Cr2+
Left electrode, Oxidation Cr Cr2+ + 2e–
Multiplying the former reaction by 2 and then adding to it the latter reaction, we get the
given cell reaction. Hence, the cell would be
 Electrochemical Cells 535

Cr | Cr2+ Cr3+, Cr2+ | Pt

with ∞ = E ∞ 3+ 2+
Ecell ∞ 2+
- ECr = - 0.40 V - (- 0.91 V) = 0.51 V
Cr , Cr | Pt | Cr

and Gº = – nFEºcell = – 2F(0.51 V) = – F(1.02 V)

In all the three cases discussed above, Eºcell is different since it depends on the make up
of the cell. It may be observed that the value of Gº is the same in all the three cases
as it depends only on the cell reaction.
Calculation of Standard Equilibrium Constant This can be calculated using the expression
G º = – RT In Kº

DG ∞ - F (1.02 V) F (1.02 V)
or ln K ∞ = - =- =
RT RT RT

Ê F ˆ 1.02
or log K ∞ = (1.02 V) Ë = = 17.25
2.303RT ¯ 0.059 13

Hence K º = 1.78 × 1017

3. Given the cell

Cd | Cd(OH)2(s) | NaOH(0.01 mol kg–1) | H2(l bar) | Pt
with Ecell = 0.0 V at 298 K. If EºCd2+ | Cd = – 0.40 V. Calculate (a) Ks for Cd(OH)2, and
(b) G, S and H for the cell reaction if ( E/ T)p = 0.002 V K–1.

Solution For the given cell

Cd | Cd(OH)2(s) | NaOH(0.01 mol kg–1) | H2(l bar) | Pt
we have:

Electrode Reduction reaction

Right 2H+ + 2e– H2 (i)
Left Cd2+ + 2e– Cd (ii)

Subtraction of Eq. (ii) from Eq. (i) gives the cell reaction:
Cd + 2H+ Cd2+ + H2
The emf of the cell is given by

RT (a 2+ )( f H2 /f ∞)
Ecell = E ∞ - ln Cd
2F (aH+ )2

Assuming fH2 = p(H2) and the fact that p(H2) = 1 bar, we get

RT Ê a 2+ ˆ
Ecell = E ∞ - ln Á Cd2 ˜ (iii)
2F Ë aH+ ¯
536 A Textbook of Physical Chemistry

(a) Equation (iii) may be written as

RT Ê a 2+ a2 - ˆ
Ecell = E ∞ - ln Á Cd2 2OH ˜
2F Ë aH+ aOH - ¯

RT K∞
= E∞ - ln s
2F K w∞2

Substituting the given data, we get

0.059 13 V Ê K∞ ˆ
0 = {0 - ( - 40 V)} - log Á s ˜
2 Ë K w∞2 ¯

Ê K∞ ˆ (0.40 V)
or log Á s ˜ = = 13.527
Ë K w∞ ¯
2 (0.029 57 V)

Ks∞
This gives = 3.36 ¥ 1013
K w∞2

Ks /M3 Ks
i.e. = 3.36 ¥ 1013 or = 3.36 ¥ 1013 M -1
K w2 / M 4 K w2

Hence Ks = (3.36 ¥ 1013 M -1 ) K w2 = (3.36 ¥ 1013 M -1 ) (10 -28 M 4 )

= 3.36 ¥ 10 -15 M3

(b) We have
DG = - nFE = 0
Ê ∂E ˆ
DS = nF Ë ¯ = 2(96 500 C mol -1 )(0.002 V K -1 )
∂T p
= 386 C V K -1 mol -1
, i.e. 386 J K -1 mol -1
DH = DG + T DS = T DS = (298 K) (386 J K -1 mol -1 )
= 115 028 J mol -11 = 115.028 kJ mol -1

4. When metallic copper is shaken with a solution of a copper salt, the reaction
Cu + Cu 2+ 2Cu + proceeds. When equilibrium is established at 298 K,
[Cu ]/[Cu ] = 1.66 × 106 (mol dm–3)–1. If the standard potential of the Cu2+ | Cu
2+ + 2

half-cell is + 0.337 V, what is the standard (reduction) potential of Cu+ | Cu half-cell?

Solution The cell producing the given reaction

Cu + Cu2+ 2Cu+
+
is Cu | Cu Cu+, Cu2+ | Pt
and its standard emf is given by
∞ = E ∞ 2+ +
Ecell ∞+
- ECu (1)
Cu , Cu | Pt | Cu
 Electrochemical Cells 537

The equilibrium constant of the reaction is

[Cu+ ]2 1
Keq = = = 6.024 ¥ 10 -7 mol dm -3
[Cu ] 1.66 ¥ 10 mol -1 dm 3
2+ 6

From the relations

G º = – nFEºcell and G º = – RT ln K ºeq
we can determine E ºcell by using the expression
RT 0.059 13 V
∞ =
Ecell ∞ =
ln Keq ∞;
log Keq (at 298 K)
nF n
Substituting the data, we get

0.059 13 V
∞ =
Ecell log (6.024 ¥ 10 -7 ) = (0.059 13 V) (- 6.22)
1
= - 0.367 8 V (2)

Now the standard potential of Cu2+ | Cu will be related to the potentials of Cu+ | Cu
and Cu2+, Cu+ | Pt. We have

Electrode Reaction Potential G°

(i) Cu+ | Cu Cu+ + e– Cu ∞+
ECu ∞+
- FECu
| Cu | Cu

(ii) Cu2+, Cu+ | Pt Cu2+ + e– Cu+ ∞ 2+ +

ECu ∞ 2+ +
- FECu
, Cu | Pt , Cu | Pt

(iii) Cu2+ | Cu Cu2+ + 2e– Cu ∞ 2+

ECu ∞ 2+
- 2FECu
| Cu | Cu

Adding reactions of Eqs (i) and (ii), we get the reaction of Eq. (iii). Therefore
∞+
- FECu ∞ 2+ +
- FECu ∞ 2+
= - 2FECu
| Cu , Cu | Pt | Cu

or ∞ 2+
ECu = 1 ∞+
[ECu ∞ 2+ +
+ ECu ] (3)
| Cu 2 | Cu , Cu | Pt

From Eqs (1), (2) and (3), we have

∞ 2+ +
ECu ∞+
- ECu = - 0.367 8 V
, Cu | Pt | Cu

∞ 2+ +
ECu ∞+
+ ECu ∞ 2+
= 2ECu = 2 ¥ 0.337 V = 0.674 V
, Cu | Pt | Cu , Cu

∞ 2+ +
Solving for ECu ∞+
and ECu , we get
, Cu | Pt | Pt

∞ 2+ +
ECu ∞+
= 0.153 V and ECu = 0.521 V
, Cu | Pt | Cu

5. When silver chloride is dissolved in a large excess of ammonia, practicaly all silver
can be assumed to exist as Agm(NH3) nm+. Compute the values of m and n using the
following two cells:
Ag | 0.379 × 10–3 M AgCl, 1 M NH3 37.9 × 10–3 M AgCl, 1 M NH3 | Ag
Ecell = 0.118 5 V at 298 K
Ag | 3.4 × 10–3 M AgCl, 1 M NH3 3.4 × 10–3 M AgCl, 0.1 M NH3 | Ag
Ecell = 0.126 3 V at 298 K
538 A Textbook of Physical Chemistry

Solution For the given cells, we have

Electrode Reduction reaction

Right (Agm(NH3) nm+)R + me– m Ag + n(NH3)R (i)
Left (Agm(NH3) nm+)L + me– m Ag + n(NH3)L (ii)

Subtraction of Eq. (ii) from Eq. (i) gives the cell reaction as

(Agm(NH3)nm+)R + n(NH3)L (Agm(NH3)nm+)L + n(NH3)R

The emf of the cell is given by

RT Ê [Ag m (NH3 )m+

n ]L [NH 3 ]R ˆ
n
Ecell = - ln Á
mF Ë [Ag m (NH3 )n ]R [NH3 ]nL ˜¯
m+

For the first cell, we have

Ê 0.059 13 V ˆ Ê 0.379 ¥ 10 -3 ˆ
0.118 5 V = - Ë ¯ log ÁË ˜
m 37.9 ¥ 10 -3 ¯
Ê 0.059 13 V ˆ
=-Ë ¯ (- 2)
m

2 ¥ 0.059 13
Hence m= =1
0.118 5

For the second cell, we have

n
Ê 0.059 13 V ˆ Ê 0.1ˆ
0.1263 V = - Ë ¯ log Ë 1 ¯
m

Since m = 1, we have

0.1263
n= 2
0.059

Thus, the formula of the complex is Ag(NH3)+2.

6. The emf of the cell

Pt | H2(g)( p = 1 bar) | HA1(0.1 M) HA2(0.1 M), QH2, Q | Pt
is found to be 0.731 4 V at 298 K, where HA1 and HA2 are two monoprotic weak acids.
Answer the following:
(a) Which of the two acids is stronger?
(b) How many times is it stronger?
(c) If the dissociation constant of the stronger acid is 2.1 × 10–4 mol dm–3, calculate the
dissociation constant of the other.
(d) What are the values of pH of the two solutions?
 Electrochemical Cells 539

Solution (a) For the given cell, we have

Electrode Reduction reaction

Right Q + 2HR+ + 2e– QH2 (i)
Left 2HL+ + 2e– H2 (ii)

Subtraction of Eq. (ii) from Eq. (i) gives the cell reaction as
H2 + Q + 2H+R 2HL+ + QH2
Since p(H2) = 1 bar, the emf of the cell is given by

RT ÏÔÊ (a + )L ˆ 2 Ê aQH ˆ ¸Ô
E = E∞ - ln ÌÁ H ˜ Á 2
˜˝
2F ÔÓË (aH+ )R ¯ Ë aQ ¯ Ô˛
Assuming aQH2 = aQ, we get
RT Ê (a + )L ˆ
E = E∞ - ln Á H ˜
F Ë (aH+ )R ¯

Now ∞
E ∞ = EQH - EH∞ + | H ∞
= EQH = 0.699 4 V
2, Q, H + | Pt 2 | Pt 2, Q, H + | Pt

With this, the previous expression becomes

RT ÏÔ (a + )L ¸Ô
E = 0.699 4 V - ln Ì H ˝
F ÔÓ (aH+ )R ˛Ô

At 298 K, we have

ÔÏ (a + )L Ô¸
E = 0.699 4 V - (0.059 13 V) log Ì H ˝
ÓÔ (aH+ )R ˛Ô

ÔÏ (a + )L Ô¸ E - 0.699 4 V
or - log Ì H ˝=
ÓÔ (aH+ )R ˛Ô 0.059 13 V

Since E = 0.731 4 V, we get

ÏÔ (a + )L ¸Ô 0.731 4 V - 0.699 4 V
- log Ì H ˝=
ÔÓ (aH+ )R Ô˛ 0.059 13 V

(aH+ )R
or log = 0.541 2
(aH+ )L

(aH+ )R
Hence = 3.477
(aH+ )L

Thus, the acid HA2 is stronger than the acid HA1.

