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Liquids, Solutions, and Interfaces

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Liquids, Solutions, and Interfaces


From Classical Macroscopic Descriptions
to Modern Microscopic Details

W. RONALD FAWCETT
University of California, Davis

1
2004

Oxford New York


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Copyright # 2004 by Oxford University Press, Inc.


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All rights reserved. No part of this publication may be reproduced,
stored in a retrieval system, or transmitted, in any form or by any means,
electronic, mechanical, photocopying, recording, or otherwise,
without the prior permission of Oxford University Press.
Library of Congress Cataloging-in-Publication Data
Fawcett, W. Ronald.
Liquids, solutions, and interfaces / W. Ronald Fawcett.
p. cm.
Includes bibliographical references and index.
ISBN 0-19-509432-8
1. Solution (Chemistry) 2. Interfaces (Physical sciences). I. Title.
QD541.F39 2004
541.3 0 4dc21
2003013539

Cover illustration: A Li+cation solvated by four tetrahedrally disposed


acetonitrile molecules. The Li+cation is the principal component of the
non-aqueous electrolyte solution used in rechargeable lithium ion
batteries found in laptop computers and cell phones. Acetonitrile is often
used as one of the solvents in these batteries.

7 6

2 1

Printed in the United States of America


on acid-free paper

To my three muses,
Zuzana, Natalka, and Tetiana

Time is a never ending Fugue


An Interplay of Slow and Fast
Of Silence . . .
And of Light and Dark
That Flickers with Hypnotic Rhythm

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Preface

This book developed from a series of lectures given to freshmen graduate students
specializing in analytical and physical chemistry and chemical engineering at the
University of California, Davis. The purpose of these lectures is to introduce the
students to modern topics in solution chemistry. Solutions are involved in every
practical chemistry laboratory, in chemical analysis, in biochemistry, in clinical
chemistry, and in chemical synthesis. When I was a student, solution chemistry
occupied a major fraction of physical chemistry textbooks. At that time it dealt
mainly with classical thermodynamics, phase equilibria, and non-equilibrium phenomena, especially those related to electrochemistry. Much has happened in the
intervening period with the development of important new experimental techniques. At the present time, solutions are examined experimentally at the molecular
level. In X-ray and nuclear diraction experiments, the structure of liquids and
solutions is described in atomic detail to give the time average of the distribution
and orientation of the component molecules and ions. Laser spectroscopy provides a route to the time resolution of molecular events occurring in the femtosecond time range. Non-linear spectroscopic techniques are being used to study
the molecular composition and structure of interfaces. Both theory and experiment have seen tremendous advances since the 1950s. The purpose of this book is
to bring the student through these developments from the classical macroscopic
descriptions to the modern microscopic details.
The subject matter in this monograph falls into three general areas. The rst of
these involves liquids and solutions at equilibrium. These subjects are discussed in
chapters 15, and include the thermodynamics of solutions, the structure of
liquids, electrolyte solutions, polar solvents, and the spectroscopy of solvation.

viii

PREFACE

An attempt is made to familiarize the student with the fundamental background


material together with important aspects of current research in each of these
areas. Chapters 6 and 7 deal with non-equilibrium properties of solutions, and
the kinetics of reactions in solutions. In the latter chapter, emphasis is placed on
fast reactions in solution and femtochemistry. Chapters 810 involve important
aspects of solutions at interfaces. These include liquids and solutions at interfaces,
electrochemical equilibria, and the electrical double layer. This subject matter is of
interest to analytical chemists, physical chemists, biochemists, and chemical and
environmental engineers.
The material in this book should be suitable for senior undergraduates and
graduate students who have completed two semesters or three quarters of chemical thermodynamics and statistical mechanics. A solid background in mathematics and physics is also necessary to understand the subject matter. The
instructor will note that detailed derivations of the thermodynamic equations
have been given. In the case of quantum mechanics and statistical mechanics,
some derivations are not given but instead, the background for the theory is
carefully described. In addition, the student is referred to the original literature.
The material is arranged in such a way that it may be presented at dierent levels.
Thus, if one wishes to present only the fundamentals of describing the structure of
liquids from chapter 2, the material dealing with the statistical mechanical
description of liquid systems can be largely avoided. The same comment applies
to most of the material in this monograph. Introductions to thermodynamics,
statistical thermodynamics, and chemical kinetics are included in chapters 1, 2,
and 7, respectively. This material is given to help students review the subject
matter from earlier courses in physical chemistry and to introduce the symbols
used in this book. General references giving other sources for the material covered
in a given chapter, and to compilations of experimental data are listed at the end
of each chapter.
As far as possible only SI units have been used in writing equations and presenting experimental data. Angstroms and calories, which still appear in the
scientic literature, are avoided. Instead, nanometers and picometers are used
for atomic and molecular dimensions, and joules for units of energy. Pressure is
discussed in terms of pascals and bars rather than torrs and atmospheres.
Equations involving the molecular dipolar properties, namely the dipole moment
and polarizability, assume units of coulomb meters and farad square meters,
respectively, for these quantities. However, tabulated data are given in the more
familiar cgs system with debyes for the dipole moment and cubic nanometers for
the polarizability. This follows the usage in most data tabulations at the present
time. The connection between the SI and cgs units is explained in chapter 2. The
symbols recommended by the International Union of Pure and Applied
Chemistry [1] are used as much as possible.
This preface would not be complete without an expression of gratitude to those
who made this project possible. First, I am grateful to those who introduced me to
the topics discussed in this book during my student years at the University of
Toronto. There are many teachers in this group but special mention goes to
Professors Frank Wetmore and Mike Dignam in the Department of Chemistry.

PREFACE

ix

Second, I would like to thank my students, especially those at UC Davis who


listened to and discussed the lectures on which this book is based. Third, I thank
my typists Elizabeth Bogren and Zuzana Kovacova, who patiently and faithfully
prepared the manuscript including all the complicated equations. Special thanks
are also due to Alex Tikanen and Dmytro Verbovy for their work with the
diagrams. Finally, I would like to thank those who reviewed individual chapters
including Rafael Andreu, Imre Bako, Bob de Levie, Dennis Evans, Manuel
Galan, Douglas Henderson, Andrzej Lasia, Shiraz Markarian, Roger Parsons,
Oleg Petrii, Dino Tinti, Nancy True, and Galina Tsirlina. I am especially indebted
to Oldr ich and Eva Fischer, who have gone through the text with painstaking care
and helped to eliminate numerous small errors and to establish a consistent
system of symbols. The helpful comments of all those involved in the review
process resulted in a signicant improvement in this monograph during the
long gestation period.
Reference
1. Mills, I.; Cvitas , T.; Homann, K.; Kallay, N.; Kuchitsu, K. Quantities, Units, and
Symbols in Physical Chemistry; Blackwell Scientic Publications: Oxford, U.K., 1986.

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Contents

Fundamental Constants xvi


1. The Thermodynamics of Liquid Solutions
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
1.10
1.11
1.12
1.13
1.14

Most Liquid Solutions Are Not Ideal, 3


Concentration Units, 4
Thermodynamic Quantities, 6
Partial Molar Quantities, 9
Ideal SolutionsRaoults Law, 15
Thermodynamics of Ideal Solutions, 16
Non-Ideal Solutions, 18
Thermodynamics of Non-Ideal Solutions, 21
Regular Solutions, 24
An Empirical Approach to Non-Ideal Solutions, 30
Ideally Dilute Solutions, 33
Thermodynamics of Ideally Dilute Solutions, 34
Experimental Determination of Solution Activities, 38
Concluding Remarks, 40
References, 41
Problems, 41

2. The Structure of Liquids


2.1
2.2
2.3
2.4
2.5

45

What Is a Liquid?, 45
The Statistical Thermodynamics of Liquids, 47
Intermolecular Forces, 52
Distribution and Correlation Functions, 61
The Experimental Study of Liquid Structure, 65
xi

xii

CONTENTS

2.6 The Direct Correlation Function and the Mean Spherical


Approximation, 70
2.7 Computer Simulations of Simple Liquids, 73
2.8 Estimation of Thermodynamic Properties from the Pair
Correlation Function, 75
2.9 The Properties of a Hard-Sphere Fluid, 79
2.10 The Structure of Water, 84
2.11 Distribution Functions for Liquid Solutions, 88
2.12 Concluding Remarks, 90
References, 91
Problems, 92
3. Electrolyte Solutions
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
3.11
3.12

95

Electrolyte Solutions Are Always Non-Ideal, 95


Ionic Size in Solutions, 97
The Thermodynamics of IonSolvent Interactions, 100
IonSolvent Interactions According to the Born Model, 102
IonSolvent Interactions According to the Mean Spherical
Approximation, 106
The Thermodynamics of Electrolyte Solutions, 111
The Experimental Determination of Activity Coecients for
Electrolytes, 116
IonIon Interactions According to the DebyeHuckel Model,
121
IonIon Interactions According to the MSA, 130
The Thermodynamics of Ion Association, 135
Ion Association According to the MSA, 140
Concluding Remarks, 143
References, 144
Problems, 145

4. Polar Solvents

148

4.1 What Constitutes a Polar Liquid?, 148


4.2 Some Important Properties of Polar Solvents, 149
4.3 The Static Solvent Permittivity on the Basis of Continuum
Models, 153
4.4 The Static Solvent Permittivity According to the MSA, 162
4.5 Dielectric Relaxation Phenomena, 169
4.6 The Permittivity of Electrolyte Solutions, 176
4.7 The Dielectric Relaxation Parameters, 180
4.8 Ion Solvation in Polar Solvents, 184

CONTENTS

xiii

4.9 Polar Solvents as Lewis Acids and Bases, 191


4.10 Concluding Remarks, 199
References, 200
Problems, 201
5. Spectroscopic Studies of Liquid Structure and Solvation

204

5.1
5.2
5.3
5.4
5.5
5.6
5.7
5.8
5.9
5.10

What Spectroscopic Techniques Are Available?, 205


X-Ray and Neutron Diraction Experiments, 206
Nuclear Magnetic Resonance Spectroscopy in Solutions, 213
NMR Studies of Ion Solvation in Water, 219
NMR Studies of Ion Solvation in Non-Aqueous Solvents, 223
Vibrational Spectroscopy in Solutions, 226
Infrared Spectroscopy of Polar Solvents, 232
Infrared Spectroscopy of Non-Electrolyte Solutions, 239
Infrared Spectroscopy of Electrolyte Solutions, 242
UltravioletVisible Spectroscopy and Solvatochromic Eects,
245
5.11 Concluding Remarks, 250
References, 251
Problems, 252
6. Non-Equilibrium Phenomena in Liquids and Solutions
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
6.10
6.11
6.12

254

Non-Equilibrium Processes Are Usually Complex, 254


The Thermodynamics of Irreversible Processes, 255
The Viscosity of Liquids, 259
Isothermal Diusion in Solutions, 264
Linear Diusion from a Wall, 266
The Electrochemical Potential, 271
The Conductivity of Electrolyte Solutions, 274
Experimental Studies of Conductivity, 283
The DebyeOnsager Model for Conductivity, 288
Transport Phenomena in Non-Aqueous Solutions, 294
Proton Transport Phenomena, 298
Concluding Remarks, 300
References, 301
Problems, 301

7. Chemical Reaction Kinetics in Solution

304

7.1 What Time Scales Are Involved for Chemical Reactions in


Solution?, 304
7.2 Fundamental Concepts, 305

xiv

CONTENTS

7.3
7.4
7.5
7.6
7.7
7.8
7.9
7.10
7.11
7.12

General Types of Solution Reactions, 312


Temperature Eects and Transition State Theory, 323
Diusion-Controlled Rapid Reactions, 329
Relaxation Techniques for Rapid Reactions, 332
Laser Spectroscopy and Femtochemistry in Solutions, 338
The Theory of Homogeneous Electron Transfer, 346
NMR Spectroscopy and Chemical Exchange Reactions, 358
Medium Eects in Solution Reactions, 366
Linear Gibbs Energy Relationships, 375
Concluding Remarks, 377
References, 378
Problems, 380

8. Liquids and Solutions at Interfaces

383

8.1 The Molecular Environment at the Interface Is Dierent than


in the Bulk, 383
8.2 The Interfacial Tension of Liquids, 385
8.3 The Thermodynamics of Fluid Interfaces, 390
8.4 The Electrical Aspects of Interfaces, 395
8.5 The Work Function for Electrons in Metals, 398
8.6 The Liquid|Gas Interface and the Adsorption Isotherm, 401
8.7 Experimental Measurement of the Volta Potential Dierence
at Interfaces, 408
8.8 The Metal|Solution Interface, 422
8.9 The Liquid|Liquid Interface, 426
8.10 Surface Films on Liquids, 433
8.11 Spectroscopy at Liquid Interfaces, 437
8.12 Concluding Remarks, 442
References, 443
Problems, 444
9. Charge Transfer Equilibria at Interfaces

447

9.1 Electrochemical Equilibria Occur at a Wide Variety of


Interfaces, 447
9.2 Electrochemical Cells, 448
9.3 The Thermodynamic Basis of the Nernst Equation, 456
9.4 The Absolute Electrode Potential, 461
9.5 Experimental Studies of Electrochemical Cells, 464
9.6 Electrochemical Cells for Electroanalysis, 474
9.7 The Liquid Junction Potential, 477
9.8 Membrane Potentials and the Donnan Eect, 484

CONTENTS

xv

9.9 Ion-Selective Electrodes, 494


9.10 p-Functions and the Denition of pH, 502
9.11 Concluding Remarks, 504
References, 505
Problems, 505
10.

The Electrical Double Layer

508

10.1 The Electrical Double Layer Is an Example of Electrostatic


Equilibrium, 508
10.2 The Thermodynamics of the Ideally Polarizable Interface, 510
10.3 The Experimental Study of the Double Layer, 516
10.4 The Structure of the Double Layer, 530
10.5 The Potential of Zero Charge and the Role of the Metal, 535
10.6 The GouyChapman Model of the Diuse Double Layer, 542
10.7 The Structure of the Inner Layer in the Absence of
Adsorption, 552
10.8 The Specic Adsorption of Ions, 558
10.9 The Adsorption of Molecules at Electrodes, 569
10.10 Concluding Remarks, 576
References, 577
Problems, 579
Appendix A. Mathematical Background
A.1
A.2
A.3
A.4

582

Laplace Transforms, 582


Fourier Transforms, 584
Complex Numbers and Functions, 585
Power Series, 586

Appendix B. The Laws of Electricity and Magnetism


Appendix C. Numerical Methods of Data Analysis
C.1
C.2
C.3
C.4
C.5
C.6
C.7

The Principle of Least Squares, 595


Linear Regression, 599
Multiple Linear Regression, 605
Numerical Methods, 608
Numerical Interpolation, 610
Numerical Integration, 612
Numerical Dierentiation, 614

Index 617

589
595

Fundamental Constants

Fundamental Constants
Velocity of light
Fundamental charge
Electron rest mass
Proton rest mass
Neutron rest mass
Avogadro constant
Planck constant
Boltzmanns constant
Gas constant
Faraday constant
Permittivity of vacuum

c
e0
me
mp
mn
NL
h
kB
R
F
"0

2:997925  108 m s1


1:602177  1019 C
9:109390  1031 kg
1:672623  1027 kg
1:67493  1027 kg
6:022137  1023 mol1
6:626076  1034 Js
1:380658  1023 J K1
8:314510 J mol1 K1
96485.3 C mol1
8:854188  1012 C2 N1 m2

T
g

273.15 K
9.80665 m s2

atm
cal
A

101,325 Pa
4.184 J
100 pm
107 J
101.325 J
1:6022  1019 J
2:9979  109 esu
3:3356  103 esu
8:9875  1011 esu
3:3356  1030 C m
104 Tesla

Dened Constants
Temperature of H2O freezing
Standard acceleration of free fall
Conversion Factors
Standard atmosphere
Thermochemical calorie
Angstrom
1 erg
1 litre atm
1 eV
1C
1V
1F
1 Debye
1 Gauss

From Cohen and Taylor, Rev. Mod. Phys., 59 (1987) 1121


xvi

Liquids, Solutions, and Interfaces

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The Thermodynamics of Liquid


Solutions

Joel Hildebrand was born in Camden, New


Jersey, in 1881. His interest in science
developed in high school and he went on to
study physics and chemistry at the University
of Pennsylvania, obtaining a B.S. degree in
1903. He stayed at Pennsylvania for a doctoral
degree in chemistry, which he obtained in 1906.
Like several young American scientists of that
period, he went to Germany to study the
emerging eld of physical chemistry.
Hildebrand spent a year at the University of
Joel Henry Hildebrand
Berlin in the laboratory of Walther Nernst and
attended lectures given by Nernst and vant
Ho. He then returned to the University of Pennsylvania, where he held the
position of instructor in chemistry until 1913. Then, at the invitation of G. N.
Lewis, he joined the faculty of the University of California at Berkeley, where
he remained for the rest of his scientic career. Hildebrands main scientic
research was in the area of the physical chemistry of liquids and non-electrolyte
solutions. He was a major contributor to the theory of regular solutions. Much
of his work in this eld is summarized in his monograph with Robert Scott,
The Solubility of Non-electrolytes [1]. He was famous at Berkeley for his
lectures, especially to freshman classes. His scientic work was recognized by
many awards during his long career, including the Priestley Medal of the
American Chemical Society in 1962. Hildebrand was also an avid sportsman
and was particularly fond of skiing in the Sierra Nevada mountains. One of his
last papers was published in the Annual Review of Physical Chemistry in 1981
at the age of 100. He died in 1983.

1.1 Most Liquid Solutions Are Not Ideal


Chemistry in the laboratory very often involves the use of liquid solutions. This is
especially true in chemical analysis, where the amount of analyte is easily manipulated when it is dissolved in a solution. Solutions are often the medium for
chemical reactions which form the basis of titrations. Other simple analytical
procedures are based on absorption spectroscopy, which is used to determine
the concentrations of an analyte in solution.
3

LIQUIDS, SOLUTIONS, AND INTERFACES

Most liquid solutions, also called liquid mixtures, are non-ideal. This follows
from the fact that the components are in intimate contact with one another, and
that the forces between the various species are usually not the same. As a result,
the physical properties of the solution, for example, the vapor pressure of a given
component, are usually not simply related to its concentration. This non-ideality
leads to the concept of the activity of a solution component. As far as the analytical chemist is concerned, only concentration is ultimately of interest. Thus, if an
analysis is based on the measurement of a physical property which in turn
depends on the activity of a component, it is very important that the relationship
between activity and concentration be understood for the system in question.
Activity and its relationship to concentration is dened within the context of
chemical thermodynamics. Using the laws which govern phase equilibria and the
laboratory observations relating to these processes one can develop a detailed
understanding of this relationship. In this chapter the macroscopic concepts of
chemical thermodynamics which are relevant to solutions are reviewed. In addition, some simple models based on molecular concepts are discussed. The examples chosen are mainly limited to non-electrolyte solutions, especially those
involving polar molecules.

1.2 Concentration Units


Concentration of one component in a two-component system can be expressed in
several ways: as a weight/weight ratio, as a volume/volume ratio, or as a weight/
volume ratio. Physical chemists clearly prefer to express concentration as a
weight/weight ratio because then one has the possibility of estimating the number
of moles of both components in the solution. In this case, solution composition is
independent of temperature and pressure. On the other hand, the analytical chemist prefers to use a weight/volume ratio. This is usually because one component,
namely, the analyte, is present at low concentration. Then, one refers to this
component as the solute, and the majority component as the solvent. However,
in this case the concentration changes when temperature or pressure is changed.
Consider the simple example of a solution of acetonitrile in water formed by
mixing 10 g of acetonitrile with 90 g of water. The concentration of acetonitrile
can be simply stated as 10% by weight. Another way of expressing the concentration is in terms of the relative number of moles of these molecules. Given that
the molecular mass of acetonitrile is 41.04 g, the number of moles of acetonitrile
nB used to form the solution is 10.000/41.04 0.2437. The corresponding number
of moles of water nA is 90.000/18.02 4.9945 where 18.02 is its molecular mass.
Thus, one may express the concentration as the mole fraction, xB , of acetonitrile
where
xB

nB
0:2437
0:0465

nA nB 4:9945 0:2437

1:2:1

Another commonly used concentration unit in physical chemistry is molality.


It is dened as the number of moles of component B per 1000 g of pure component A, which is regarded here as the solvent. In the present case, the molality is

THE THERMODYNAMICS OF LIQUID SOLUTIONS

0:2437  1000=90 2:708 m. This is still a weight/weight ratio but has units of
mol kg1 . The relationship between mole fraction and molality can be written
xB

mB
1000=MA mB

1:2:2

where MA is the molecular weight of the solvent, that is, component A. In dilute
solutions for which mB  1000/MA this relationship becomes
xB

m B MA
1000

(dilute solutions)

1:2:3

For example, a 0.02 m solution of acetonitrile in water corresponds to a mole


fraction xB equal to 3:6  104 .
The concentration unit used for analysis is molarity, that is, the number of
moles of solute per liter of solution. It should be noted that the molarity involves a
weight/volume ratio, and that the volume involved is that of the total solution. In
order to determine the molarity of the system being considered here, one must
know the density of the solution. In general, this property cannot be determined
from the densities of the individual components but must be found in an independent experiment. The density of acetonitrilewater solutions as a function of
the weight fraction of acetonitrile is shown in g. 1.1. From these data one nds
that the density of the solution made of 10 g acetonitrile and 90 g water is 0.979 g
mL1 at 25 C. Thus, the volume of the same solution is 102.15 mL and the
corresponding molarity, 0.2437/0.10215 2.386 M. The relationship between
the molarity cB and mole fraction xB is
xB

cB
1000 r  cB MB =MA cB

1:2:4

Fig. 1.1 Plots of the density of aqueous solutions of acetonitrile (AcN,*) and sodium
hydroxide (^) against their weight fraction in the solution.

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 1.1 Concentration of Acetonitrile in Aqueous Solutions


Using Different Expressions for the Relative Amounts of
Acetonitrile and Water at 25 C
Weight
Percent

Mole
Fraction/xB

Molality,
mB /mol kg1

Molarity,
cB /mol L1

Solution Density,
r=g L1

0.01
0.1
1
10

4:39  105
4:39  104
4:42  103
0.0465

2:44  103
2:44  102
0.246
2.708

2:44  103
2:44  102
0.245
2.386

0.997
0.997
0.995
0.979

where r is the density of the solution in g mL1 . When the solution is dilute, one
may neglect the terms in the denominator involving cB so that the expression for
xB becomes
xB

cB MA
1000 rA

(dilute solutions)

1:2:5

where rA is the density of the pure solvent A. On comparing equations (1.2.3) and
(1.2.5), one sees that for aqueous solutions where rA 1:0, the molarity is equal
to the molality when the solution is dilute. These calculations are illustrated in
table 1.1 for a change in acetonitrile concentration by a factor of 1000 in the range
of dilute solutions. It is clear that molality and molarity are equal for dilute
aqueous solutions. However, if water is not the solvent, the density of the solution
is probably suciently dierent from unity that these quantities are no longer
equal. Notice also that the denition of molarity is temperature dependent
because the volume of the system depends on temperature. Thus, the analyst
should always cite the temperature at which solutions were prepared.
A plot of the density of sodium hydroxide solutions of varying composition is
also shown in g. 1.1. Electrolyte solutions are considerably more dense than
water when they are concentrated. The important point to remember about
these systems is that their compositions cannot be varied over the whole range
because the solute is normally a solid at room temperature. Thus, the range of the
weight fraction scale is determined by the solubility of the solid solute. In order to
convert from molality to molarity, the solution density must be determined.
Density data for common solutions can be found in data compilations such as
the LandoltBornstein tables.