(b) The acid HA2 is 3.477 times stronger than the acid HA1.
(c) For the two acids, we have
(aH+ )L (aA - ) (aH+ )R (aA - )
1 2
K1 = and K2 =
aHA1 aHA2
540 A Textbook of Physical Chemistry

Assuming
(aH+ )L = aA -
1

(aH+ )R = aA -
2

(aH+ )2L
we get K1 = or (aH+ )L = (K1aHA1 )1/2
aHA1

(aH+ )2R
K2 = or (aH+ )R = (K2aHA2 )1/2
aHA2

1/2
(aH+ )R Ê K aHA2 ˆ
Thus =Á 2 ˜
(aH+ )L Ë K1 aHA1 ¯

As the acids are weak, we may assume

aHA1 = aHA2
1/2
(aH+ )R ÊK ˆ
Thus = Á 2˜
(aH+ )L Ë K1 ¯

Since (aH+)R/(aH+)L is equal to 3.477, we get

1/2
Ê K2 ˆ
ÁË K ˜¯ = 3.477
1

Now K2 = 2.1 × 10–4 mol dm–3, therefore

K2 2.1 ¥ 10 -4 mol dm -3
K1 = 2
= = 1.74 ¥ 10 -5 mol dm -3
(3.477) (3.477)2

(d) Assuming activities equal to concentrations, we have

(cH+ )R = (K2cHA2 )1/2 = {(2.1 ¥ 10 -4 mol dm -3 ) (0.1 mol dm -3 )}}1/2

= 4.58 ¥ 10 -3 mol dm -3
(pH)R = - log{(cH+ )R /mol dm -3} = 2.34
(cH+ )L = (K1cHA1 )1/2 = {(1.74 ¥ 10 -5 mol dm -3 ) (0.1 mol dm -3 )}1/2
= 1.32 ¥ 10 -3 mol dm -3
(pH)L = - log {(cH+ }L /mol dm -3} = 2.88

7. Determine the degree of hydrolysis and hydrolysis constant of anilinium hydrochloride

in M/32 solution of salt at 298 K from the following cell data at 298 K:
M
Pt | H2(l bar) | H+(a = 1) || C6H5NH2HCl soln. | H2(l bar) | Pt
32
Ecell = – 0.188 V.
 Electrochemical Cells 541

Solution Since Ecell = ER – EL

therefore ER = Ecell = – 0.188 V

RT ( pH2 /p∞)1/2
Now ER = - ln
F ([H + /c∞])
RT
= ln ([H + ]/c∞); (as p(H 2 ) = 1 bar)
F

Ê F ˆ
Thus log {[H + ]/c∞} = ER Ë
2.303RT ¯

At 298 K, we have

- 0.188 V
log ([H + ]/c∞]) = = – 3.179
(0.059 13 V)

or [H+] = 6.62 × 10–4 mol dm–3

The hydrolysis reaction is
C6H5NH3+ + H2O C6H5NH2 + H3O+
Let α be the degree of hydrolysis. It is obvious that
[H3O+] = cα
where c is the concentration of anilinium hydrochloride solution.

[H3O+ ]
Thus a=
c
Substituting the values, we get

6.62 ¥ 10 -4 M
a= = 2.118 ¥ 10 -2
(1/32) M

[C6H 5NH 2 ][H3O+ ] (ca ) (ca ) ca 2

Now Kh = = =
[C6H 5NH3+ ] c(1 - a ) 1-a
(1 mol dm -3 /32) (2.118 ¥ 10 -2 )2
=
(1 - 0.021 18)
= 1.43 ¥ 10 -5 mol dm -3

8. The standard potentials of the two half-cells

A(x+n)+, Ax+ | Pt and B(y+m)+, By+ | Pt
are E1º and E2º, respectively. If E2º is greater than E1º, answer the following.
(i) The cell
Pt | Ax+(m), A(x+n)+(km) B(y+m)+(n), By+(kn) | Pt
542 A Textbook of Physical Chemistry

was constructed, where k has some constant value. The cell was operated reversibly up
to its exhaustion point, i.e. to a point where no more reaction in the cell takes place and
hence no more current can be withdrawn from the cell. Show that
(a) the half-cell potentials at the exhaustion point are given by the expression

nEL∞ + mER∞
E=
(n + m)

(b) The value of k at the exhaustion point at 298 K is given by the relation

nm( ER∞ - EL∞ )

log ke =
(0.059 13 V)(m + n)

(ii) Which of the following two cells will give a spontaneous cell reaction when
k < ke?
Pt | A(x+n)+(km), Ax+(m) B(y+m)+(n), By+(kn) | Pt
and
Pt | B(y+m)+(n), By+(kn) A(x+n)+(km), Ax+(m) | Pt
Which of the four species is more powerful oxidant and reductant?
Solution (i) The given cell is
Pt | Ax+(m), A(x+n)+(km) By+(kn), B(y+m)+(n) | Pt
Its cell reaction may be obtained as follows:

Electrode Reduction reaction

Right B(y+m)+ + me– By+ (i)
(x+n)+ –
Left A + ne Ax+ (ii)

Multiplying Eq. (1) by n and Eq. (2) by m and then subtracting the latter from the former,
we get
mAx+ + nB(y+m)+ mA(x+n)+ + nBy+ (3)
The cell potential would be

RT Ï [A(x +n)+ ]m [B y + ]n ¸
∞ -
Ecell = Ecell ln Ì x + m (y +m)+ n ˝ (4)
mnF Ó[A ] [B ] ˛

Now as the cell operates, concentrations Ax+ and B(y+m)+ will decrease and those of
A(x+n)+ and By+ will increase. If the concentration x of Ax+ disappear, concentrations of
various species will be:

[A x + ] = m - x
n Ê m - xˆ
[B(y +m)+ ] = n - x = nË
m m ¯
(x +n )+
[A ] = km + x
n Ê km + x ˆ
[B y + ] = kn + x = nË
m m ¯
 Electrochemical Cells 543

From these concentrations, it follows that at any stage of the reaction, we will have

[A x + ] [A(x +n)+ ] m
(y +m )+
= = (5)
[B ] [B y + ] n

(a) The electrode potentials of the two half-cells are given by

RT Ê [B y + ] ˆ
ER = ER∞ - ln Á (y +m)+ ˜ (6)
mF Ë [B ]¯

RT Ê [A x + ] ˆ
EL = EL∞ - ln Á (x +n)+ ˜ (7)
nF Ë [A ]¯

At the exhaustion point (when no current can be withdrawn from the cell), the two
potentials will become identical. The electrode potentials at the exhaustion point can be
obtained by multiplying Eq. (6) by m, and Eq. (7) by n and then adding the resultant
expressions. Thus, we have

RT Ï [B y + ][A x + ] ¸
(mER + nEL ) = (mER∞ + nEL∞ ) - ln Ì (y +m)+ ˝
F Ó[B ][A(x +n)+ ] ˛

RT Ï [A x + ][B y + ] ¸
or (m + n)Ee = (mER∞ + nEL∞ ) - ln Ì (y +m)+ ˝
F Ó[B ][A(x +n)+ ] ˛

Making use of Eq. (5), we get

(m + n)Ee = mER∞ + nEL∞

mER∞ + nEL∞
or Ee = (8)
m+n
(b) At the exhaustion point, Ecell will be zero. Thus from Eq. (4), we get

RT Ï [A(x +n)+ ]m [B y + ]n ¸
∞ =
Ecell ln Ì x + m (y +m)+ n ˝
mnF Ó[A ] [B ] ˛

Let k at the exhaustion point be represented as ke. Substituting the concentrations of

various species in the above expression, we get
RT ÏÔÊ k m ˆ Ê k n ˆ
m n
¸Ô
∞ =
Ecell ln ÌË e ¯ Ë e ¯ ˝
mnF ÓÔ m n ˛Ô
RT
= ln (ke )m+n
mnF
Ê m + n ˆ RT
=Ë ln ke (9)
mn ¯ F
Hence
Ê nm ˆ F ∞
ln ke = Ë Ecell
m + n ¯ RT
544 A Textbook of Physical Chemistry

At 298 K, we have

nm 1
ln ke = (ER∞ - EL∞ ) (10)
m + n (0.059 13 V)
(ii) Let us take the cell
Pt | Ax+(m), A(x+n)+(km) B(y+m)+(n), By+(kn) | Pt
Its emf as given by Eq. (4) is

RT Ï [A(x +n)+ ]m [B y + ]n ¸
∞ -
Ecell = Ecell ln Ì x + m (y +m)+ n ˝
mnF Ó[A ] [B ] ˛

Substituting the given concentrations, we get

ÔÏÊ km ˆ Ê kn ˆ Ô¸
m n
RT RT
∞ -
Ecell = Ecell ln ÌË ¯ Ë ¯ ˝ = Ecell ∞ - ln k m+n
mnF ÔÓ m n Ô˛ mnF

∞ -Ê
m + n ˆ RT
= Ecell Ë mn ¯ F ln k

Making use of Eq. (9), we get

Ê m + n ˆ RT Ê m + n ˆ RT
Ecell = Ë ¯ ln ke - Ë ln k
mn F mn ¯ F

Ê m + n ˆ RT k
Ecell = Ë ln e (11)
mn ¯ F k
Now since k < ke, it follows that ke/k will be greater than one. Thus Ecell as given
by Eq. (11) will be positive. Hence the cell reaction will be spontaneous. Obviously,
the given second cell will not produce the spontaneous cell reaction. From Eq. (3), it
follows that Ax+ is the most powerful reducing agent and B(y+m)+ is the most powerful
oxidizing agent.