1.3 Thermodynamic Quantities


The composition of a solution is obviously one of its important properties. In the
preceding section various ways of describing the composition of a two-component
system were described. Other properties include its volume, V, internal energy, U,
and entropy, S. In order to specify any one of these, one must specify not only the
amounts of each of the components but also the temperature, T, and pressure, P.
These quantities are known as the independent variables of the system. They are

THE THERMODYNAMICS OF LIQUID SOLUTIONS

to some extent arbitrary, but nevertheless convenient. If the system possesses


more than two components, the number of variables required to be specied to
determine any quantity such as V is N 2, where N is the number of components.
Consider rst of all the volume of the solution. The volume of any solution
may be estimated from the mass of each component and its density. Volume is an
extensive property, since its value depends on the total amount of solution. A
quantity of more fundamental interest is the specic volume, Vs , that is, the
volume per gram. It is simply the reciprocal of the density. This is an intensive
quantity, since its value does not depend on the size of the solution, only on its
composition, temperature, and pressure. From the point of view of chemists, an
even better way to describe this property is in terms of the molar volume, that is,
the volume per mole of solution. For a two-component solution, the molar
volume Vm is related to the density as follows:
Vm

M A xA M B xB
r

1:3:1

Notice that the units of this quantity are L mol1 if the density is expressed in
g L1 . To calculate the volume from the molar volume one must know the number
of moles of each component, nA and nB . Thus,
V nA nB Vm

1:3:2

where the relative amounts of nA and nB are those required to give the mole
fractions xA and xB .
It was pointed out above that the volume is a function of the number of moles
of each component, temperature, and pressure. Thus, one may write for a twocomponent system
V VnA ; nB ; T; P

1:3:3

It follows that the total derivative of the volume dV is given by




 
 
 
@V
@V
@V
@V
dnA
dnB
dT
dP
dV
@nA nB ;T;P
@nB nA ;T;P
@T nA ;nB ;P
@P nA ;nB ;T
1:3:4
where each partial derivative species the change in the volume with a given
independent variable, holding the other independent variables constant. It is
very important that this specication be made; otherwise one does not know
exactly what change is being measured.
The internal energy of the system, U, is dened on the basis of the rst law of
thermodynamics, which, in simple terms, states that energy cannot be created or
destroyed. For a closed system, the gain in internal energy during a process
involving a change in the values of its independent variables is equal to the
heat gained by the system, q, plus the work done on the system, w.
Mathematically, this is expressed as
U q w

1:3:5

If the changes in q and w are innitesimally small, this relationship may be written
dU dq dw

1:3:6

LIQUIDS, SOLUTIONS, AND INTERFACES

Furthermore, if the work is limited to pressurevolume changes, then


dU dq  PdV

1:3:7

The relationship dw PdV reects the fact that when mechanical work is done
on the system, its volume decreases. Otherwise stated, if the volume of the system
increases during a change in state, the system must do work against the surrounding pressure, which leads to a net loss in its internal energy.
The second law of thermodynamics states that all spontaneous processes lead
to an increase in disorder, which is quantitatively measured by means of the
systems entropy, S. For an innitesimally small process involving a ow of
heat into the system, dq, the entropy change, dS, is given by
dS

dq
T

1:3:8

Combining equations (1.3.7) and (1.3.8), one obtains an important result summarizing the rst and second laws in dierential form:
dU TdS  PdV

1:3:9

One must remember that this expression applies to a closed system, that is, one in
which no matter enters or leaves (dni 0). If one relaxes this condition for a twocomponent system, then the general expression for the change in internal energy
becomes


 
@U
@U
dnA
dn
1:3:10
dU TdS  PdV
@nA nB ;S;V
@nB nA ;S;V B
where the last two derivatives describe the change in internal energy with the
number of moles of each component. Since equation (1.3.10) gives the total
dierential of U, one arrives at the following denitions of temperature and
pressure:
 
@U
T
1:3:11
@S nA ;nB ;V
 
@U
1:3:12
P
@V nA ;nB ;S
Furthermore, equation (1.3.10) suggests that the internal energy is best described
as a function of entropy, volume, and the number of moles of each component,
that is
U US; V; nA ; nB

1:3:13

As a result, chemists have introduced other thermodynamic functions so that the


properties of a system may be considered with respect to more convenient independent variables, especially temperature and pressure.
The three remaining thermodynamic variables and their denitions are as
follows: the enthalpy,
H U PV
the Helmholtz energy,

1:3:14

THE THERMODYNAMICS OF LIQUID SOLUTIONS

A U  TS

1:3:15

G U  TS PV

1:3:16

and the Gibbs energy,


The dierential form of the enthalpy for a closed system may be found by writing
the total derivative:
dH dU PdV VdP

1:3:17

Combining this result with equation (1.3.9), one obtains


dH TdS VdP

1:3:18

For the Helmholtz energy, the corresponding result is


dA SdT  PdV

1:3:19

dG SdT VdP

1:3:20

and for the Gibbs energy


It follows that the Gibbs energy for a closed system is conveniently described as
a function of temperature and pressure. Relaxing the condition that the system be
closed, the total derivative of G in an open two-component system becomes


 
@G
@G
dn
dn
1:3:21
dG SdT VdP
@nA nB ;T;P A
@nB nA ;T;P B
This is a very important equation in discussing chemical equilibria, and is the
starting point for deriving other important results. One sees that the entropy can
be dened from the temperature dependence of the Gibbs energy,
 
@G
S
1:3:22
@T P;nA ;nB
and the volume from the pressure dependence
 
@G
V
@P T;nA ;nB

1:3:23

The thermodynamic variables, U; S; H; A; and G introduced above are extensive quantities like the volume V. Thus, the amount of internal energy in a sulfuric
acid solution depends on whether one has 250 mL beaker, a 4 L bottle, or a full
railway tank car. Just as for volume, it is necessary to dene intensive variables
giving the internal energy per gram, Us , or the internal energy per mole, Um . Since
the present discussion is concerned with chemistry, we will use only the molar
quantities Um , Sm , Hm , Am , and Gm which are dened from the corresponding
extensive quantity by equations like equation (1.3.2).

1.4 Partial Molar Quantities


Partial molar quantities are used to describe the change in properties of a multicomponent system when one component is added at constant temperature, pres-

10

LIQUIDS, SOLUTIONS, AND INTERFACES

sure, and amounts of all other components. In the present section, partial molar
quantities will be considered with respect to the volume of a two-component
system. For example, the partial molar volume of component A is dened as


@V
A
1:4:1
@nA nB ;T;P
and that of B as


B

@V
@nB


1:4:2
nA ;T;P

It follows from equation (1.3.4) that, at constant temperature and pressure, a


change in the volume of a two-component solution is given by
dV A dnA B dnB

1:4:3

This expression may be integrated under conditions that the relative amounts of
nA and nB , that is, the composition of the solution, do not change:
V  A n A B n B

1:4:4

The resulting equation states that the volume of the solution may be calculated
given the number of moles of each component and their partial molar volumes. In
terms of the molar volume, this equation becomes
Vm A xA B xB

1:4:5

It can be shown that there is a relationship between the partial molar volumes for
a given solution composition. Taking the total derivative of the volume on the
basis of equation (1.4.4), one obtains at constant temperature and pressure
dV A dnA nA dA B dnB nB dB

1:4:6

Comparing equations (1.4.3) and (1.4.6), one nds that


nA dA nB dB 0

1:4:7

or dividing by the total number of moles, nA nB ,


xA dA xB dB 0

1:4:8

This equation, which is one example of the GibbsDuhem equation, shows that
changes in the partial molar volume of one component may be related to changes
in the same quantity for the other component. Experimentally, it means that one
only has to measure one partial molar volume as a function of composition
provided one has a value of the second partial molar volume at a reference
point. In order to illustrate this point, equation (1.4.8) is written in a form suitable
for calculating A from B :

xB
d
1:4:9
dA 
xA B
If the reference point for the integration is a solution consisting of pure component A (xB 0), then the integration constant required is the molar volume of
pure component A, and one may write

THE THERMODYNAMICS OF LIQUID SOLUTIONS

11

Fig. 1.2 Plots of the molar volume of aqueous solutions of acetonitrile (AcN) and
methanol (MeOH) against their mole fraction in solution.
xB

A  VmA 
xB 0

xB
d
xA B

1:4:10

Since the data tabulated in the literature for thermodynamic quantities are
intensive, one needs a method of determining partial molar quantities from
these data. However, the partial molar quantity involves the rst derivative of
an extensive quantity such as the volume with respect to the number of moles of a
particular component. Although the resulting derivative is intensive in nature, it
itself implies that it comes from extensive quantities. The raw data that are used to
estimate @V=@ni are normally the molar volume Vm as a function of the mole
fraction of a given component xi . Thus, it is reasonable to examine the relationship between @V=@ni and @Vm =@xi . A plot of Vm against xB , the mole fraction of
acetonitrile, is shown in g. 1.2 using the data given in table 1.2 for the acetonitrilewater system. Considering the relationship between V and Vm (equation
(1.3.2)),




@V m
1
@V
V


1:4:11
@nA nB nA nB @nA nB nA nB 2
Furthermore,

@xB
@nA

nB

nB
nA nB 2

1:4:12

Now dividing equation (1.4.11) by (1.4.12), one obtains the result that
@V m

V
 A
@xB
x B nB
This equation is rearranged to give

1:4:13

12

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 1.2 Molar Volume Data for the AcetonitrileWater System at


25 C
Partial Molar Volumes
Mole Fraction Molar Volume
Excess
of Acetonitrile of the Solution Molar Volume
Water
Acetonitrile
1
xAcN
Vm /mL mol1 V ex
AcN / mL mol1 w /mL mol1
m /mL mol
0
0.2
0.4
0.6
0.8
1.0

18.07
24.56
31.48
38.60
45.85
53.01

0
0.50
0.56
0.44
0.17
0

Vm A xB

51.83
52.51
53.03
53.08
53.01

@V m
@xB

18.07
17.75
17.46
16.95
16.91

1:4:14

One may interpret this equation by relating it to the equation for a simple straight
line. Referring to g. 1.2, it follows that a line drawn with a slope equal to @Vm
=@xB at the point (Vm , xB ) will intersect the Vm axis at A , which is the y intercept.
Such a line is shown on the molar volume plot in g. 1.2 at the point ^ (xB 0.5)
for the methanolwater system. In a similar way, it is easily shown that
Vm B xA

@V m
@xA

1:4:15

Since a plot of the molar volume against the mole fraction of B is easily converted
to one against the mole fraction of A (xA 1  xB ), equation (1.4.15) shows that
the intercept on the right-hand ordinate of g. 1.2 (xB 1, xA 0) gives the
partial molar volume of component B.
On the basis of the above analysis it has been shown the partial molar quantities are easily obtained from intensive quantities like the molar volume Vm when
this quantity is plotted as a function of an intensive composition variable like the
mole fraction. The plots in g. 1.2 show that the molar volume is almost a linear
function of the mole fraction of solute. If the curves in g. 1.2 were actually
perfect straight lines, the partial molar volumes would be constant independent
of solution composition. Such a situation would arise if the solution were perfectly
ideal. In reality, very few solutions are ideal, as will be seen from the discussion in
the following section. In order to see more clearly the departure from ideality, one
denes and calculates a quantity called the excess molar volume. This quantity is
equal to the actual molar volume less the molar volume for the solution if it were
ideal. The latter can be considered as the volume of the solution that would be
found if the molecules of the two components form a solution without expansion
or contraction. Thus, the ideal molar volume can be dened as
V id
m xA VmA xB VmB

1:4:16

and is calculated directly from the molar volumes of the pure components A and
B. It follows that the excess molar volume is given by

THE THERMODYNAMICS OF LIQUID SOLUTIONS


id
V ex
m Vm  V m Vm  xA VmA  xB VmB

13

1:4:17

The excess molar volume is also called the molar volume of mixing.
Plots of V ex
m against the mole fraction of solute are shown for the acetonitrile
water and methanolwater systems in g. 1.3. The V ex
m function focuses attention
on the non-ideality of the solution. The plots demonstrate clearly that the behavior of these solutions is not simple. Both systems have negative excess volumes.
This indicates that the molecules occupy a smaller volume in solution than they
do as pure liquids. Such an observation is undoubtedly due to attractive forces
between the two components, which are stronger than the forces between molecules in the pure liquids.
The partial molar volumes may be calculated from the data for the excess
molar volume in a manner similar to that used with the molar volume data. On
the basis of equation (1.4.17), one may write
@V ex
@V m
m

VmA  VmB
@xB
@xB

1:4:18

Then substituting equation (1.4.13), one obtains after rearrangement


A Vm  xB

@V ex
m
xB VmA  VmB
@xB

1:4:19

Using the denition of V ex


m given by equation (1.4.17), this simplies to
A V ex
m  xB

@V ex
m
VmA
@xB

1:4:20

In a similar way, one may show that

Fig. 1.3 Plots of the excess molar volume for the acetonitrile (AcN)water and methanol
(MeOH)water systems against the mole fraction of these solutes.

14

LIQUIDS, SOLUTIONS, AND INTERFACES

B V ex
m  xA

@V ex
m
VmB
@xA

1:4:21

EXAMPLE

The application of equations (1.4.20) and (1.4.21) to determine partial molar


volumes in the methanolwater system is now illustrated. The excess molar
volume for this system is fairly symmetrical with respect to the mole fraction of
methanol, and can be tted with reasonable accuracy by a cubic equation using
least squares. The result is
V ex
m 0:0286  4:163xB 4:341xB2  0:1977xB3

1:4:22

The resulting curve is shown in g. 1.3, drawn through the experimental points.
On the basis of this analytical expression, one may now write an analytical
expression for the rst derivative at any point on the curve. This equation is
@V ex
m
4:163 8:682xB  0:5931xB2
@xB

1:4:23

Now, suppose one wants the values of the partial molar volumes at xB 0.4.
1
Substituting into equation (1.4.22), one nds that V ex
m 0:955 mL mol ;
ex
1
similarly, from equation (1.4.23), @V m =@xB 0:785 mL mol . The molar
volume of pure water, VmA , is 18.07 mL mol1 , and that of pure methanol,
VmB , 40.72 mL mol1 . Calculating the partial molar volume of water from
equation (1.4.20), one obtains
A 0:955 0:4  0:785 18:07
17:43 mL mol1

1:4:24

Similarly, from equation (1.4.21) for the partial molar volume of methanol,
B 0:955  0:6  0:785 40:72
39:29 mL mol1

1:4:25

These calculations can be carried out for any value of xB .


Partial molar quantities can be dened for any of the remaining thermodynamic functions including the internal energy U, the enthalpy H, the Helmholtz
energy A, and the Gibbs energy G. Those most used in chemistry are the chemical
potentials, which are dened from the Gibbs energy for the system. Thus, the
chemical potential of component A is dened as


@G
1:4:26
mA
@nA nB ;T;P
and that for component B as

@G
mB
@nB


1:4:27
nA ;T;P

THE THERMODYNAMICS OF LIQUID SOLUTIONS

15

These quantities are connected to the molar Gibbs energy for the solution by the
equation
Gm xA mA xB mB

1:4:28

The application of these quantities to understanding physical and chemical equilibria in solutions is investigated in the sections which follow.

1.5 Ideal SolutionsRaoults Law


The concept of an ideal solution is important in the development of an understanding of the properties of real solutions. In a liquid solution, molecules are in
intimate contact with one another so that the question of ideality is determined by
the nature of the intermolecular forces. Suppose a solution is formed by mixing
two liquids, A and B. Then, the solution is ideal if the intermolecular forces
between A and B molecules are no dierent from those between A and A, or B
and B molecules.
An indication of whether or not the above condition for ideality is met is
obtained from the vapor pressure of the solution. At a given temperature, the
vapor pressure of a pure liquid is a measure of the ability of molecules to escape
from the liquid to the gas phase. By studying the vapor pressure of a solution as a
function of its composition at constant temperature one may assess the solutions
ideality or its degree of departure from ideality. For an ideal solution, the tendency of molecule A to escape is proportional to its mole fraction, that is, to its
concentration expressed in terms of the fraction of molecules which are of type A.
The proportionality constant must be the vapor pressure of pure component A
because this vapor pressure is reached when the mole fraction is unity. This result
is Raoults law, which is expressed mathematically as
PA PA xA

1:5:1

Similarly, for the other component B,


PB PB xB

1:5:2

A system which is close to ideal in its behavior is a solution of benzene and


toluene. These molecules are very similar in structure so that the intermolecular
forces between benzene and toluene do not dier greatly from those between
benzene molecules or toluene molecules in each pure liquid. The vapor pressure
diagram for this system at 25 C is shown in g. 1.4. Since toluene has a higher
molecular weight, its vapor pressure as a pure liquid is lower (3.25 kPa) than that
of benzene (12.69 kPa). The total vapor pressure PT is obtained by adding those
of components A and B, so that
PT PA PB PA PB  PA xB

1:5:3

The total vapor pressure also a linear function of the mole fractions xA and xB .
It is clear from the above that Raoults law denes ideality by relating the
properties of the liquid solution to the vapor with which it is in equilibrium.
Since one knows how to deal with the thermodynamic properties of ideal gaseous

16

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 1.4 Vapor pressure of benzene, PBZ , and toluene, PTL , and total vapor pressure, PT ,
plotted against the mole fraction of toluene xTL for benzenetoluene solutions at 25 C.

solutions, one now has a route to develop the thermodynamics of ideal liquid
solutions.

1.6 Thermodynamics of Ideal Solutions


The thermodynamic equations for ideal solutions are derived by considering the
equilibrium between a given component in the vapor phase and liquid solution.
Thus, for component A in a solution containing two components,
Aliquid Avapor

1:6:1

The thermodynamic condition for equilibrium is that the chemical potential of A


in the liquid phase be equal to that of A in the vapor, that is,
msA mvA

1:6:2

where msA is the chemical potential of A in the liquid solution, and mvA , that for A
in the vapor phase. If one now assumes that the vapor phase behaves ideally, one
may write
mvA mv;
A RT ln PA

1:63

where mv;
A is the standard chemical potential of A in the vapor phase measured
when the partial pressure of A is 1 bar, and PA , the actual partial pressure of A.
Since Raoults law applies when the liquid solution is ideal, one may also write
v;
msA mvA mA
RT ln xA PA

1:6:4

THE THERMODYNAMICS OF LIQUID SOLUTIONS

17

where xA is the mole fraction of A and PA the partial pressure of the pure liquid
v;
and PA are constants for any given temperature and pressure,
A. Since mA
equation (1.6.4) may be rewritten as
msA ms;
A RT ln xA

1:6:5

s;

mv;
mA
A RT ln PA

1:6:6

where
s;
mA

Thus,
is the standard chemical potential of component A in the liquid solution, which can be measured when the mole fraction of A is one (pure A). A
similar analysis for the other component B leads to the equation
msB ms;
B RT ln xB

1:6:7

v;

ms;
B mB RT ln PB

1:6:8

where

The thermodynamic quantities associated with the mixing of pure liquids to


form a solution are important in assessing solution properties. Suppose nA moles
of component A are combined with nB moles of component B to form a solution.
The Gibbs energy change associated with this process is given by
s;
 nB ms;
mix G nA msA nB msB  nA mA
B

1:6:9

On the basis of equations (1.6.5) and (1.6.7), this may be rewritten as


mix G nA RT ln xA nB RT ln xB

1:6:10

Dividing both sides by the total number of moles, nA nB , one obtains


mix Gm xA RT ln xA xB RT ln xB

1:6:11

where the subscript m indicates that the Gibbs energy change is given on a
molar (intensive) basis. It is easy to see that this result can be generalized to a
multicomponent system with n components by writing
mix Gm

n
X

xi RT ln xi

1:6:12

i1

Since the mole fraction xi is less than one, its logarithm is negative. Thus, mix Gm
is a negative quantity, indicating that the mixing process is spontaneous, as one
would expect.
The entropy change associated with mixing can be obtained by taking the
temperature derivative of mix Gm . Accordingly,
mix Sm 

n
X
@mix Gm

xi R ln xi
@T
i1

1:6:13

This quantity is clearly positive, since the mixing process results in an increase in
entropy.
On the basis of the denitions of Gibbs energy and enthalpy (equations
(1.3.14) and (1.3.16), the enthalpy of mixing is given by

18

LIQUIDS, SOLUTIONS, AND INTERFACES

mix Hm mix Gm Tmix Sm

1:6:14

Substituting in equations (1.6.12) and (1.6.13), one obtains


mix Hm 0

1:6:15

This result gives one of the important properties of ideal solutions, namely, that
the mixing process does not involve any heat. Since the components of the solution interact with each other in exactly the same manner that they interact with
themselves in the pure liquid, mixing is neither exothermic nor endothermic.
By taking the pressure derivative of mix Gm , one may determine the volume
change associated with mixing:
mix Vm

@mix Gm
0
@P

1:6:16

The fact that the volume change associated with mixing the components is zero
gives another important property of an ideal solution. On the other hand, a
volume change does accompany the formation of most solutions. One example
was analyzed above in section 1.4. This change is another reection of the fact
that the energy due to the intermolecular forces between the components changes
with solution composition.
In summary, there are three important characteristics of ideal solutions that
one should remember in assessing the properties of any non-ideal system: (i) the
vapor pressure of each component is proportional to its mole fraction in solution
over the whole composition range (Raoults law); (ii) the enthalpy of mixing is
zero; (iii) the volume change associated with mixing is zero. The sections which
follow deal with non-ideal solutions.

1.7 Non-Ideal Solutions


Most solutions are non-ideal. This is simply a result of dierences in the chemical
nature of the molecular components in the solution, and in the way in which they
interact with each other. A convenient way of examining intermolecular forces in
a pure liquid is in terms of its internal pressure, Pi , which is dened as
 
@U
1:7:1
Pi
@V T
This quantity was investigated extensively by Hildebrand [1], who showed that the
internal pressure is approximately equal to the enthalpy of vaporization divided
by the molar volume. Thus,
Pi

vap H m
Vm

1:7:2

Values of the internal pressure for some commonly used solvents are given in
table 1.3. It is apparent that the internal pressure varies considerably from one
solvent to another, water having the highest value among those considered.

THE THERMODYNAMICS OF LIQUID SOLUTIONS

19

Table 1.3 Values of Internal Pressure for Some Common Solvents at


25 C

Solvent
Acetonitrile
Acetone
Carbon tetrachloride
Chloroform
Dimethylsulfoxide
Hexane
Nitrobenzene
Methanol
Propylene carbonate
Water

Molar Volume
Vm =cm3 mol1

Enthalpy of Vaporization
vap Hm / kJ mol1

Internal
Pressure
Pi /kJ dm3

52.9
74.0
97.1
80.7
71.3
131.6
102.7
40.7
85.2
18.07

33.2
30.8
32.4
32.2
52.9
31.55
52.5
37.43
42.8
43.99

628
416
334
399
742
240
511
917
502
2434

Thus, one has a clear indication that intermolecular forces are signicantly
dierent in these liquids. Under these circumstances, a solution formed from
two of them would not be ideal and would generally exhibit positive deviations
from Raoults law. It is also obvious that not every pair of liquids formed from
those shown in the table are miscible. Thus, a very non-polar solvent such as
hexane is immiscible with a very polar one like water. For those which are
miscible, the dierence in internal pressure gives a good indication of the extent
of departure from ideality. A very few systems show a negative deviation from
Raoults law behavior. This occurs when there is a strong attraction between the
two molecules forming the solution, a well-known example being the chloroformacetone system.
An example of a system exhibiting a small positive deviation from Raoults
law is a methanolwater solution (see g. 1.5). It should be noted that when the
concentration of methanol is small (xMeOH < 0.1), the vapor pressure of water is
close to the value expected on the basis of Raoults law. Similarly, for a dilute
solution of water in methanol (xMeOH > 0.9, xw < 0.1), the vapor pressure of
methanol is approximately equal to that in an ideal solution. These conditions
are often observed in dilute solutions and have important consequences with
respect to their thermodynamic properties, as will be seen in the following
section.
A much more complex behavior is demonstrated by the acetonitrilewater
system [2] (g. 1.6). The vapor pressure curves show an interesting change in
slope at a mole fraction of acetonitrile close to 0.8. However, when the mole
fraction of acetonitrile is less than 0.06, the vapor pressure of water is close to
the value predicted by Raoults law.
As mentioned above, a few systems show negative deviations from Raoults
law, a well-known example being the acetonechloroform system (g. 1.7). In this
case there is attractive interaction between the two components, specically,
between the electron-rich oxygen in acetone, and the hydrogen atom in chloroform. As a result, the escaping tendency of either molecule from the solution is

20

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 1.5 Vapor pressure of methanol and water for methanolwater solutions plotted
against the mole fraction of methanol at 40 C. The left-hand ordinate scale gives the
vapor pressure of water and the right-hand scale that of methanol.

less than it would be if the chemical interaction did not occur. These systems are
similar to those showing positive deviations from Raoults law in that the vapor
pressure of the predominant component approaches ideal behavior when the mole
fraction of the minority component is very small, that is, with a mole fraction less
than 0.1.
Now we proceed to examine the thermodynamic properties of non-ideal
solutions.