REVISIONARY PROBLEMS

8.1 (a) What is the difference between a galvanic cell and an electrolytic cell? Set up
galvanic cells for the following spontaneous reactions:
(i) Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
(ii) Zn(s) + 2AgCl(s) 2Ag(s) + Zn2+(aq) + 2Cl–(aq)
(b) What are the sign conventions of electrodes in galvanic and electrolytic cells?
What types of reaction take place at these electrodes?
8.2 Illustrate with suitable examples, the distinction between a reversible and an irreversible
cell. State the conditions for a thermodynamically reversible cell.
8.3 (a) Explain, why we cannot use a voltmeter for determining the electromotive force
(emf) of a galvanic cell. Describe, briefly the potentiometric method for determining
the emf of a cell.
(b) Describe briefly the construction and working of Weston standard saturated cell.
8.4 (a) Illustrate by taking the example of Daniell cell, the conventions which are adopted
while writing an electrochemical cell.
(b) An electrochemical cell is written as
Pt | H2(g)( p = 1 bar) | HCl(soln)(a1) | AgCl(s) | Ag(s)
 Electrochemical Cells 545

Answer the following:

(i) Which electrode serves as the negative terminal and which one as the positive
terminal?
(ii) In which direction the electrons flow in the external circuit (not shown)?
(iii) What are the half-cell reactions occurring in the left and right half-cells?
(iv) What is the overall cell reaction ?
Suppose now the cell is written in the reverse direction, i.e.,
Ag(s) | AgCl(s) | HCl(soln) (a1) | H2(g)(p = 1 bar) | Pt
What would be the answers to the above four questions? How would you determine
experimentally which of the above two cells lead to the spontaneous reaction?
8.5 Show by taking the typical example of the cell
Pt | H2(g) | H+(a1) Zn2+(a2) | Zn
that the cell reaction can be generated by subtracting the reduction reaction of the
left half-cell (L) from that of the right half-cell (R). Correspondingly, the emf of
the cell can be determined by subtracting the reduction potential of the left half-cell
from that of the right half-cell.
Suppose that the above cell is written in the reverse direction, i.e.
Zn | Zn2+(a2) H+(a1) | H2(g) | Pt
Show that the value of emf of this cell is the same as that of the previous cell but
with the opposite sign.
8.6 Derive the relation between the emf of a cell and the change in the free energy of its
cell reaction. Hence show that the emf of the cell is an intensive property. How would
you predict the nature of a cell reaction (whether spontaneous, or nonspontaneous
or at equilibrium) from the sign of its emf value?
8.7 (a) The escaping tendency of a species carrying zi charge from a phase is represented
~
by the electrochemical potential m defined as
m = m + zi Ff
where μ is the chemical potential and φ is the electrical potential of the phase. Derive
the above expression.
8.8 Derive the Nernst equation for the following half-cells.
(1) Gas-ion half-cell:
(i) The hydrogen-hydrogen ion half-cell.
(ii) The chlorine-chloride ion half-cell.
(iii) The oxygen-hydroxide ion half-cell.
(2) The metal-metal ion half-cell:
(i) Zn-Zn2+ half-cell.
(ii) M-Mn+ half-cell where M can be any metal.
(3) Metal-insoluble salt-anion half-cell:
(i) Silver-silver chloride-chloride half-cell.
(ii) Mercury-mercuric oxide-hydroxide half-cell.
(iii) The calomel half-cell.
(iv) Antimony-antimony oxide-hydroxide half-cell.
8.9 (a) What do you understand by the term standard electrode potential?
(b) Comment upon the statement: The absolute value of an electrode potential cannot
be determined. However, its value relative to a reference electrode whose potential
is taken to be zero may be determined.
(c) Explain to which electrode this arbitrary zero potential is assigned and how are
the values of other electrode potentials determined relative to this electrode?
546 A Textbook of Physical Chemistry

8.10 Justify the following statements:

∞ n+
(a) If the standard potential EM is positive, then Mn+ ions can be reduced to
|M
M by hydrogen gas under standard conditions.
(b) If the standard potential EM ∞ n+ is negative, then Mn+ ions cannot be reduced
|M
by hydrogen gas under standard conditions. In fact, reverse of the reaction, occurs,
i.e. H+ will be reduced to H2 gas by the metal M.
(c) The compounds of active metals such as Zn, Na and Mg are not reducible by
hydrogen gas under standard conditions while those of noble metals such as Cu and
Ag are reducible by hydrogen gas.
(d) Sign of the electrode potential determines the nature of the electrode (whether a
positive terminal or a negative terminal) of a cell constituted by combining the given
electrode with the standard hydrogen-hydrogen ion electrode and having a positive
emf.
(e) Comparison of the values of two electrode potentials is equivalent to comparing
the relative easiness with which the two reduction reactions can be carried out.
(f) If the two half-cells are combined to make a voltaic cell, the half-cell of a more
positive potential forms a positive terminal whereas the half-cell of lesser positive
potential forms a negative terminal.
(g) Substance which forms the soluble complex (or precipitate) with the oxidized
member of the couple (oxidized form + ne– = reduced form) reduces the reduction
potential of the electrode.
(h) The classification of a metal into noble or active is not absolute but very much
dependent upon its environment. For example, ordinarily Ag is a noble metal but in
the presence of I–, S2– or CN– ions; it becomes an active metal.
8.11 What effect the change in the ionic activity has on the value of electrode potential
involving a reaction M n+ + ne– M? Show how can this change be utilized in
determining the charge on the ion?
8.12 (a) Show that the metal-metal ion half-cell potential EAg+ | Ag is related to the corresponding
metal-insoluble salt-anion half-cell potential EX– | AgX | Ag through the relation
2.303 RT
EX∞ - | AgX | Ag
∞ +
= EAg | Ag
- pKs∞ (AgX)
F
where X– is the halide ion (Cl– or Br– or I–).
(b) It is known that
Ks (AgCl) > Ks (AgBr) > Ks (AgI)
Arrange the potential EX– | AgX | Ag (where X– can be Cl–, Br– and I–) in increasing
order of magnitude.
8.13 Justify the statement:
For a given overall reaction, the value of G is a constant quantity but the emf of
the cell which produces this overall reaction depends on the make up of the cell.
Thus, various cells which produce the same cell reaction and which differ from each
other may have different values of the emf.
Support your answer by constructing cells out of the following half-cells.
(a) Fe2+ + 2e– Fe; ∞ 2+
EFe = – 0.440 V
| Fe

(b) Fe3+ + 3e– Fe; ∞ 3+

EFe = – 0.036 V
| Fe

(c) Fe3+ + e– Fe2+; ∞ 3+ 2+

EFe = 0.771 V
, Fe | Pt
 Electrochemical Cells 547

so as to produce the following cell reaction:

Fe + 2Fe3+ 3Fe2+
8.14 What is a reference half-cell? Outline its merits relative to that of the hydrogen-
hydrogen ion half-cell. Describe the calomel half-cell and derive its Nernst equation.
8.15 Starting from the Gibbs-Helmholtz equation and the relation G = – nFE, derive
the following expressions of H and S.

È Ê ∂E ˆ ˘
DH = - nF Í E - T Á ˜ ˙
Î Ë ∂T ¯ p ˚
Ê ∂E ˆ
DS = nF Á ˜
Ë ∂T ¯ p

What are the units of G, H and S if F is expressed in coulomb mole–1 and E in

volt?
8.16 (a) Show that the standard equilibrium constant of the cell reaction at 298 K can be
computed from the relation

n(E ∞ /volt)
log K ∞ =
0.059 13
(b) Show that the essential condition for a cell reaction to be at equilibrium is
ER = EL
Show from the above equality, how the equilibrium constant of a reaction can be
computed.
8.17 Explain, how can an accurate value of the standard half-cell potential be determined
experimentaly?
8.18 Set up an electrochemical cell which can determine accurately the dissociation
constant of a given weak acid.
8.19 Set up an electrochemical cell with the help of which it is possible to determine
accurately the ionic-product of water.
8.20 Explain by taking an example of AgCl, how solubility product of the latter can be
determined from the emf measurement of a suitable electrochemical cell.
8.21 (a) Define the term pH of a solution. Explain, how the pH value of a solution is
determined by employing the following half-cells.
(i) The hydrogen-hydrogen ion half-cell
(ii) The quinhydrone half-cell.
(iii) The glass half-cell.
(iv) Antimony-antimony oxide-hydroxide half-cell.
(b) Justfy the statement that the linear relationship between the quinhydrone half-cell
potential and pH of the solution, i.e.
2.303 RT
EQ, QH ∞
= EQ, - pH
2, H + | Pt QH 2, H + | Pt
F
holds good only up to certain pH value ( up to 8.5). Beyond this pH, the half-cell
potential is no longer linear and hence cannot be employed in determining the pH
of highly alkaline solutions.
(c) Describe the glass electrode. Explain, how the pH of a solution is determined
by using the glass electrode.
548 A Textbook of Physical Chemistry

8.22 (a) What do you understand by the terms:

(i) Concentration cell without liquid junction?
(ii) Concentration cell with liquid junction?
8.23 Derive the following expressions as applicable to the appropriate concentration cell
without transference.
RT a
(a) Ecell = ln 1 for a cell involving amalgam electrodes
2F a2

RT p
(b) Ecell = ln 1 for a cell involving two gas electrodes operating at different
2F p2
pressures
2 RT (a )
(c) Ecell = ln ±2 for a cell involving different electrolytic concentrations
F (a±1 )
8.24 (a) Describe the factors which are responsible for the liquid junction potential. Derive
the following expressions for a concentration cell with transference involving 1 : 1
electrolyte.
RT (a )
Ewlj = ± 2t ln ±2
F (a±1 )

RT (a )
Ewolj = ± ln ±2
F (a±1 )

Elj = 2t Ewolj

RT (a )
Elj = (1 - 2t ) ln ±2
F (a±1 )
where the upper and lower signs are meant for cells involving electrodes reversible with
cations and anions, respectively, and a±2 and a±1 are the activities of the electrolytes
in the right and left half cells, respectively.
(b) Explain, how is the transport number of either cation or anion determined from
the study of cells with and without transport?
(c) Justify the use of KCl (or NH4NO3) in the salt bridge.
8.25 The standard potentials of the two reactions
Mn+ + ne– = M
and Mm+ + me– = M
are E M
º n+ | M and E ºMm+ | M, respectively, with n > m. Show that for reaction
Mn+ + (n – m)e– = Mm+
the standard potential is given by
∞ n+
nEM ∞ m+
- mEM
∞ n+ m+
EM = |M |M
,M | Pt
(n - m)
8.26 Explain the essential features on which the potentiometric titrations are based. Describe
them with suitable examples.
8.27 Construct the curves of E versus V, E/ V versus V and 2E/ V2 versus V for the
following titrations:
(a) 50 cm3 of 0.1 M HCl versus 0.1 M NaOH.
 Electrochemical Cells 549

(b) 50 cm3 of 0.1 M Fe2+ versus 0.1 M Ce4+.

(c) 50 cm3 of an acid solution (pH = 1.0) of 0.1 M Fe2+ versus 0.016 67 M
(= 0.1 N) Cr2O72–.
(d) 50 cm3 of 0.1 M Cl– versus 0.1 M Ag+.
8.28 What are redox indicators? Describe the working of redox indicators.
8.29 Discuss the role of phosphoric acid in the volumetric titration of Fe2+ versus
Cr2O72– using diphenylamine as the internal indicator.
8.30 Show that the emf of the cell
M | MxXy(a±1) | AxXn(s) | A – A | AxXn(s) | MxXy(a±2) | M
is given by

Ê x + y ˆ RT Êa ˆ
E =-Ë ¯ ln Á ±1 ˜
x yF Ë a±2 ¯
8.31 Show that the emf of the cell
A | AxXn(s) | MxXy(a±1) | M-M | MxXy(a±2) | AxXn(s) | A
is given by

Ê x + y ˆ RT Êa ˆ
E =-Á ˜ ln Á ±2 ˜
Ë y ¯ xF Ë a±1 ¯
8.32 Show that the emf of the cell
M(s) | MxXy(a±l) MxXy(a±2) | M(s)
is given by

Ê x + y ˆ RT Êa ˆ
E = - t- Ë ln Á ±1 ˜
x ¯ yF Ë a±2 ¯
8.33 Show that the emf of the cell
A(s) | AxXn(s) | MxXy(a±1) MxXy(a±2) | AxXn(s) | A(s)
is given by

Ê x + y ˆ RT Êa ˆ
E = - t+ Ë ln Á ±2 ˜
x ¯ xF Ë a±1 ¯

TRY YOURSELF PROBLEMS

8.1 From the standard potential values, predict that out of the members of Group 1 of
the periodic table, lithium and sodium are, respectively, the best and poorest reducing
agents.
8.2 Will the permanganate ion under standard conditions be stable in aqueous medium?
8.3 Compute the potential values given in Example 8.9.6 in an acidic solution having
[H+] = 1 M. From the obtained values, show that:
(i) the reduction potential of the reaction
1
2
Br2 + e - Æ Br -
remains unchanged.
(ii) The BrO3– ion is a better oxidizing agent (more easily reduced) in an acidic
solution than in a basic solution.
550 A Textbook of Physical Chemistry

(iii) Br2 will not disproportionate in acidic solution to Br– and HOBr or to Br– and
BrO–3.
(iv) HOBr, will however, disproportionate in the acidic solution to give Br2 and
BrO3–.
The values of potentials are

8.4 (a) Given below are the potential (in volts) data on halogens.

Show that
(i) Cl2, Br2, and I2 disproportionate in basic solution as follows:
3X2 + 6OH– XO3– + 5X– + 3H2O.
(ii) Cl2, Br2 and I2 are stable in acidic medium.
(iii) Cl2 can displace Br2 from Br– and Br2 can displace I2 from I–.
(iv) The standard equilibrium constant for the disproportionation of ClO3– to Cl–
and ClO4– is 1020.
(v) The lO3–/I– couple oxidizes much better in acid media (pH = 0) then in basic
media (pH = 14).
(b) Justify the statement:
Thermodynamic predictions are not always kinetically reliable.
8.5 Is water easier to oxidize or reduce as the pH increases?
8.6 Calculate the equilibrium constants for the following reactions:
(a) 2Cu+ Cu2+ + Cu
(b) Cu2O + H2O Cu(OH)2 + Cu
by using the potential data given below
 Electrochemical Cells 551

8.7 (i) Calculate the solubility product of the following (the required data are shown
along with the reaction):
(a) Cd(OH)2
Cd(OH)2 + 2e– Cd + 2OH–; E º = – 0.81 V at pH = 14
E° = – 0.40 V at pH = 0
(b) Pb(OH)2
Pb(OH)2 + 2e– Pb + 2OH–; Eº = 0.07 V at pH = 14
Eº = 0.09 V at pH = 0
(ii) Calculate the potential of the Fe2+ | Fe couple at pH 7.
Given: Eº = 0.036 V at pH = 0 and K sº (Fe(OH)2) = 6 × 10–38.
8.8 (a) The commonly observed formation of rust when iron is exposed to moist air may
be explained on the basis of reactions given below, followed by the conversion of
Fe2+ to reddish brown Fe2O3.
(i) In acidic medium:
Fe Fe2+ + 2e–
O2 + 4H+ + 4e– 2H2O(1)
(ii) In neutral solutions:
Fe Fe2+ + 2e–
O2 + 2H2O + 4e– 4OH–
Show that under standard conditions, the overall reactions given above will take
place spontaneously.
(b) One way to prevent a buried iron pipe from rusting is to connect it with a piece
of wire to a magnesium or zinc rod. What is the electrochemical principle for this
action?
8.9 Justify the value – 0.828 V for E º of the following half-cell in basic solution:
1
H2O(l) + e– 2 H2(g) + OH–

8.10 What will be the potential of standard hydrogen electrode at 323 K?

8.11 In the metal amalgam-metal ion electrode, if the amalgam is saturated with the solute
metal, the electrode is equivalent to the pure metal-metal ion electrode. Explain, why
is it so?
8.12 Can you employ potassium chloride salt bridge as a connecting devise to connect
silver nitrate solution?
8.13 The emf of a cell is found to be 0.30 V. What would happen if this cell is connected
to a 1.5 V battery with its negative terminal connected to the (a) negative terminal
of the battery, and (b) positive terminal of the battery?
8.14 In the titration of Fe2+ versus Cr2O72–, the internal indicator N-phenylanthranilic acid
is usually used in the presence of larger amount of H+ ions. Discuss, what effect
the latter has on the transition potential of the indicator and how far it is helpful in
locating the end point.
8.15 Derive the following expressions:
(a) For 1 : 1 electrolyte (e.g., HCl)
m+ = m– = m±
(b) For 1 : 2 electrolyte (e.g., SnCl2)
552 A Textbook of Physical Chemistry

1
m+ = m± and m- = (2)1/3 m±
(2)2/3
(c) For 1 : 3 electrolyte (e.g., FeCl3)
1
m+ = m± and m- = (3)1/4 m±
(3)3/4
(d) For 1 : 4 electrolyte (e.g., SnCl4)
1
m+ = m± and m- = (4)1/5 m±
(4)4/5

NUMERICAL PROBLEMS

Construction of 8.1 Construct the galvanic cell for each of the following reactions. Draw the diagram of
Galvanic Cell the cell indicating clearly the anode, cathode and the direction of flow of electrons
in the external circuit.
1
(i) 2 Br2(l) + Ag(s) AgBr(s)
1 1
(ii) 2 Br2(l) + I–(aq) Br–(aq) + 2 I2(s)
(iii) 2Hg(l) + Cl2(g) Hg2Cl2(s)
1
(iv) AgCl(s) + 2 H2(g) HCl(aq) + Ag(s)
1
(v) H2(g) + 2 O2(g) H2O(l)
(vi) HgO(s) + H2(g) Hg(l) + H2O(l)
(vii) AgCl(s) + I–(aq) AgI(s) + Cl–(aq)
Cell Reaction and 8.2 Write the cell reactions for the following cells and determine the emfs of the cells under
Cell Potential standard conditions.
(i) Pb | PbSO4(s) | SO42– (aq) Cu2+ (aq)| Cu
(ii) Ag | AgBr(s) | Br– (aq) Cl– (aq)| AgCl(s) | Ag
8.3 Determine the cell reaction, E ºcell and Ecell for the following cells at 298 K. Assume
activity and fugacity equal to molar concentration and pressure, respectively.
(i) Cu | CuSO4(0.02 M) Fe2+(0.2 M), Fe3+(0.01 M) | Pt
(ii) Zn | ZnCl2(0.02 M) Na2SO4(0.1 M) | PbSO4(s) | Pb
(iii) Pt | Fe2+(a = 1.0), Fe3+(a = 0.1) Cl–(a = 0.001) | AgCl(s) | Ag
(iv) Pt | Cl2(g, 1.12 bar) | Cl–(a = 0.526) I–(a = 0.10) | Agl(s) | Ag(s)
8.4 Write the cell reactions and potentials of the following cells:
Pt | H2(g, 0.4 bar) | HCl(a± = 3.0) | AgCl(s) | Ag
Pt | H2(g, 1 bar) | H2SO4(m = 0.05 mol kg–1, γ = 0.34) | Hg2SO4(s) | Hg
Computation of Cell 8.5 Given are the following data.
Potential
MnO–4 + 8H+ + 5e– Mn2+ + 4H2O; Eº = 1.51 V
3+ – 2+
Mn +e Mn ; Eº = 1.51 V
Calculate the standard potential for
MnO–4 + 8H+ + 4e– Mn3+ + 4H2O (Ans. 1.51 V)
 Electrochemical Cells 553

8.6 (a) For a 1 : 1 electrolyte in aqueous solution the extended Debye-Hückel law is
given as
log γ± = – 0.509 m 1/2 + Bm
where B is constant and m = m/mº (here mº is 1 mol kg–1). Show that emf of the cell
Pt | H2(g, 1 bar) | HCl(m) | AgCl | Ag
is given by

∞ - |AgCl|Ag - 0.118 3 V) Bm¢

Ecell + (0.118 3 V) log m¢ - (0.06 V) m¢ = ECl

(b) If a plot is drawn between Ecell + (0.118 3 V) log m – (0.06 V) m¢ and m ,

what will be its slope and intercept?
(c) Given the following data for the cell
Pt | H2(g, 1 bar) | HCl(m) | AgCl(s) | Ag
–1
m/mol kg 0.009 0.014 0.025 0.055
E/V 0.469 5 0.447 8 0.419 6 0.381 2
∞-
Compute ECl AgCl Ag
(d) What will be the mean activity coefficient of 0.02 mol kg–1 HCl at 298 K?
(e) The emf of the cell given in part (c) is 0.352 4 V at 298 K when the HCl is at
a concentration of 0.1 mol kg–1. What is (i) the activity of the HCl, (ii) the mean
activity coefficient of the HCl at this concentration, and (iii) the pH of the acid?
(Ans. (c) 0.225 V, (d) 0.875, (e) 0.080, 0.795, 1.10)
8.7 The standard free energy change for the reaction
1
H2(g, 1 atm) + 2 O2(g, 1 atm) H2O(1)
–1
is – 237.19 kJ mol at 298 K. (i) Write the electrode reactions if the reaction is
to occur in a galvanic cell. (ii) Calculate the standard electrode potential for the
electrodes OH– | O2 | Pt and H+ | O2 | Pt. The cell potential producing the reaction
H2O(1) H+(a = 1) + OH–(a = 1)
is – 0.827 7 V.
(Ans. 0.403 V, 1.229 V)
Computation of 8.8 For the lead storage cell
Thermodynamic
Pb | PbSO4 | H2SO4(m = 1 mol kg–1) | PbSO4 | PbO2 | Pt
Data
the emf is found to vary
Ecell/V = 1.917 31 + 51.1 × 10–6(t/°C) + 108 × 10–8(t/°C)2
in the temperature range 0 to 60 °C
(a) Calculate G, H and S for the cell reaction at 273 K and 298 K.
(b) For the half-cells at 298 K
PbO2(s) + SO42– + 4H+ + 2e– PbSO4(s) + 2H2O; E º = 1.684 9 V
–
PbSO4(s) + 2e Pb(s) + SO42–; E º = – 0.355 3 V
554 A Textbook of Physical Chemistry

Calculate the mean ionic activity coefficient in 1 molal H2SO4 at 298 K. Assume
that the activity of water is unity.
(Ans. (a) at 0 °C: G = – 370.03 kJ mol–1; H = – 366.80 kJ mol–1;
S = 10.83 J K–1 mol–1
at 25 °C: G = – 370.43 kJ mol ; H = – 364.11 kJ mol–1;
–1