Fig. 1.6 Vapor pressure of acetonitrile and water for acetonitrilewater solutions at 25 C
plotted against the mole fraction of acetonitrile. The left-hand ordinate scale gives the
vapor pressure of water and the right-hand scale, that of acetonitrile.

THE THERMODYNAMICS OF LIQUID SOLUTIONS

21

Fig. 1.7 Vapor pressure of acetone and chloroform for acetonechloroform solutions at
35 C plotted against the mole fraction of acetone.

1.8 Thermodynamics of Non-Ideal Solutions


The starting point for developing the thermodynamics of non-ideal solutions is
the same as that for ideal solutions. Thus, one considers the equilibrium between
each component in the liquid solution and its vapor. It follows from section 1.6
that one may write in general for component A,
msA mvA mv;
A RT ln PA

1:8:1

This equation states that chemical potentials of component A in the liquid solution and vapor are equal and that each relates to the vapor pressure of A.
However, one would like to have a way of relating the chemical potential of A
to its mole fraction in solution. This is achieved by relating the vapor pressure of
A to its mole fraction in the liquid solution using a correction factor to make the
value of PA predicted by Raoults law equal to the true value. Thus, one writes
PA gA xA PA

1:8:2

where gA is the correction factor, known as the activity coecient of A. It is clear


that gA is greater than unity when the system exhibits positive deviations from
Raoults law, and less than unity when the deviations are negative. Furthermore,
the value of gA depends on xA , since the extent of departure varies with solution
composition (see gs. 1.51.7). Combining equations (1.8.1) and (1.8.2), one
obtains
msA ms;
A RT ln gA xA

1:8:3

s;
is given by equation (1.6.6). It is emphasized that the standard state for
where mA
this denition of the activity coecient is based on the properties of pure component A. As the mole fraction of A approaches unity, the activity coecient gA
also approaches unity, as can be seen from the vapor pressure plots presented
earlier. It is also emphasized that the standard chemical potential has the same

22

LIQUIDS, SOLUTIONS, AND INTERFACES

value as it would have in an ideal solution because it only depends on the properties of pure component A. The product gA xA is known as the activity of component A in solution. Thus, one may also write
s;
RT ln aA
msA mA

1:8:4

a A g A xA

1:8:5

where

In a similar way, one may write for component B,


s;
msB ms;
B RT ln aB mB RT ln gB xB

1:8:6

where mBs; is given by equation (1.6.8) and


gB PB =xB PB

1:8:7

It is interesting to evaluate the thermodynamic functions of mixing for the nonideal solution. On the basis of equations (1.8.3) and (1.8.6),
mix G nA RT ln gA xA nB RT ln gB xB

1:8:8

mix Gm xA RT ln gA xA xB RT ln gB xB

1:8:9

or on a molar basis

In the case of non-ideal solutions the mixing functions are often referred to the
value they would have in an ideal solution, mix Gid
m , thereby dening the excess
Gibbs energy of solution formation:
id
mix Gex
m mix Gm  mix Gm xA RT ln gA xB RT ln gB

1:8:10

In order to calculate the other excess functions one must know the temperature
and pressure derivatives of the activity coecients gA and gB . The excess entropy
of mixing is given by
mix Sex
m xA R ln gA  xA RT

@ ln gA
@ ln gB
 xB R ln gB  xB RT
@T
@T

1:8:11

and the excess enthalpy by


2
mix H ex
m xA RT

@ ln gA
@ ln gB
 xB RT 2
@T
@T

1:8:12

Finally, the excess volume of mixing is obtained from the pressure derivatives of
the activity coecients:
mix Vmex xA RT

@ ln gA
@ ln gB
xB RT
@P
@P

1:8:13

EXAMPLE

The vapor pressure of acetonitrile above an acetonitrilewater solution with a


mole fraction of 0.395 in acetonitrile is 9.727 kPa at 25 C. The corresponding
vapor pressure of water is 2.874 kPa. At the same temperature the vapor

THE THERMODYNAMICS OF LIQUID SOLUTIONS

23

pressures of the pure liquids are 11.983 kPa and 3.166 kPa for acetonitrile and
water, respectively. Estimate the Raoult law activity coecients for each component, the molar Gibbs energy of mixing, and the excess value of this function. The enthalpy of mixing for this solution is 876.1 J mol1 . Estimate the
entropy of mixing and its excess value.
The Raoult law activity coecient for acetonitrile is
gAcN

9:727
2:055
0:395  11:98

1:8:14

The corresponding quantity for water is


gw

2:874
1:500
0:605  3:166

1:8:15

The molar Gibbs energy of mixing is


mix Gm 0:395  2479:4  ln2:055  0:395
0:605  2479:4  ln1:500  0:605

1:8:16

349:9 J mol1
The excess molar Gibbs energy of mixing is
mix Gex
m 0:395  2479:4 ln2:055 0:605  2479:4 ln1:500
1313:6 J mol1

1:8:17

The enthalpy of mixing is also the excess enthalpy of mixing because an ideal
solution has zero enthalpy of mixing. Now, the entropy of mixing can be
calculated:
mix S m

mix H m  mix Gm 876:1 349:9


4:111 J K1 mol1

298:2
T

1:8:18

and
mix Sex
m

ex
mix H ex
876:1  1313:6
m  mix Gm
1:467 J K1 mol1

298:2
T
1:8:19

Values of the excess Gibbs energy, enthalpy, and entropy for the acetonitrile
water system which show signicant departures from ideality are shown as a
function of solution composition in g. 1.8. The excess enthalpy is positive over
the whole composition range, reaching a maximum value of 1067 J mol1 in the
vicinity of an acetonitrile mole fraction equal to 0.7. These data give a direct
measure of the endothermic nature of the mixing process. The excess entropy
displays a rather complex behavior, being negative at lower concentrations of
acetonitrile and positive for values of xAcN greater than 0.7. Excess thermodynamic data such as those shown in g. 1.8 provide a convenient way of recording
the properties of non-ideal solutions and are often found in tables for liquidvapour equilibria. However, they provide information about the solution as a

24

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 1.8 Excess Gibbs energy, enthalpy, and entropy for acetonitrilewater solutions at
25 C plotted against the mole fraction of acetonitrile.

whole, not about the individual components. If one wants the activity coecients
for each component, one must also have vapor pressure data for each component
as a function of solution composition.
In assessing the above treatment of non-ideal solutions, it must be kept in mind
that it is applicable to a limited number of systems. This follows from the fact that
we are often dealing with solutions of solids in liquids, and also because not all
liquids are miscible over the whole composition range. Under these circumstances
it is not convenient to dene the standard state for one component in terms of the
pure substance. Thus, for the majority of solutions, the majority component is
treated as the solvent and its thermodynamics discussed with respect to its pure
state within the context of Raoults law. The other minority component, which is
the solute, is discussed using a standard state based on the properties of an ideally
dilute solution. These systems are considered in more detail later in this chapter.

1.9 Regular Solutions


In examining the properties of non-ideal solutions, it became clear that some
systems dier from ideality in a manner which could be treated by quite simple
statistical mechanical models. The solution non-ideality is often reected in the
experimental observation that the enthalpy of mixing is not zero, so that AB
interactions are dierent from AA and BB interactions. On the basis of his
study of the properties of a large number of liquid solutions, Hildebrand [1, 3]
introduced the concept of a regular solution. This is a system for which the
enthalpy of mixing is non-zero and the entropy of mixing has its ideal value so
that Sex is zero. This is equivalent to assuming that the molecules are randomly
distributed in the mixture so that the dierences in the intermolecular forces
which lead to the non-zero value of H ex cannot be large. Guggenheim [4, 5]

THE THERMODYNAMICS OF LIQUID SOLUTIONS

25

discussed strictly regular solutions which have the additional restriction that
mix V ex
m be zero. These types of systems are considered in this section.
Consider a mixture of two molecules A and B which are both approximately
spherical in shape. As perfect spheres they can pack together in a face-centered
cubic lattice to form a liquid with a coordination number c of 12 in each pure
liquid. The mixture packs in the same way provided the molecular sizes are not
too dierent, more specically, provided the molecular volumes do not dier by
more than a factor of two [4]. If the free volume between molecules in the mixture
does not dier from the sum of those in the two pure liquids used to form the
mixture, then the volume of mixing is eectively zero, and the interaction energy
experienced by a given molecule in the mixture may be calculated by summing the
contributions from nearest neighbors. Mixtures with these properties are strictly
regular.
Let us now consider how one can estimate the enthalpy of mixing given the
enthalpies associated with AA, AB, and BB interactions at the molecular level.
If each molecule has c nearest neighbors, then the number of interactions experienced by type A molecules is cnA /2, and the number of B molecules, cnB /2, where
the factor of two appears in order to avoid counting the interactions twice. If one
denes the number of AA interactions as nAA , the number of BB interactions as
nBB , and the number of AB interactions as nAB , it follows that
cnA 2nAA nAB

1:9:1

cnB 2nBB nAB

1:9:2

and

By adding these equations, one obtains an expression for twice the total number
of interactions in the solution.
Suppose that the enthalpy associated with an AA interaction is hAA , that with
BB, hBB , and that with an AB interaction, hAB . Then the enthalpy of nA molecules in pure A associated with intermolecular interactions is
cn
1:9:3
HA A hAA
2
Similarly, for pure B,
HB

cnB
h
2 BB

1:9:4

The enthalpy of the solution formed from these pure liquids, associated with
intermolecular interactions is
Hsl nAA hAA nBB hBB nAB hAB

1:9:5

As a result, the enthalpy of mixing becomes


mix H Hsl  HA  HB


hAA hBB
nAB hAB 
2

1:9:6

In order to develop this model further one has to obtain an expression for nAB
in terms of nA and nB . The assumption used is that the molecular composition

26

LIQUIDS, SOLUTIONS, AND INTERFACES

around a given molecule is completely random and therefore reects the overall
solution composition. This is precisely the assumption used by Hildebrand to
dene a regular solution. Thus, the number nAB can be calculated from the
mole fractions dening solution composition, and is given by
nAB cnxA xB

1:9:7

where n is the total number of molecules (n nA nB ). The enthalpy of mixing


can now be expressed as
mix H cnxA xB h

1:9:8

where
h hAB 

hAA hBB
2

1:9:9

Since the mixing process is completely random, one may use the value of Smix
for an ideal solution, which for the present system is given by
mix S nA R ln xA  nB R ln xB

1:9:10

Thus, the expression for the Gibbs energy of mixing becomes


mix G nA RT ln xA nB RT ln xB cnA nB xA xB h

1:9:11

One can now derive expressions for the chemical potentials of the individual
components. Since the Gibbs energy of the solution is
s;
nB mBs; mix G
Gsl nA mA

1:9:12

the chemical potential of A is obtained by dierentiating Gsl with respect to nA


(equation (1.4.26)):
2
mA ms;
A RT ln xA cxB h

1:9:13

Similarly, one nds for B,


mB mBs; RT ln xB cx2A h

1:9:14

Thus, according to the model for a regular solution the activity coecients gA and
gB are given by
ln gA

cx2B h
RT

1:9:15

ln gB

cx2A h
RT

1:9:16

and

These quantities, in turn, may be related to the vapor pressure of each component
over the solution using equations. (1.8.2) and (1.8.7):
!
cx2B h

PA xA PA exp
1:9:17
RT
and

THE THERMODYNAMICS OF LIQUID SOLUTIONS

PB xB PB exp

cx2A h
RT

27

1:9:18

A plot of vapor pressure data for a hypothetical system, assuming ch=RT is


unity, is shown in g. 1.9. The positive deviations from ideality indicate that the
mixing process is endothermic. As the parameter h is increased, the deviations
increase in the positive direction. Obviously, the theory also predicts negative
deviations from Raoults law when h is negative, that is, when the mixing
process is exothermic. Under these conditions the intermolecular forces between
the two species A and B are attractive, and the escaping tendency of each is less
than it would be if the solution were ideal (h 0).
EXAMPLE

Estimate the vapor pressure of the two components in a regular solution for
which ch=RT 1 and xA 0.4 given that the vapor pressure of pure
component A is 15.0 kPa and that of pure B, 20.0 kPa. Also calculate the
Raoult law activity coecients. Repeat the calculation for the case that
ch=RT 1.
From equation (1.9.17) at xA 0.4, the vapor pressure of A is
PA 0:4  15:0 exp 1  0:36 8:60 kPa

1:9:19

The vapor pressure of B is


PB 0:6  20:0 exp 1  0:16 14:08 kPa

1:9:20

The activity coecients are


gA

PA
8:60
1:433


xA pA 0:4  15:0

1:9:21

Fig. 1.9 Vapor pressure for a hypothetical regular solution for which chRT 1 plotted
against the mole fraction of component B. The vapor pressure of pure component B is 26.7
kPa, and that of component A, 20.0 kPa. The broken lines show Raoult law behavior.