S = 21.23 kJ mol–1
(b) 0.130).
8.9 For the cell
Pt | H2(g, 1 bar) | NaOH(l M), NaCl(l mol dm–3) | AgCl(s) | Ag
the potentials at different temperatures are
t/°C 20 25 30
E/V 1.047 68 1.051 88 1.056 08
(a) Calculate the values of pKºw at these temperatures.
(b) Calculate the enthalpy and entropy of ionization of water at 298 K.
Given: E Cl
º – | AgCl | Ag = 0.222 5 V
(Ans. 14.185, 14.018, 13.858, 55.86 kJ mol–1, – 81.049 J K–1 mol–1)
8.10 The emf of the cell
1
Cd | CdCl2 2 2 H2O, sat. solution | AgCl | Ag

at 298 K is 0.675 33 V and ( E/ T)p is – 6.5 × 10–4 V K–1. Calculate G, H and

S for the cell reaction at 298 K.
(Ans. – 130.33 kJ mol–1, – 167.74 kJ mol–1 and – 125.52 J K–1 mol–1)
8.11 The emf of the cell
Ag | AgCl(s) | KCl(soln) | Hg2Cl2(s) | Hg
is 0.045 5 V at 298 K and the temperature coefficient is 3.38 × 10–4 V K–1. What is
reaction that takes place in the cell and what are free energy, enthalpy and entropy
changes at 298 K?
(Ans. – 8.81 kJ mol–1, 10.66 kJ mol–1 and 63.43 J K–1 mol–1)
8.12 At 273 K, a calorimetric determination of H for the reaction
Zn + 2AgCl ZnCl2 + 2Ag
yielded – 217.78 kJ mol–1, while the emf of the corresponding cell was 1.015 4 V.
What was ( E/ T)p of the cell? (Ans. – 4.14 × 10–4 V K–1)
8.13 Consider the following cell arrangement.
Ag(s) | AgCl(s) | NaCl(aq) | Hg2Cl2(s) | Hg
(a) Write down the half-cell reactions.
(b) The standard emfs of the cell at various temperatures are as follows:
T/K 291 298 303 311
E º/mV 43.0 45.4 47.1 50.1
Calculate G, S and H for the reaction
2Ag(s) + Hg2Cl2(s) 2AgCl(s) + 2Hg(l)
 Electrochemical Cells 555

8.14 At 298 K the free energy of formation of H2O(1) is – 237.23 kJ mol–1, while that
of its ionization to hydrogen and hydroxyl ions is 79.71 kJ mol–1. Determine the
emf at 298 K of the cell
Pt | H2(g, 1 bar) | H+(1 M) OH– (1 M) | O2(g, 1 bar) | Pt (Ans. 0.403 V)
Computation of 8.15 Evaluate the standard equilibrium constant for the formation of the triiodide ion
Equilibrium
I2(aq) + I– I3–
Constant
from the knowledge that
I2(aq) + 2e– 2I–; E º = 0.619 7 V
and I3– + 2e – –
3I ; Eº = 0.535 5 V (Ans. 708)
8.16 Given that
Ag(CN)2– + e– Ag + 2CN–; E º = – 0.31 V
+ –
and Ag + e Ag; Eº = + 0.80 V
Calculate the standard equilibrium constant for the reaction
Ag(CN)2– Ag+ + 2CN– (Ans. 1.68 × 10–19)
8.17 Given the information that
Cu2+ + 2e– Cu; E º = 0.34 V
+ –
Cu + e Cu; Eº = 0.52 V
2+ – –
Cu + Cl + e CuCl(s); Eº = 0.54 V
Calculate the standard solubility product of CuCl. (Ans. 3.6 × 10–7)
8.18 Calculate the partial equilibrium pressure of O2 above H2O2 at 298 K.
(Ans. 2.758 × 10–12 atm)
8.19 Calculate the standard equilibrium constant for each of the following reactions:
(i) Fe2+ + Cu2+ Fe3+ + Cu+
2+
(ii) 5Fe + MnO4– + 8H+ 5Fe3+ + Mn2+ + 4H2O
(iii) Zn2+ + 4CN– Zn(CN)42–
(iv) PbSO4 Pb2+ + SO42–
(v) 2Fe2+ + Cl2 2Cl– + 2Fe3+
(vi) AlF63– Al3+ + 6F–
(Ans. (i) 3.6 × 10–11, (ii) 8.0 × 1061,
(iii) 8.0 × 10–16, (iv) 1.7 × 10–8, (vi) 1.6 × 10–21)
8.20 Compute the standard equilibrium constant of the reaction at 298 K
2Au + Au3+ 3Au+. Given:
Au3+ + 2e– Au+; E º = 1.41 V
3+ –
Au + 3e Au; Eº = 1.50 V
(Ans. 7.37 × 10–10)
556 A Textbook of Physical Chemistry

8.21 The emf of the cell

Ag | 0.1 M AgNO3 | sat. NH4NO3 | AgCl in 0.1 M KC1 | Ag
is – 0.45 V at 298 K. Calculate the standard solubility product and solubility of AgCl
in water. Given that 0.1 M KC1 is 85% and 0.1 M AgNO3 is 82% dissociated.
(Ans. 1.707 × 10–10, 1.875 × 10–5 mol dm–3)
8.22 The standard equilibrium constant for the reaction
2Cu+ Cu2+ + Cu(s)
at 298 K is 1.646 × 106. (a) Construct a cell in which the reaction could occur.
(b) Calculate the standard emf of the cell. (c) Evaluate the standard potential of
Cu+ | Cu electrode.
(Ans. (b) 0.368 V, (c) – 0.521 V)
8.23 Calculate the equilibrium constants of the reactions
Hg + Hg2+ Hg22+
Cu + Cu2+ Cu22+
8.24 How would you use the arrangement
Ag | AgCl sat. soln. |AgCl(s) | Ag
to determine the solubility product of silver chloride at 298 K.
8.25 (a) Calculate K sº for CrSO4 from the following data:
Cr + SO42– CrSO4(s) + 2e– º
E 298K = 0.4 V
3+ –
Cr Cr + 3e E º = 0.5 V
(b) Given E º is 0.152 V for Ag + I = Agl + e– at 298 K and E º for Ag
–
Ag+
–
+ e is – 0.80 V at 298 K, calculate Kºs for Agl.
(Ans. (a) 10–6, (b) 1.2 × 10–17)
8.26 The solubility of AgBr is 2.1 × 10–6 mol kg–1 at 298 K. Find the emf of the cell
Ag | AgBr sat. solution | AgBr(s) | Ag (Ans. – 0.536 V)
8.27 Calculate ideally the free energy change upon diluting 1 mol NaCl from 0.020 mol
kg–1 to 0.001 mol kg–1 at 298 K.
(Ans. – 148 40 J)
8.28 Calculate Gº and the standard equilibrium constant for the reaction
H2(g) + O2(g) H2O2(l)
at 298 K. At what pressure would G be equal to zero? Given that:
O2 + 2H+ + 2e– = H2O2; Eº = 0.682 V
(Ans. – 131.26 kJ mol–1, 1.148 × 1023, 5.9 × 10–12 atm)
8.29 At 298 K, the potential of the cell
Ag | AgI | KI(1 M) AgNO3(0.001 M) | Ag
is 0.72 V. The mean ionic activity coefficient of 1 M KI may be taken as 0.65,
and of 0.001 M AgNO3 as 0.98. (a) What is the solubility of AgI? (b) What is the
solubility of AgI in pure water? (Ans. 6.59 × 10–16 M, 2.07 × 10–8 M)
 Electrochemical Cells 557

8.30 If the standard solubility product of Hg2Cl2 is 4.2 × 10–18 for the reaction
Hg2Cl2(s) Hg22+ + 2Cl–
and if the decimolar calomel electrode with half-cell reaction
1
2 Hg2Cl2(s) + e– Hg(l) + Cl–(0.1 M)
has electrode potential of 0.334 V, find E º of the half reaction
1
2 Hg22– + e– Hg(l) (Ans. 0.788 V)
8.31 (a) Excess solid silver is placed in a solution of 0.1 M ferric ion. Calculate the
equilibrium concentration of Ag+ and Fe3+ ions.
(b) Finely divided Ni is added to a solution in which the activity of Sn2+ is 0.1.
What will be the activities of Ni2+ and Sn2+ when equilibrium is established.
(Ans. (a) [Ag+] = 0.08 M (b) aNi2+ = 0.1, aSn2+ = 5.7 × 10–5)
Computation of pH 8.32 For the cell
Pt | H2(l bar) | HCl | AgCl | Ag
E º = 0.222 V and E = 0.332 V at 298 K. What is the pH of the HCl solution?
(Ans. 0.93)
8.33 A hydrogen electrode and calomel cell are used to determine the pH of a solution
on a mountain where the barometric pressure is 500 Torr. The hydrogen is allowed
to bubble out of the electrode at the atmospheric pressure prevailing there. If the
pH is calculated to be 4.0, what is the correct pH of the solution?
Liquid Junction 8.34 Calculate the emf of the following cell at 298 K.
Potential
Ag | AgCl(s) | NaCl(a = 0.01) NaCl(a = 0.025) | AgCl(s) | Ag
The transport number of Na+ is 0.39. (Ans. – 0.018 4 V)
Concentration Cell 8.35 Calculate the emf of the amalgam concentration cell at 333 K:
Zn(Hg)(c1) | ZnSO4(aq) | Zn(Hg)(c2)
when c1 and c2 are 6.08 × 10–5 and 2.28 × 10–3 mol dm–3, respectively. The amalgams
may be considered ideal. (Ans. – 0.046 6 V)
8.36 If activities equal concentrations, what is the potential at 298 K of
Pt | Na(0.2% in Hg) | NaCl(0.15 mol kg–1) | AgCl(s) | Ag | AgCl(s) |
NaCl (0.037 2 mol kg–1) | Na (0.2% in Hg) | Pt
(Ans. – 0.072 V)
8.37 Determine the cell reaction and potential of the cell
Zn(s) | ZnCl2(m = 0.02 mol kg–1, γ = 0.643) | AgCl(s) | Ag – Ag | AgCl(s)
| ZnCl2(m = 1.50 mol kg–1, γ = 0.290) | Zn(s)
(Ans. 0.093 V)
8.38 For the cell with transference
Pt | H2( p = 1 bar) | H2SO4(m = 0.005 mol kg–1, γ = 0.643) H2SO4
(m = 2.0 mol kg–1, γ = 0.125) | H2( p = 1 bar) | Pt
E = 0.03 V at 298 K. Find the cell reaction and the transport number of the
hydrogen ions. (Ans. 0.82)
558 A Textbook of Physical Chemistry

8.39 The concentration cell

Ag(s) | AgCl(s) | KCl(0.5 M) | K(Hg) | KCl(0.05 M) | AgCl | Ag
has an emf of – 0.107 4 V at 298 K. (a) Formulate the corresponding cell with
transference, (b) Write the equations for the cell reactions for the withdrawal of 2F
of electricity, (c) The emf of the cell in (a) is 0.053 57 V. Calculate t(Cl–).
(Ans. 0.55)
8.40 The emf at 298 K is – 0.335 V for the cell
Pt | H2(l bar) | HCl(0.1 mol kg–1) | AgCl | Ag – Ag | AgCl |
HCl(10–4 mol kg–1, γ± = 1) | H2(l bar) | Pt
Calculate (a) G for the cell reaction at 298 K (write down the cell reaction), (b)
the mean activity coefficient of 0.1 mol kg–1 HCl, and (c) G for the cell reaction
at 273 K, assuming H to be zero and S independent of temperature.
(Ans. G = 32 200 J mol–1, γ± = 0.69, G º(273 K) = 29 600 J mol–1)
8.41 Given the cell
Ag | AgCl(s) | KCl(0.01 mol kg–1, γ± = 0.90) KC1(0.1 mol kg–1,
γ± = 0.80) | AgCl(s) | Ag
(a) Write the cell reaction and (b) Calculate the emf of the cell at 298 K. Given
t– = 0.60.
(Ans. t + K + (0.01 mol kg –1 ) + t + Cl – (0.01 mol kg –1 ) t + K + (0.1 mol kg –1 )
+ t+Cl (0.1 mol kg–1); E = – 0.045 V)
–
Annexure I
Concept of Activity

The variation of chemical potential with pressure of an ideal gas is given by

Êp ˆ
mi = mi∞ + RT ln Á i ˜ (1)
Ë p∞ ¯
where μ iº is the standard chemical potential of the ith gas at the standard-state
pressure (pº) of 1 bar. To have the same type of dependence of any substance
(gas, liquid, solid), G.N. Lewis modified Eq. (1) as

mi = mi∞ + RT ln ai (2)

where ai, a dimensionless quantity, is known as activity of the ith substance.

The activity of a substance existing in different conditions may be defined
as follows.

We have

pi
Ideal gas ai = (3)
p∞

fi
Real gas ai = (where f is fugacity of the gas) (4)
f∞

The variation of chemical potential of a liquid or solid with pressure is given by

mi = mi∞ + Vm, i ( p - p∞) (5)

Comparing this with Eq. (2), we get

RT ln ai = Vm, i ( p – pº) (6)

or ai = exp{Vm, i(p – pº)/RT}

Small variations in pressure do not have a significant effect on the activity.

Since each component of liquid solution is in equilibrium with its vapour, we

will have

mi (l) = mi (g)

559
560 A Textbook of Physical Chemistry

The expressions of μ i(l) and μi(g) are

mi (l) = mi∞ (l) + RT ln ai

Êp ˆ
mi (g) = mi∞ (g) + RT ln Á i ˜ (assuming vapour to behave ideally)
Ë p∞ ¯

Êp ˆ
Hence mi∞ (l) + RT ln ai = mi∞ (g) + RT ln Á i ˜
Ë p∞ ¯

For a pure liquid, ai = 1 and pi = p*i . Thus

Ê p* ˆ
mi∞ (l) = mi∞ (g) + RT ln Á i ˜
Ë p∞ ¯

Substituting this in previous expression, we get

Ê p ˆ
RT ln ai = RT ln Á i ˜
Ë pi* ¯

Ê p ˆ
or ai = Á i ˜ (7)
Ë pi* ¯

Since the liquid solution behaves ideally, pi = xi pi* (Raoult’s law), we get
ai = xi (8)
The components of a nonideal solution exhibit deviations from Raoult’s law.
To account for the nonideality, the activity is defined as
ai = xiγi (9)
where γi, known as activity coefficient, is a measure of deviations from Raoult’s
law. Since the activity of a component approaches its amount fraction as xi
approaches unity, we will have
γi 1 as xi 1 (10)
The components exhibiting positive deviations from Raoult’s law, γi is greater
than unity, and those exhibiting negative deviations, γi is less than unity.
Since ai = ( pi /p*i ), we will have

pi
xig i =
pi*

pi
or gi = (11)
xi pi*
 Annexure I 561

In dilute real solutions, solute follows Henry’s law whereas solvent follows
Raoult’s law, i.e.

For solvent pi = xi pi* (Raoult’s law)

For solute pi = xi kH (Henry’s law)
Proceeding similarly to nonideal solution, it can be shown that
pi
For solvent gi = (12)
xi pi*
pi
For solute g i¢ = (13)
xi kH
The activity coefficient for solute follows the following characteristics.
(i) γ i 1 as xi 0
(ii) γ i > 1 if there are positive deviations from Henry’s law
(iii) γ i < 1 if there are negative deviations from Henry’s law
The chemical potential of a completely dissociated electrolyte is given by

m (M x X y ) = x m (M y + ) + y m (X x - )

Since μ = μ º + RT ln a, we get
m (M x X y ) = x[ m ∞(M y + ) + RT ln aM y+ ] + y[ m ∞(X x - ) + RT ln aX x - ]
= x m ∞(M y + ) + y m ∞(X x - ) + RT ln {(aM y + ) x (aX x - ) y ]
= m ∞(M x X y ) + RT ln aM x X y (14)

where aM x X y = (aM y + ) x (aX x - ) y (15)

written simply as
a = (a+ ) x (a- ) y (16)

While dealing with electrolytic solution, it is customary to use the molality. The
expressions relating activities of ions with the corresponding molalities are

Êm ˆ
a+ = Ë + ¯ g + (17)
m∞

Êm ˆ
a- = Ë - ¯ g - (18)
m∞
where mº is the standard-state molality and is equal to 1 mol kg–1. Here after,
Eqs (17) and (18) are simply written as
a+ = m+¢ g + and a- = m-¢ g - (19)

where m + = m+/mº and m – = m–/mº.

562 A Textbook of Physical Chemistry

Since individual activities cannot be determined, it is more appropriate to

express the activity of an ion in terms of mean activity of the electrolyte. The
expression is
(a±)ν = (a+)x(a–)y (20)
where ν = x + y is the total number of ions produced due to the dissociation
of 1 molecule of electrolyte MxXy. Comparing Eqs (16) and (20), we get
a = (a±)ν
Now since a+ = m+ γ+ and a– = m– γ–, it follows that
(a± )n = (m+¢ g + ) x (m-¢ g - ) y = (m+¢ x m-¢ y ) (g +x g -y ) = m±¢n g n±

or a± = m±¢ g ± (21)

To write mean molality m ± of the electrolyte MxXy in terms of its molality,

we proceed as follows.

m±¢ x + y = m+¢ x m-¢ y = ( x m ¢ ) x ( y m¢ ) y = x x y y m¢ x + y

Thus m±¢ = (x x y y )1/(x +y ) m ¢ (22)

The above relations may be supplemented by the following examples.

a(MX ) = a±2 = m±¢ 2g ±2 = (m+¢ m-¢ )g ±2 = m ¢ 2g ±2

a(MX 2 ) = a±3 = m±¢ 3g ±3 = (m+¢ m-¢ 2 )g ±3 = (m ¢ )(2 m ¢ )2 g ±3 = 4 m ¢ 3g ±3
a(MX 3 ) = a±4 = m±¢ 4g ±4 = (m+¢ m-¢ 3 )g ±4 = (m ¢ )(3m ¢ )3 g ±4 = 27m ¢ 4g ±4
a(M2 X3 ) = a±5 = m±¢ 5g ±5 = (m+¢ 2 m-¢ 3 )g ±5 = (2 m ¢ )2 (3m ¢ )3 g ±5
= 108m ¢ 5g ±5
Annexure II
Derivation of Debye-Hückel Law

Because of ionic interactions, many of bulk properties of a solution containing

an electrolyte are not related directly with the actual concentration of electrolyte
but with the effective concentration or activity of the electrolyte.
Depending on the way the concentration is expressed, the actual
concentration c and the activity a are related to each other through the expression

a = (c/cº)γc

a = (m/mº)γm (1)

a = xγx

where γx is known as the rational activity coefficient whereas γc and γm are

practical activity coefficients.
The individual ion activities and activity coefficients cannot be determined
experimentally. Since both the positively- and negatively-charged ions produced
from a given electrolyte determine the bulk properties of a system, mean ion
activity (a±) and mean ion activity coefficients (γ±) are used instead of individual
ion activities and activity coefficients. These are defined by

(a± )ν = (a+)ν+ (a–)ν– (2)

and (γ±)ν = (γ+)ν + (γ–)ν– (3)

where ν+ and ν– are the number of cations and anions, respectively, derived
from each molecule of the electrolyte and ν = ν+ + ν–.
The chemical potential μi of an ion i in an ideal solution is given by

mi = mi* + RT ln xi (4)

For nonideal solution, Eq. (4) is written as

mi = mi* + RT ln ai

or mi = mi* + RT ln xi + RT ln g i (5)

The activity coefficient can theoretically be predicted on the basis of the Debye-
Hückel theory of ionic atmosphere. According to the latter, each ion in a
solution is surrounded by a spherical and symmetrical ionic atmosphere consisting
of other ions whose net charge is opposite to that of the central ion. The activity

563
564 A Textbook of Physical Chemistry

coefficient expression in Eq. (5) may be considered as the contribution of this ionic
atmosphere. Since μi represents the change in free energy of the system which
would occur if 1 mol of the ith ions were added to a large quantity of it, the term
RT ln γi in Eq. (5) may be regarded as the contribution of ion atmosphere towards
the total energy of the ion. The contribution per ion is kT ln γi and may be equated
to the work which must be performed to give an ion of electrical potential φ i (due
to its atmosphere) its charge zi e. The work done in this process is given by
zi e
w= Ú0 fi d(zi e)

Equating this with kT ln γi, we get

zi e
kT ln g i = Ú0 fi d(zi e) (6)

The electrostatic potential φ at a given point in the vicinity of a positive (or

negative ion is related to the charge density ρ at the given point by the Poisson
equation, viz.,

∂ 2f ∂ 2f ∂ 2f r
2
+ 2
+ 2
=- (7)
∂x ∂y ∂z e
where x, y and z are the rectangular coordinates of the given point and ε is the
permittivity of the solvent. In terms of polar coordinates, Eq. (7) is given by

1 ∂ Ê 2 ∂f ˆ r
2 ∂r Ë
r ¯ =- (8)†
r ∂ r e

Let the charge density per unit volume at some point in the vicinity of an ion
(positive or negative ion) be required. On the average there will be more ions
of opposite charge in the vicinity of a given ion. The concentrations of positive
and negative ions (N+, N–) in terms of the total concentrations of these ions
(N 0+, N 0–) may be written following the Boltzmann distribution law as
N+ = N+0 exp(– z+eφ /kT) (9a)
N_ = N–0 exp(– z–eφ / kT) (9b)
where φ is the electrical potential at the point under study and z+ and z– are the
charge numbers (including sign) of positive and negative ions, respectively. If it
be assumed that kT is much larger than z+ eφ or | z– | eφ, Eqs. (9) may be simplified
by expanding the two exponential terms and ignoring all but the first terms in the
expansion. Thus, we get
N+ = N+0 (1 – z+eφ /kT) (10a)
N– = N–0 (1 – z–eφ /kT) (10b)

†
There is no angular dependence in Eq. (8) as the charge density is spherical symmetrical
in the vicinity of a positive ion.
 Annexure II 565