28

LIQUIDS, SOLUTIONS, AND INTERFACES

and
gB

PB
14:08
1:173

xB PB 0:6  20:0

1:9:22

In the case that the mixing process is exothermic and ch=RT 1, the
vapor pressures are
PA 0:4  15:0 exp1  0:36 4:19 kPa

1:9:23

PB 0:6  20:0 exp1  0:16 10:23 kPa

1:9:24

and

The activity coecients are


gA

PA
4:19
0:698

xA PA 0:4  15:0

1:9:25

gA

PB
10:23
0:853

xB PB 0:6  20:0

1:9:26

and

It is clear that there must be a limit to the endothermicity associated with the
mixing process, if a stable solution is to be formed. As the enthalpy of mixing
increases at a given composition, eventually a value is reached where the Gibbs
energy of mixing is zero. This follows from the fact that the entropy of mixing for
a regular solution is constant for xed solution composition and equal to the ideal
value (equation (1.9.10)). Values of mix Gm for a regular solution as a function of
composition for increasing values of ch=RT are shown in g. 1.10. When this
parameter reaches a value of 3, mix Gm increases over part of the composition

Fig. 1.10 The molar Gibbs energy of mixing in units of RT plotted against the mole
fraction of component B for regular solutions with increasing values of the ratio
w chRT.

THE THERMODYNAMICS OF LIQUID SOLUTIONS

29

range; this result indicates that a solution does not form. One may regard the
diagrams in this gure as referring to a unique system at dierent temperatures.
Thus, as temperature decreases, and ch=RT increases, one eventually reaches a
temperature at which the solution separates into its component liquids. The temperature at which phase separation begins to take place is called the critical
temperature, and for regular solutions corresponds to ch=RT equal to 2. It is
easily apparent that the value of mix Gm is approximately constant over most of
the composition range for this value of ch=RT.
The critical temperature at which phase separation begins is dened by the
conditions [4]
@2 mix Gm RT
0
@x2B

1:9:27

@3 mix Gm =RT 
0
@x3B

1:9:28

and

In other words, the slope of a plot mix Gm against xB must be constant and equal
to zero over the composition region where the critical phenomenon is observed.
From equation (1.9.11), it follows that
@2 mix Gm =RT
1
1
2ch
0


xA xB
RT
@x2B

1:9:29

@3 mix Gm =RT
1
1
2 2 0
3
@xB
xA xB

1:9:30

Thus, at the critical temperature, when xA xB ,


ch
2
RT

1:9:31

At lower temperatures, this ratio is larger, and phase separation occurs.


The important feature of the above treatment, which is also known in statistical mechanics as the BraggWilliams approximation [6], is that the molecular
composition around a given molecule reects the bulk composition. This cannot
be the case in general because of the dierences in intermolecular forces between
the solution components. Thus, if molecule A interacts more strongly with molecule B than with itself, the local composition of B around A is higher than the
average value. Recognition of this fact leads to more complex descriptions of
mixing phenomena such as that based on the quasi-chemical or Bethe approximation [5]. However, as soon as one accepts that the local molecular composition is
not the same as the average bulk composition, it follows that the entropy of
mixing is not given by the ideal value (equation (1.9.10)) and that the solution
is no longer regular. The quasi-chemical model and other models for non-ideal
molecular solutions have been considered in some detail in the development of
theories for molecular liquid solutions but are not considered further here.

30

LIQUIDS, SOLUTIONS, AND INTERFACES

1.10 An Empirical Approach to Non-Ideal Solutions


Most real solutions are neither ideal nor regular. As a result a realistic description
of their thermodynamic properties must consider the fact that both the excess
enthalpy of mixing, mix H ex , and excess entropy, mix S ex , are non- zero. Wilson
[7] has proposed an empirical description of the excess thermodynamic properties
of non-ideal systems which provides an excellent description on the basis of two
adjustable parameters. His approach includes systems in which the component
molecules have dierent sizes, and estimates the Gibbs energy of mixing on the
basis of the local volume fractions of each component. It is presented here for the
case of binary mixtures but can easily be extended to systems with more components.
Consider the solution composed of two molecules A and B. The number of
AA interactions, nAA , with respect to the number of AB interactions, nAB , is
given by the overall ratio of A to B in the solution weighted by factors which
account for the enthalpy associated with these interactions, namely, hAA and hAB .
Thus, one writes
nAA nA exphAA =RT

nAB nB exphAB =RT

1:10:1

Similarly, estimating the ratio of the number of BB interactions to AB interactions, one obtains
nBB nB exphBB =RT

nAB nA exphAB =RT

1:10:2

The volume fractions of each molecule, A and B , are then dened using these
ratios and the molar volumes of the two pure components, VmA and VmB :
A

nA V mA exp  hAA =RT


nA V mA exp  hAA =RT nB V mB exp  hAB =RT

1:10:3

B

nB V mB exp  hBB =RT


nA V mA exp  hAB =RT nB V mB exp  hBB =RT

1:10:4

and

The Gibbs energy of mixing is then assumed to be


mix Gm RTxA ln A RTxB ln B

1:10:5

Subtracting o the Gibbs energy of mixing for the ideal solution (equation
(1.6.11)), one obtains for mix Gex
m :
mix Gex
m RTxA lnA =xA RTxB lnB =xB

1:10:6

This may be rewritten as


mix Gex
m RTxA ln1  rBA xB  RTxB ln1  rAB xA

1:10:7

where
rBA 1 

V mB exp  hBB =RT


V mA exp  hAB =RT

1:10:8

THE THERMODYNAMICS OF LIQUID SOLUTIONS

31

and
rAB 1 

V mA exp  hAA =RT


V mB exp  hAB =RT

1:10:9

The parameters rAB and rBA are treated as adjustable and are chosen to obtain a
good t with the experimental data.
One may now derive expressions for the activity coecients of the two components. On the basis of equation (1.8.10)
mix Gex nA RT ln gA nB RT ln gB

1:10:10

so that


@ mix Gex =RT
@ ln gA
@ ln gB
ln gA nA
nB
@nA
@nA
@nA

1:10:11



@ mix Gex =RT
@ ln gA
@ ln gB
ln gB nA
nB
@nB
@nB
@nB

1:10:12

and

From the GibbsDuhem relationship (see equation (1.4.8) and associated discussion), the last two terms in equations (1.10.11) and (1.10.12) are equal to zero. It
follows that the derivatives of mix Gex =RT with respect to nA and nB give
directly the activity coecients of components A and B. Thus, dierentiating
equation (1.10.7) with respect to nA and simplifying, one obtains
ln gA  ln1  rBA xB 

xA xB rBA
x2B rAB

1  rBA xB 1  rAB xA

1:10:13

In a similar way, the expression for ln gB is


ln gB  ln1  rAB xA 

xA xB rAB
x2A rBA

1  rAB xA 1  rBA xB

1:10:14

Wilson [7] demonstrated the eectiveness of this model using data for both
binary and ternary systems, one example being the carbon tetrachlorideacetonitrile system. This system shows positive deviations from Raoults law, as shown
from the data for mix Gex
m presented in g. 1.11. Wilson [7] found that the best
values of the parameters rBA and rAB are 0.6118 and 0.8287 at 25 C, respectively,
where B refers to carbon tetrachloride and A to acetonitrile. The tted curve is
also shown in the gure, from which it is clear that there is excellent agreement
between the model and experiment.
EXAMPLE

Using Wilsons parameters for the carbon tetrachlorideacetonitrile system,


estimate the Raoult law activity coecients for each component in a equimolar
solution. Then estimate the molar Gibbs energy of mixing.
If acetonitrile is component A, then its activity coecient is given by equation (1.10.13) so that

32

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 1.11 Plot of the excess Gibbs energy of mixing for the carbon tetrachlorideacetonitrile system against the mole fraction of acetonitrile at 45 C. The points show the
experimental results and the solid curve was calculated using equation (1.10.7) with
the parameters given by Wilson [7] (see text).

ln gA  ln1  0:6118  0:5 

0:52  0:6118
0:52  0:8287

1  0:6118  0:5 1  0:8287  0:5

0:3651  0:2204 0:3538 0:4985

1:10:15

The value of gA is 1.646.


Similarly, for carbon tetrachloride which is component B
ln B  ln1  0:8287  0:5 

0:52  0:8287
0:52  0:6118

1  0:8287  0:5 1  0:6118  0:5

0:5350  0:3538 0:2204 0:4016

1:10:16

The value of gB is 1.494.


The molar Gibbs energy of mixing is given by equation (1.8.9) so that
mix Gm 0:5  8:3145  298:2 ln1:646  0:5 0:5  8:3145
 298:2 ln1:494  0:5
603:1 J mol1

1:10:17

Equation (1.10.7) can also be used to derive expressions for the excess entropy
and enthalpy functions. Dierentiating this equation with respect to temperature,
the expression for mix Sex
m is
mix Sex
m RxA ln1  rBA xB RxB ln1  rAB xA


RTxA xB @rBA RT xA xB @rAB



1  rBA xB @T
1  rAB xA @T

1:10:18

THE THERMODYNAMICS OF LIQUID SOLUTIONS

33

Combining equations (1.10.7) and (1.10.18), the expression for mix H ex


m is
mix H ex
m 

RT 2 xA xB @rBA RT 2 xA xB @rAB

1  rBA xB @T
1  rAB xA @T

1:10:19

The two derivatives @rBA =@T and @rAB =@T constitute two additional parameters
which are obtained by tting mix H ex
m data to the model. Obviously, description
of the entropy requires four parameters.
The eectiveness of Wilsons model lies in the fact that only two parameters are
required to describe the Gibbs energy at a given temperature. Its weakness lies in
the fact that there is no clear molecular interpretation of these parameters.
Wilsons approach works for a great variety of systems but when the departures
from ideality are complex, more detailed models are required. Some extensions of
Wilsons work have been discussed by Renon and Prausnitz [8] but they require
introduction of more adjustable parameters.

1.11 Ideally Dilute Solutions


For many solutions, it is not possible to vary the composition of the components
over the whole range of mole fractions. This is obviously true of solutions made
up of a solid and a liquid. For these systems it is better to choose a standard state
which is based on the properties of a dilute solution. This leads to the denition of
an ideally dilute solution. Such a system is easily dened on a molecular basis as
one in which the solute molecule only comes in contact with solvent molecules,
and never with another solute molecule. In the previous discussion of regular
solutions it was concluded that, when the two components are of equal size, the
coordination number for the other molecules around a central one is twelve. This
suggests that an ideally dilute solution must have a solute mole fraction which is
less than 1/13, that is, 0.08.
The above approximate guideline for an ideally dilute solution can only be
made more exact by examining vapor pressure data for a specic system. The case
of the methanolwater system discussed earlier is used as an illustration. For very
dilute solutions, that is, when xMeOH is less than 0.04, the vapor pressure of
methanol is linear in its mole fraction. This is the region where Henrys law is
obeyed. As the mole fraction increases, the actual vapor pressure falls below that
predicted by Henrys law, quite signicant deviations being found when xMeOH
reaches 0.1. Henrys law for component B in a two-component system of A and B
may be expressed as
PB kH xB

1:11:1

where kH is the slope of the Henry law line. Raoult law behavior is also shown in
g. 1.12. For this non-ideal system, which exhibits positive deviations from
Raoults law, the slope of the Raoult law line, which is equal to the vapor pressure
of pure methanol, is much less than that for the Henry law line. It should be
remembered that in the concentration range over which Henrys law holds for the
solute, Raoults law is valid for the solvent (see g. 1.5). This fact gives one

34

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 1.12 Vapor pressure of methanol for dilute solutions of methanol in water plotted
against the mole fraction of methanol. The straight line shows the vapor pressure according
to Henrys law, and the broken line, that according to Raoults law.

another convenient guideline for judging the concentration range for ideally dilute
behavior.
The value of the Henry law constant and concentration range over which this
law is valid depends very much on the system. This is easily seen by comparing the
behavior of the methanolwater and acetonitrilewater systems (gs. 1.5 and 1.6).
In the latter case ideally dilute solution behavior is observed for a lower range of
mole fractions of the solute, that is, when xAcN is less than 0.03.
The most important application of low concentration behavior of solutes is for
solid solutes, especially electrolytes. Electrolyte solutions are examined in detail in
chapter 3. Some general thermodynamic methods for describing the properties of
very dilute solutions are considered in the following section.

1.12 Thermodynamics of Ideally Dilute Solutions


Just as was done previously, one develops the thermodynamic description of an
ideally dilute solution by considering the equilibrium between the dilute solute
component in the liquid solution and in the vapor phase. If the minority component is designated B, then one may write its chemical potential as
msB mvB mBv; RT ln PB

1:12:1

Since Henrys law holds when the solution is ideally dilute, this can be rewritten as
msB ms;
B RT ln xB

1:12:2

mBs; mBv; RT ln kH

1:12:3

where

THE THERMODYNAMICS OF LIQUID SOLUTIONS

35

It should be noted that ms;


B gives the standard chemical potential for the ideally
dilute solute in a hypothetical system in which the mole fraction of B is unity. This
is obviously a ctitious state which is impossible in reality but whose properties
are obtained by extrapolating the Henrys law line to xB 1 (see g. 1.12). When
Henrys law is not obeyed, an activity coecient gH
B is introduced so that the
product gH
k
x
is
equal
to
the
vapor
pressure
P
B . The activity of the dilute
B H B
H
is
dened
to
be
g
x
.
Thus,
the
general
expression for the concomponent aH
B
B B
centration dependence of msB becomes
H
s;
H
msB ms;
B RT ln aB mB RT ln gB xB

1:12:4

where gH
B is the Henrys law activity coecient on the mole fraction scale.
Because of the inconvenient nature of the standard state dened above, the
concentration units used to describe the concentration dependence of the chemical
potential are usually dierent. More convenient choices for concentration are
molality and molarity. When the solution is dilute the relationship between
mole fraction and molality is quite simple (see equation (1.2.3)). In terms of
molality, the expression for the concentration dependence of the chemical potential of component B becomes
msB mBs; RT ln mB
where


v;
ms;
B mB RT ln

kH MA
1000

1:12:5

1:12:6

and MA is the molecular weight of the solvent. Now, the standard chemical
potential is that for a hypothetical system which obeys Henrys law for a solute
concentration of 1 m. For the methanolwater system, xB is equal to 0.018 at this
concentration. Not only is this a dilute solution by the criteria that have been
discussed here, but it is also a system which approximately obeys Henrys law
on the basis of the data shown in g. 1.12. It should be emphasized that this will
not always be the case, signicant departures from Henrys law being observed
for very low concentrations for some systems, for example, acetonitrilewater
mixtures.
When the dilute system does not obey Henrys law, one introduces an activity
coecient as above to correct to the experimentally observed value. Thus, in
general, one may write
PB

gH
B kH MA
mB
1000

1:12:7

where gH
B is the Henrys law activity coecient for component B on the molality
scale. Then, on the basis of equation (1.12.1), the chemical potential of component B may be written
s;
H
msB mBs; RT ln aH
B mB RT ln gB mB

1:12:8

where aH
B is the activity of B on the molality scale with the standard state dened
according to Henrys law (equation (1.12.6)).

36

LIQUIDS, SOLUTIONS, AND INTERFACES

Alternatively, one may use molarity as the concentration unit. In this case, one
must know the density of the solution to order to relate mole fraction to molarity.
For very dilute solutions, using equation (1.2.5), the concentration dependence of
the chemical potential is given by
msB mBs; RT ln cB

1:12:9

where
mBs; mv;
B RT ln

k H MA
1000rA

1:12:10

rA being the density of the solvent. When the system does not obey Henrys law,
one introduces an activity coecient, gH
B which is the multiplicative correction
factor required to make the vapor pressure of B predicted by Henrys law equal to
that observed experimentally. Thus, gH
B is dened by the equation
PB

gH k H M A
c
1000rA B

1:12:11

and the expression for the concentration dependence of msB becomes


H
s;
H
msB ms;
B RT ln aB mB RT ln gB cB

1:12:12

EXAMPLE

Carbontetrachloridebenzene solutions can be regarded as regular with an


enthalpy parameter ch equal to 324 J mol1 at 25 C. Given that the vapor
pressure of pure carbon tetrachloride is 14.13 kPa, determine the Henrys law
constant for this component by examining its vapor pressure at mole fractions
in the range 0.001 to 0.1. Then estimate the Henrys law activity coecient at a
mole fraction of 0.1 on the mole fraction and molality scales.
From the theory for regular solutions, the Raoult law activity coecient for
component B in a solution of A and B is
ln gR
B

chx2A
RT

1:12:13

Values of gR
B were estimated for values of xB in the range 0.001 to 0.005 and are
recorded in the following table. Then, the partial pressure of B (carbon tetrachloride) was estimated using the relationship

PB gR
B PB xB

1:12:14

Finally, the ratio PB =xB was also calculated.


xB

gR
B

PB / Pa

PB =100xB

mB

0.001
0.002
0.003
0.004
0.005

1.139
1.139
1.139
1.138
1.138

16.1
32.1
48.3
64.4
80.4

161
161
161
161
161

0.013
0.026
0.039
0.051
0.064

It is clear from these results that the Henrys law constant is 16,100 Pa.

THE THERMODYNAMICS OF LIQUID SOLUTIONS

37

At xB 0.1, PB is equal to 1571 Pa. Henrys law predicts that PA is 1610 Pa.
Therefore, the Henrys law activity coecient is 0.976.
The molality is easily calculated from the mole fraction using the relationship
mB

1000xB
MA xA

1:12:15

where MA is the molecular mass of benzene (78.1). Values of the molality for
the dilute solutions are also recorded in the table. The Henrys law constant on
this scale is 1253 Pa kg mol1 . A mole fraction of 0.1 in carbon tetrachloride
corresponds to a molality of 1.42 m. Thus, the predicted vapor pressure by
Henrys law is 1780 Pa. As a result the Henrys law activity coecient is 0.883.
On the basis of the above, the denitions of the standard state (equations
(1.12.3), (1.12.6), and (1.12.10)) and of the activity coecient gH
B (equations
(1.12.4), (1.12.7), and (1.12.11)) depend on the choice of concentration units
used for the dilute solution component. It is emphasized that one must always
state the concentration units in dening these two quantities. This point is further
illustrated in table 1.4, where activity coecients for the components in dilute
aqueous solutions of methanol are tabulated. Notice rst of all that the molality
of methanol has reached 6.2 m when the mole fraction is 0.1. This is due to the
dierence between the molecular mass of water (18 g) and that of methanol (32 g).
On the basis of the Raoult law activity coecients the behavior of water is ideal
over most of this concentration range, the activity coecient being 1.000 to four
Table 1.4 Raoult Law and Henry Law Activity
Coefcients for Dilute Solutions of Methanol in
Water at 40 C
Activity Coecients
Methanol Concentration Raoults Law

xMeOH

mMeOH
/mol kg1

gR
MeOH

gR
w

0.0001
0.0002
0.0005
0.001
0.002
0.005
0.01
0.02
0.05
0.1

0.006
0.011
0.028
0.056
0.111
0.279
0.561
1.133
2.921
6.167

1.7054
1.704
1.704
1.704
1.702
1.696
1.687
1.669
1.618
1.539

1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.001
1.005

Henrys Law*
gH
gH
MeOH
MeOH
x s:s (m s:s
1.000
1.000
1.000
1.000
0.999
0.996
0.990
0.979
0.949
0.903

1.000
1.000
1.000
1.000
1.000
0.997
0.987
0.967
0.908
0.819

*The rst column gives the Henry law activity coefcient for
methanol on the basis of a standard state of xMeOH 1 and the
second on the basis of a standard state of mMeOH 1.

38

LIQUIDS, SOLUTIONS, AND INTERFACES

signicant gures up to a mole fraction of 0.02. At the same time, the behavior of
methanol with respect to Raoults law is non-ideal over the range considered. Since
deviations from ideal behavior are positive (see g. 1.5), the Raoult law activity
coecient for methanol is greater than one; in addition, it changes signicantly in
this concentration range, decreasing steadily in magnitude as the mole fraction
increases. On the other hand, the values of gH
MeOH are unity at the lowest concentrations in the region where Henrys law holds. As concentration increases, these
activity coecients fall below unity and dier according to the choice of standard
state. By multiplying the concentration in particular units by the appropriate
activity coecient, one obtains the Henry law activity. For instance when
xMeOH 0.1, the activity of methanol on the mole fraction scale is 9:90  103 .
On the molality scale, the activity is 0.554 mol kg1 of water. By multiplying the
latter quantity by MA =1000, that is, 0.018 kg mol1 for water, one obtains approximately the activity on the mole fraction scale (see equation (1.2.3)).
The results recorded in table 1.4 emphasize the necessity of clearly stating the
standard conditions for dening activity coecients in liquid solutions. As stated
above, the molality scale is preferred to the mole fraction scale for most systems,
especially those which are not miscible over the whole composition range. The
molality scale is preferred over the molarity scale because the denition of solution
concentration is independent of temperature and pressure. On the other hand, the
molarity concentration scale is so popular in chemistry that one often nds activity
coecients also recorded in the literature using a Henrys law scale on the basis of
molarity. This is especially true of electrolyte solutions, which are always nonideal. When one recognizes that the majority of solutions involve solid solutes,
the importance of the Henrys law denition of the standard state becomes clear.
These solutes usually have a negligible vapor pressure for the conditions that the
solutions are used. Thus, a question arises regarding determination of the activity
of non-volatile solutes. This is dealt with in the following section.