The charge density at the given point will be given by

r = N + z+ e + N - z - e
where e is the elementary charge (i.e. magnitude of electronic charge).
Substituting for N+ and N_ from Eqs. (10), we get
r = z+ eN +0 (1 - z+ ef /kT ) + z- eN -0 (1 - z- ef /kT )
Making use of electroneutrality condition
N +0 z+ e + N -0 z- e = 0
in the above expression, we get
r = - (N +0 z+2 e 2f /kT ) - (N -0 z-2 e 2f /kT )

that is r = - Â N i0 zi2 e 2f /kT (11)

i
where the summation is to be carried over all the ions.
Substituting Eq. (11) in Eq. (8), we get
φ

{Â N z e f /kT }
1 ∂ Ê 2 ∂f ˆ 1 0 2 2
2 ∂r Ë
r ¯ = i i (12a)
r ∂r e i

1 ∂ Ê 2 ∂f ˆ
or r = k 2f (12b)
r 2 ∂r Ë ∂r ¯
1/2
Ï 1 Ê e2 ˆ ¸
where k = Ì ÁË ˜¯ (S N i0 zi2 )˝ (13a)
Ó e kT ˛
The expression of κ in terms of molar concentrations of ions is
1/2 1/2
È 1 Ê e2 ˆ ˘ È 2 Ê e2 N A ˆ ˘
k = Í ÁË ˜¯ {S (N A ci )zi2 ˙ = Í ÁË ˜m (13b)
Î e kT ˚ Î e kT ¯ ˙˚

where NA is the Avogadro’s constant and μ is the ionic strength of the solution
defined as 1
2
S ci zi2 .
The general solution of Eq. (12b) is given by

A exp(- k r ) A¢ exp(k r )
f= +
r r
where A and A are constants. In order to have finite value of φ for larger value
of r and the fact that φ 0 as r , the constant A must be set equal to
zero. Thus, we have
A exp(- k r )
f= (14)
r
566 A Textbook of Physical Chemistry

The condition of electroneutrality requires that the total charge of the atmosphere
A around a given charged ion (zie) must be equal and of opposite sign of the charge
of the ion itself, i.e. – zie. The charge around the ion can be determined by
considering the charge carried by a spherical shell of thickness dr at a distance
r from the ion and then integrating the expression from the closest distance a
that atmosphere and central ion may approach to a distance of infinity. Thus,
we have

•
- zi e = Úa r(4πr 2 ) dr (15)

The dependence of ρ on r can be found by substituting the expression of φ

from Eq. (14) in Eq. (11). Thus, we have

r = - Â N i0 zi2 (e 2 /kT )f
i

= - Â N i0 zi2 (e 2 /kT )
i
{ A exp(- k r )
r }
which on making use of Eq. (13a) becomes

exp(- k r )
r = - Ak 2 e (16)
r
Substituting Eq. (16) in Eq. (15), we get

•
- zi e = - Ú (4πAk 2 e )r exp(- k r ) dr
a

•
È exp(- k r ) exp(- k r ) ˘
= - (4πAk 2 e ) Í r - ˙˚
Î (- k ) k2 a

Ê k a + 1ˆ
= - (4πAk 2 e ) Á exp(- k a)
Ë k 2 ˜¯

= - 4πAe (k a + 1) exp(- k a)

zi e exp(k a)
or A= (17)
4πe k a + 1

Substituting Eq. (17) in Eq. (14), we get

zi e exp(k a) exp(- k r )
f= (18)
4πe 1 + k a r
 Annexure II 567

For the distance a of closest approach to the given ion, Eq. (18) becomes

zi e 1 zi e ze k
f= or f= - i (19)
4πe a 1 + k a 4πe a 4πe 1 + k a
Equation (19) indicates that the electrical potential is composed of two
terms; the first term represents the potential due to the given ion itself and the
second term represents the potential on the ion due to its ionic atmosphere, i.e.
f = f (ion) + f (atmosphere) (20)

zi e
where f (ion) = (21)
4πe a

zi e k
f (atmosphere) = - (22)
4πe 1 + k a
Substituting the expression of φ from Eq. (22) in Eq. (6), we get
γi μ
zi e (zi e) k
kT ln g i = - Ú d(zi e)
0 4πe 1 + k a

zi2 e 2 k
or ln g i = - (23a)
2 kT (4 πe ) 1 + k a

zi2 e 2 k
or log g i = -
(2.303)(2 kT )(4 πe ) 1 + k a
Substituting the expression of κ (Eq. 13b), we get

zi2 e 2 {(2e 2 N A /e kT )m}1/2

log g i = -
(2.303)(2kT )(4πe ) 1 + {(2e 2 N A /e kT )m}1/2 a
zi2 A m
=- (24)
1 + Ba m

1/2
e2 Ê 2e 2 N A ˆ
where A= Á ˜ (25)
(2.303)(2kT )(4πe ) Ë e kT ¯
1/2
Ê 2e 2 N A ˆ
B = ÁË ˜ (26)
e kT ¯

Since g n± = g +n + g n-- , we get

ν log γ± = ν+ log γ+ + ν_ log γ–
568 A Textbook of Physical Chemistry

Substituting log γ+ and log γ– from Eq. (24), we get

(n + z+2 + n - z-2 )A m
n log g ± = - (27)
1 + Ba m

Using the condition of electroneutrality ν+z+ = – ν– z–, we get

2
Ê n z ˆ Ên ˆ
n + z+2 + n - z-2 = n + Á - - - ˜ + n - z-2 = n - z-2 Á - + 1˜
Ë n+ ¯ Ë n+ ¯
Ên ˆ
= Á - ˜ z-2 (n + + n - ) = - z+ z- (n + + n - )
Ë n+ ¯

With this Eq. (27) becomes

(z+ z- )A m
log g ± = (since n = n + + n - ) (28)
1 + Ba m
The values of A and B for water at 298 K are as follows.

A B È (1.6 ¥ 10 -19 C)2 ˘

A= Í -23 -1 -12 ˙
Í (2.303)(2)(1.38 ¥ 10 J K )(298 K)(4)(3.14)(78 ¥ 8.854 ¥ 10
2 2 -11 -3 ˙
Í C s kg m ) ˙
Î ˚
1/2
È 2(1.6 ¥ 10 -19 C)2 (6.022 ¥ 1023 mol -1 ) ˘
¥Í -12 2 2 -1 -3 -23 -1 ˙
Î (78 ¥ 8.854 ¥ 10 C s kg m )(1.38 ¥ 10 J K )(298 K) ˚

= (1.558 ¥ 10 -10 m)(1.042 ¥ 108 m1/2 mol1/2 )

= 0.016 24 m 3/2 mol -1/2 = (0.016 24)(103/2 dm3/2 mol -1/2 )

= 0.514 mol -1/2 dm 3/2

1/2
È 2(1.6 ¥ 10 -19 C)2 (6.022 ¥ 1023 mol -1 ) ˘
B= Í -12 2 2 -1 -3 -23 -1 ˙
Î (78 ¥ 8.854 ¥ 10 C s kg m )(1.38 ¥ 10 J K )(298 K) ˚

= 1.042 ¥ 108 m1/2 mol -1/2 = 1.042 ¥ 108 (10 dm)1/2 mol -1/2

= 3.30 ¥ 108 dm1/2 mol -1/2

For a very dilute solution Ba m << 1 , hence Eq. (28) simplies to

log g ± = - z+ | z- | A m (29)

Equation (29) is known as the limiting form of the Debye-Hückel equation.

According to Eq. (29), log γ± decreases with increase in the ionic strength of the
solution. In actual practice, activity coefficients first decreases and show a turning
 Annexure II 569

point at some value of μ, after which they progressively increase. Equation (28) may
be modified by adding a term which increases with increase in ionic strength such as

A z+ | z - | m
log g ± = - + bm (30)
1 + Ba m

Equation (30) is usually referred to as extended Debye-Hückel equation.

Annexure III
Operation of Definition of pH

The defining equation pH = – log aH (or commonly used definition pH = – log

{[H+]/mol dm–3} in dilute solution) is replaced by the following operational
definition.

ES – EX
pH(X) = pH(S) –
( RT ln 10)/F

where ES is the emf of the cell

Reference Solution S
KCl (aq, m > 3.5 mol kg–1) H2(g) Pt
electrode of known pH
and EX is the emf of the cell in which the solution S in the above cell is replaced
by the solution X of unknown pH.
The various solutions S at different temperatures are available. For example,
the following aqueous solutions at 25 ºC may be used
(i) KH tartrate (saturated solution) pH = 3.557
(ii) KH phthalate (m = 0.05 mol kg–1) pH = 4.008
(iii) KH2PO4 (m = 0.025 mol kg–1)
+ Na2HPO4 (m = 0.25 mol kg–1) pH = 6.865
(iv) KH2PO4 (m = 0.008 695 mol kg–1)
+ Na2HPO4 (m = 0.030 43 mol kg–1) pH = 7.413
(v) Na2B4O7 (m = 0.01 mol kg–1) pH = 9.180

The reference electrode is usually a calomel electrode, silver | silver chloride

electrode or a thallium amalgam | thallous chloride electrode. In practice, a glass
electrode is used in place of hydrogen electrode.
In the restricted range of dilute aqueous solution (concentration < 0.1 mol
dm–3) which is neither strongly acidic or alkaline (2 < pH < 12), the above
procedure yields pH which lies in the range
pH = – log {([H+]/mol dm–3) γ±} ± 0.02
where γ± denotes the mean ionic activity coefficient of a typical unit-univalent
electrolyte in the solution.

570
Appendix I
Units and Conversion Factors

CGS Units vis-à-vis SI Units

Physical quantity CGS units SI units

Name Symbol Name Symbol
length centimetre cm metre m
Angstrom (10–8 cm) Å
mass gram g kilogram kg
time second s second s
Ïcelsius Ï∞C
temperature Ì Ì kelvin K
Ókelvin Ó∞K
energy calorie cal joule J
kilocalorie kcal kilojoule kJ
litre-atmosphere lit-atm
ergs erg
electric current ampere A ampere A

Units Derived From the Basic SI Units

Physical quantity Name of unit Symbol and definition

force newton N = kg m s–2 or J m–1
energy joule J = kg m2 s–2 or N m
electric charge coulomb C=As
potential difference volt V = kg m2 s–3 A–1 or J A–1 s–1
resistance ohm = kg m2 s–3 A–2 or V A–1
frequency hertz = cycle per second Hz
area square metre m2
volume cubic metre m3
density kilogramme per cubic metre kg m–3
velocity metre per second m s–1
angular velocity radian per second rad s–1
acceleration metre per square second m s–2
pressure newton per square metre N m–2 or Pa
or pascal

571
572 A Textbook of Physical Chemistry

Conversion of CGS Units to SI Units

Quantity Unit Equivalent*

length Å 10–10 m = 10–1 nm = 102 pm
volume litre 10–3 m3 = dm3
force dyne 10–5 N
energy erg 10–7 J
cal 4.184 J
eV 1.602 1 × 10–19 J
eV/mole 96.5 kJ mol–1
pressure atmosphere 101.325 kN m–2
mmHg (or Torr) 133.322 N m–2
bar (106 dynes/cm2) 105 N m–2
viscosity poise 10–1 kg m–1 s–1
* Symbols used for fractions and multiples are as follows.

Fraction Prefix Symbol Multiples Prefix Symbol

–1
10 deci d 10 deca da
10–2 centi c 102 hecto h
10–3 milli m 103 kilo k
10–6 micro 106 mega M
10–9 nano n 109 giga G
10–12 pico p 1012 tera T
10–15 femto f 1015 peta P

Values of Some Physico-Chemical Constants

Constant SI units
Acceleration of gravity, g 9.806 65 m s–2
Avogadro’s constant, NA 6.022 05 × 1023 mol–1
Bohr magneton, μB 9.274 08 × 10–24 A m2
Bohr radius, a0 5.2971 77 × 10–11 m
Boltzmann constant, k 1.380 66 × 10–23 J K–1
Elementary charge, e 1.602 19 × 10–19 C
Electronic rest mass, me 9.109 53 × 10–31 kg
Faraday constant, F 9.648 46 × 104 C mol–1
Gas constant, R 8.314 J K–1 mol–1
Molar volume of ideal gas
at 0 °C and 1 atm, Vm 2.241 4 × 10–2 m3 mol–1
Planck’s constant, h 6.626 18 × 10–34 J s
Proton rest mass, mp 1.672 65 × 10–27 kg
Vacuum speed of light, c0 2.997 925 × 108 m s–1
Standard atmospheric 101.325 kPa
pressure
Permittivity of vacuum, ε0 8.854 188 × 10–12 C2 s2
kg–1 m–2
Relative permittivity 78
of water at 25 °C
 Index
in ideal solution, 45
Absorption coefficient, 114
pressure dependence of, 4
Activity, 559
temperature dependence of, 3
Activity coefficient, 560
Clapeyron equation, 6
Amalgam electrode, 422
applied to liquid-vapour equilibrium, 11
Amount fraction, 35
applied to solid-liquid equilibrium. 8
Anode, 410
applied to solid-solid equilibrium, 20
Ascending type solid solution, 287
applied to solid-vapour equilibrium, 11
Azeotrope, 175
integrated form of, 9, 12
Clapeyron-Clausius equation, 12
Benzoic acid distribution, 196
Coefficient of solubility, 114
Binary liquid solution
Colligative properties, 34
fractional distillation of, 144, 151
of electrolytic solution, 77
temperature versus amount fraction
of strong and weak electrolytes, 75
curves of, 155
origin, 47
vapour pressure versus composition
curves of, 135, 163 Component
Binodal curve, 347 definition of, 95
Boiling point Composition-pressure diagram, 135, 163
diagram, 155 Composition-temperature diagram, 155
elevation constant, 52 Compound
elevation of, 50 congruent, 267
pressure dependence of, 5 incongruent, 273
Bubble-cap column, 161 Concentration cell
with liquid junction potential, 519
Calomel half-cell, 425, 463 without liquid junction potential, 514
Cast iron, 334 Congruent melting point, 267
Cathode, 409 Conjugate solutions, 179
Cell Consolute temperature, 182
classification of, 409 effect of impurity on, 187
concentration, 514 effect of pressure on, 186
diagram, 417, 427 lower, 184
electromotive force of a, 414 upper, 182
electrochemical, 409 Critical solution temperature, 182
electrolytic, 409 Cryohydrate, 311
formulation of a, 409 Cryscopic constant, 59
fuel, 530
galvanic, 410 Daniell cell, 410
reaction, 426 Debye-Hückel law, 563, 569
reversible and irreversible, 413 Degree of freedom, 97
sign convention, 412 Depression of freezing point, 57
with liquid junction, 519 Distillation
without liquid junction, 514 fractional, 157
Chemical potential steam, 192
and criterion of equilibrium, 3 Distribution coefficient, 194
574 Index

Distribution law isobaric, 157

application of phase rule, 194 isothermal, 144
definition, 194 Fractionating column, 161
thermodynamic derivation of, 195 Freezing point
limitation of, 196 depression constant, 59
Donnan membrane equilibrium, 90 depression of, 57
Dry cell, 528 Fuel cell, 530
Duhem-Margules equation, 124, 167
Galvanic cell, 410
Ebullioscopic constant, 52 Gas-ion half-cell, 419
Edison cell, 530 Gibbs-Duhem equation, 167
Electrical and electrochemical Glass electrode, 490
potentials, 418
Electrochemical cells Half-cell, 417
classification of, 409 potentials, 436
sign convention of, 412 Henry’s law, 115
standard state of, 421 and distribution law, 118
Electrode and Raoult’s law, 120
gas-ion, 419 constant, 121
glass, 490 derivation from kinetic-molecular theory, 126
mercury-mercurous chloride-chloride ion, 463 for solute, 124
mercury-mercuric oxide-hydroxide ion, 424, temperature dependence of, 129
464 thermodynamic derivation of, 117
mercury-mercurous sulphate-sulphate ion, 464 Hydrogen-hydrogen ion half-cell, 420
metal amalgam-metal ion, 422
metal-insoluble salt-anion, 423 Ideal law of solubility, 84
metal-metal ion, 421 Ideal solution, 130
oxidation-reduction, 425 boiling point, 153
potential, 436 isobaric fractional distillation, 157
silver-silver chloride-chloride, 423, 463 isothermal fractional distillation, 144
types of, 419 temperature-composition curve of, 152
Electrolytic cell thermodynamic of, 130
sign convention, 409 vapour pressure curves of, 135
Electromotive force vapour pressure of, 134
definition, 414 Ideally dilute solution, 164
determination of, 414 Ideal solubility of gases, 112
equilibrium constant from, 478 Immiscible liquids, 192
ionic product from, 484 Incongruent fusion, 273
measurement of, 415 Ionic product of water from emf, 490
Nernst equation and, 426 Ionic strength, 565
pH from, 486 Isobaric fractional distillation, 157
solubility product from, 480 Isopleth, 251
temperature coefficient of, 470 Isothermal fractional distillation, 144
thermodynamic data from, 470
Elevation of boiling point, 50 Konowaloff s rule, 170, 175
Enaniotropy, 225 Lamda transition, 25
Equilibrium between phases, 1 Lead storage cell, 529
Eutectic Leclanche cell, 528
point, 255 Lever rule, 141, 182, 259
phase diagram, 250 Liquidus curve, 140, 253
Liquid junction potential, 521
Ferric-ferrous half-cell, 425 Lower consolute temperature, 184
First-order phase transition, 23 Lowering of vapour pressure, 41
Fractional crystallization, 290
Fractional distillation, 157 Maximum type solid solution, 294
 Index 575

Mean activity, 562 cupric nitrate-water system, 320

Mean activity coefficient, 562 ferric chloride-water system, 312
Melting point ferrous sulphate-water system, 320
congruent, 267 incongruently melting compound, 272
iron system, 333
incongruent, 273
lead-antimony system, 260
Mercury-mercuric oxide-hydroxide half-
one-component systems, 217
cell, 424, 464
peritectic system, 273
Mercury-mercurous sulphate half-cell, 464
potassium bromide-water system, 255
Metal amalgam-metal ion half-cell, 422 phosphorus system, 232
Metal-insoluble salt-anion half-cell, 423 potassium iodide-water system, 311
Metal-metal ion half-cell, 421 silicone-germanium system, 292
Minimum type solid solution, 293 sodium chloride-water system, 319
Molality, 35 sodium hydroxide-water system, 322
Molarity, 35 sodium iodide-water system. 320
Molar mass determination sodium-potassium system, 277
mass average, 69 sodium sulphate-water system, 317
number average, 69 solid solution, 284
from elevation of boiling point, 57 sulphur, 227
from osmotic pressure, 68 sulphuric acid-water system. 315
from relative lowering of vapour pressure, 44 three-component systems, 336
Monotropy, 230 two-component systems, 245
water, 220
Nernst distribution law, 194 Phase equilibria
Nernst equation, 420 thermodynamic criterion of, 1
Nicad cell, 529 Phase rule
Nonideal solution, 162 derivation for nonreactive system, 98
fractional distillation of, 173 derivation for reactive system, 101
positive and negative deviations, 162, 163 Phase transition first-order, 23
temperature-composition diagram of, 172 second-order, 25
Number of components, 95 Plait point, 347
Polymorphism, 225
One-component system, 217 Potential
Osmosis, 64 chemical, 2
Osmotic pressure, 49, 64 electrical, 418
Oxidation-reduction half-cell, 425 electrochemical, 418
half-cell table of, 437
Partially miscible liquids, 179 Potentiometric titrations, 493
Critical solution temperature, 182 acid-base, 495
distillation of, 188 precipitation, 510
lower consolute temperature, 184 redox, 498
phase rule applied to, 183 Primary cells, 528
temperature-composition diagram, 181
theoretical consideration, 179 Quinhydrone electrode, 487
Peritectic
reaction, 273 Raoult’s law, 42
temperature, 273 and Henry’s law, 120
pH determination, 486 for solvent, 124
Phase, 95 kinetic-molecular treatment of, 126
Phase diagram of Rast method, 89
auric-lead system, 281 Redox indicators, 507
calcium-aluminium system, 282 Reduction potentials, 415
calcium chloride-water system, 319 Reference half-cell, 435, 462
carbon dioxide, 12 Relative lowering of vapour pressure, 43
congruently melting compound, 267 Reversible cells, 413
576 Index

Retrograde solubility, 349 Study of equilibria by distribution

Ruben-Mallory cell, 529 measurement, 200
Systems
Salt bridge, 411, 526 nonreactive, 98
Salting out, 396 one-component, 217
Schreinmakers residue method, 398 reactive, 101
Secondary cells. 529 three-component, 336
Second-order phase transition, 23, 25 two-component, 245
SI units, 571
Silver-cadmium cell, 530 Theoretical plate, 158
Silver-silver chloride half-cell, 423, 463 Thermal analysis, 246
Silver-zinc cell, 530 Thermodynamic criterion of phase equilibria, 1
Solid solution Thermodynamic data from emf measurements, 470
ascending type, 287 Thermodynamics of an ideal solution, 130
maximum type, 294
Three-component systems, 336
minimum type, 293
Tie line, 140
Solidus curve, 253
Transference number, 520
Solubility of
Triangle plot, 336
gases in liquids, 84
Triple point, 221
solute in ideal solution, 83
Trouton’s rule, 15
Solubility of gases
Two-component systems, 245
pressure dependence of, 115
temperature dependence of, 113
Van’t Hoff equation, 67
Solubility product from emf data, 455, 480
Van’t Hoff factor, 75
Solute, 34
Vapour pressure
Solutions
effect of pressure on, 26
dilute, 36
lowering of, 41
ideal, 128
of an ideal binary liquid system, 134
ideally dilute, 164
of a nonideal solution, 162
nonideal, 162
relative lowering of, 43
solid, 284
Vaporous curve, 173
Solvent extraction, 203
Variance of a system, 97
Standard
half-cell potentials, table of, 437
Water, phase diagram of, 220
potential, 434
Weston standard cell, 416
state, 421
Stannic-stannous half cell, 426
Zone refining, 291
Steam distillation, 192
Steel, 335