1.13 Experimental Determination of Solution Activities


In order to determine the activity of a component in solution, one must measure
its vapor pressure. In the case of volatile liquids such as those discussed in most of
this chapter, vapor pressure measurement is not a problem so that very accurate
determination of activity is possible over the whole composition range for which a
solution is formed. However, many solutes, for example, most solids, have negligible vapor pressures. Under these circumstances, one makes use of the Gibbs
Duhem relationship between the activities of the two-components in solution.
Since the vapor pressure of the solvent can be measured, its activity can be
determined, and then used to estimate the activity of the solute.
On the basis of equation (1.4.28), for any innitesimal change in a twocomponent system, one may write
dGm xA dmA mA dxA xB dmB mB dxB

1:13:1

From the rst and second laws of thermodynamics for this system (equation
(1.3.21)), one has

THE THERMODYNAMICS OF LIQUID SOLUTIONS

dGm Sm dT Vm dP mA dxA mB dxB

39

1:13:2

Therefore, in general, one may write


Sm dT  Vm dP xA dmA xB dmB 0

1:13:3

and at constant temperature and pressure


xA dmA xB dmB 0

1:13:4

This is the form of the GibbsDuhem equation needed to relate the activity of
component B in solution to that of component A. Choosing the Raoult law
activity for the solvent A, and the Henry law activity for the solute B, equation
(1.13.4) may be rewritten as


xA
d ln aH
dln aR
B 
A
xB

1:13:5

In the limit of very dilute solutions, both activity coecients approach unity so
that the activity of A can be replaced by xA , and the activity of B by its molality
(assuming that one has chosen molality as the concentration unit). However, as xB
becomes very small the ratio xA /xB becomes very large. Thus, in practice, one may
not choose the innitely dilute solution as a reference point but instead a very
dilute solution for which Henrys law is valid. Then, integrating equation (1.13.5)
between this very dilute concentration designated m1 , to any other concentration
m2 , one obtains
2
H
ln aH
B ln gB m2 ln m1 
1

xA  R 
d ln aA
xB

1:13:6

An example of application of the GibbsDuhem relationship to determination


of the activity coecients of sucrose in aqueous solutions is shown in table 1.5.
Sucrose (C12 H22 O11 ) has a very high molecular mass (342 g) compared to water so
that solutions with very low solute mole fractions have relatively high molalities.
By measuring the water vapor pressure as a function of sucrose concentration
down to very low concentrations, one is able to determine its activity coecient
and thus its activity on the Raoult law scale. It should be noted that the vapor
pressure of water begins to depart from ideal behavior at a quite low sucrose mole
fraction (0.005). By carrying out the integration dened by equation (1.13.6) one
is able to calculate the Henrys law activity for sucrose and, thus, the activity
coecients given in table 1.5.
It should be noted that the values of gH quickly become non-unity and are
greater than one. This is indicative of strong attractive solutesolvent interactions
and negative deviations from Raoult law behavior. In the case of the methanol
water system for which positive deviations from Raoults law is observed (table
1.4), the Henry law activity coecients are less than one.
The above procedure for determining activity coecients for solid solutes is
often applied to electrolytes. This important class of solutes always behaves nonideally. The properties of electrolyte solutions are considered in detail in chapter 3.

40

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 1.5 Activity Coefcient Data for Sucrose and


Water as Determined from Water Vapor Pressure
Measurements for Their Solutions at 25 C
Concentration of Sucrose

Activity Coecients

Water
Sucrose
Molality (Raoults Law) (Henrys Law)
gR
gH
Mole Fraction /mol kg1
w
s
1  104
1  103
5  103
0:02
0:04
0:07
0:1

5:6  103
0:056
0:279
1:134
2:315
4:182
6:173

1:000
1:000
0:9999
0:998
0:990
0:968
0:939

1:000
1:001
1:042
1:206
1:52
2:15
2:91

1.14 Concluding Remarks


The material in this chapter explains the relationship between the concentration of
a solution component and its activity. The activity is monitored through the vapor
pressure of the components, which are volatile for most of the examples considered. Thus, it is very easy to understand why the activity of a given component
can also be dened as its escaping tendency. It is obvious from the fact that most
solutions are non-ideal that the relationship between activity and concentration is
not simple. When the solution is very dilute, Henrys law holds for the solute and
Raoults law for the solvent. Then the activity is proportional to the concentration
over a nite concentration range which must be determined for each system.
A review of chemical thermodynamics, especially as it relates to the properties
of liquid solutions, has also been presented. Partial molar quantities such as the
chemical potential are an important feature of the treatment of this subject. It is
often the case that the activity and chemical potential of one quantity is relatively
easy to determine directly by experiment, whereas that of another component is
not. Under these circumstances, the change in chemical potential of one component can be related to that of another through the GibbsDuhem equation. This
relationship and its use in estimating thermodynamic properties are extremely
important in solution chemistry.
Two simple models for non-ideal solutions have been discussed. These are the
HildebrandGuggenheim model for regular solutions, and Wilsons empirical
approach to non-ideal solutions. They give the avor of the subject but represent
only a very small fraction of the theoretical work done in this area. The extension
of the model for regular solutions using the quasi-chemical approximation was
mentioned earlier. In this way, the approximation that the distribution of molecules is random in solution is relaxed. Another subject which has been examined
in detail in the literature is solutions with strong association. This association is
often due to hydrogen bonding and therefore is important in understanding the
properties of solutions formed with water and the alcohols. Polymer solutions

THE THERMODYNAMICS OF LIQUID SOLUTIONS

41

have also been considered and their thermodynamic properties derived. More
details regarding this subject and an introduction to the original literature in
this eld can be found in the monographs by Prigogine [9] and Marcus [10].
General References
G1. Hirata, M.; Ohe, S.; Nagahama, K. Computer Aided Data Book of Liquid-Vapor
Equilibria; Elsevier: Amsterdam, 1975.
G2. Levine, I. N. Physical Chemistry, 4th ed.; McGraw-Hill: New York, 1995.
G3. Landolt-Bornstein. Densities of Binary Aqueous Systems and Heat Capacities of Liquid
Systems; New Series, Group IV; Springer-Verlag: Berlin, 1977; Vol. 1b.
References
1. Hildebrand, J. H.; Scott, R. L. The Solubility of Non-Electrolytes, 3rd ed.; Dover: New
York, 1964.
2. Treiner, C.; Tzias, P.; Chemla, M.; Poltoratsky, G. M. J. Chem. Soc., Faraday Trans. I
1976, 72, 2007.
3. Hildebrand, J. H. J. Am. Chem. Soc. 1929, 51, 66.
4. Fowler, R. H.; Guggenheim, E. A. Statistical Thermodynamics; Cambridge Press,
1939; Chapter 8.
5. Guggenheim, E. A. Mixtures; Oxford University Press 1952; Chapter 4.
6. Rushbrooke, G. A. Introduction to Statistical Mechanics; Oxford University Press, 1949.
7. Wilson, G. M. J. Am. Chem. Soc., 1964, 86, 127.
8. Renon, H.; Prausnitz, J. M. AIChE J. 1968, 14, 135.
9. Prigogine, I.; Bellemans, A.; Mathot, V. The Molecular Theory of Solutions; North
Holland: Amsterdam, 1957.
10. Marcus, Y. Introduction to Liquid State Chemistry; Wiley-Interscience: New York, 1977.

Problems
1. The density of LiClO4 solutions in dimethylsulfoxide at 25 C is given by
r 1.0965 6.204  102 c
where r is the density in g mL1 and c, the concentration of LiC1O4 in M.
Calculate the molality and mole fraction of the solute for solutions with
concentrations of 0.1, 0.2, and 0.5 M.
2. The following density data are reported for the carbon tetrachlorideacetonitrile system at 25 C.
Mole Fraction
Acetonitrile

Density
/g mL1

0
0.1657
0.3145
0.4406
0.5498
0.6473
0.7348
0.8113

1.5844
1.5066
1.4248
1.3441
1.2640
1.1827
1.1003
1.0194

42

LIQUIDS, SOLUTIONS, AND INTERFACES

0.8797
0.9430
1.0000

0.9390
0.8575
0.7766

Calculate the excess molar volume for the solution and partial molar volumes
of the two components at mole fractions equal to 0, 0.2, 0.4, 0.6, 0.8, and 1.0.
Use the appropriate numerical interpolation and dierentiation techniques
(see appendix C).
3 The following results are reported for the carbon tetrachlorideacetonitrile
system at 45 C.
Mole Fraction CCl4

Total Vapor Presure

Liquid

Vapor

/kPa

0
0.0347
0.1914
0.3752
0.4790
0.6049
0.8069
0.9609
1.000

0
0.1801
0.4603
0.5429
0.5684
0.5936
0.6470
0.8001
1.000

27.783
33.062
44.796
48.604
49.274
49.466
48.362
41.908
34.501

Use an interpolation method to obtain the values of the mole fraction of CCl4
in the vapor and the total vapor pressure for values of the mole fraction in the
liquid phase equal to 0.2, 0.4, 0.6, and 0.8. Then calculate the vapor pressure
and the activity coecient of each component for the same values. Finally
estimate the molar Gibbs energy of mixing on the Raoult law scale at these
four points.
4. The following data are reported for the molar enthalpy of mixing for the
system discussed in question 3.
Mole Fraction of CCl4
Liquid

mix Hm
/J mol1

0
0.128
0.317
0.407
0.419
0.631
0.821
1.0

0
414
745
862
858
930
736
0

Determine the value of mix Hm at xCCl4 equal to 0.2, 0.4, 0.6, and 0.8.
Combine these data with those obtained in question 3 to prepare a plot of
mix Gm , mix Hm , and Tmix Sm against xCCl4 .

THE THERMODYNAMICS OF LIQUID SOLUTIONS

43

5. Calculate the excess Gibbs energy, entropy, and enthalpy of mixing for the
carbon tetrachlorideacetonitrile system discussed in questions 3 and 4.
Prepare a plot of these data and compare the results with those obtained in
the previous question.
6. The following data are available for solutions of acetone and chloroform at
50 C.
Mole Fraction of Acetone

Total Pressure

Liquid

Vapor

/kPa

0
0.10
0.20
0.30
0.38
0.40
0.50
0.60
0.70
0.80
0.90
1.00

0
0.071
1.165
0.279
0.380
0.408
0.550
0.684
0.789
0.890
0.955
1.000

69.5
66.0
63.2
61.7
61.1
61.3
62.5
65.2
68.1
72.0
76.8
81.6

Calculate the Raoult law activity coecients of both components and plot
them as a function of the mole fraction of acetone. Determine the range of
composition with respect to acetone that the solution can be regarded as
regular. Calculate the enthalpy parameter for acetonechloroform interactions on the basis of a one-parameter least-squares t of the data in this
range using an appropriate plot.
7. J. J. Van Laar gave a useful semiempirical equation for the molar excess
Gibbs energy of solutions,
mix Gex
m

b12 x1 x2
b1 x1 b2 x2

where b12 , b1 , and b2 are characteristic constants. Show that the Van Laar
relation implies that
p

A12 x1
1 1=2
1

p
ln g1
B12 x2
A12
p


1 1=2
1
B12 x2

p
ln g2
A12 x1
B12


where A12 b12 =b2 RT and B12 b12 =b; RT

44

LIQUIDS, SOLUTIONS, AND INTERFACES

8. The following vapor pressure data are found for methanolwater solutions at
40 C.
xMeOH

PMeOH =kPa

0.04
0.08
0.12
0.2
0.4
0.6
0.8
1.0

2.1
4.3
6.4
9.9
17.2
23.3
29.3
36.0

Calculate the Raoult law and Henry law activity coecients for methanol on
the mole fraction scale.

The Structure of Liquids

Douglas (Doug) Henderson was born in


Calgary, Alberta, Canada in 1934. He grew up
in Vancouver, British Columbia and attended
the University of British Columbia where he
obtained a bachelors degree in mathematics in
1956. Henderson then went to the University of
Utah in Salt Lake City to work with Henry
Eyring on the theory of liquids. He obtained
his Ph.D. in physics under Eyrings direction in
1961. After leaving graduate school he held
faculty positions at universities in both the
Douglas James Henderson
United States and Canada. During 196667,
Henderson was an invited scientist at the Commonwealth Scientic and
Industrial Research Organization (CSIRO) in Melbourne, Australia. There he
began a long and very successful collaboration with John Barker. One of the
major results of their work was the perturbation theory of liquids, some of
which was outlined in Reviews of Modern Physics in 1976 in their well-known
paper What is liquid? Understanding the states of matter [1]. Barker and
Henderson moved together to the IBM Almaden Research Center in San Jose,
California as research scientists in 1969. Hendersons research interests in the
statistical mechanics of condensed phases involve many aspects, an important
one in recent years being the electrical double layer. He was instrumental in
bringing our understanding of interfacial phenomena at polarizable interfaces
beyond the primitive level. He is currently professor of chemistry at Brigham
Young University in Provo, Utah. His career is noteworthy for the
international collaborations which he has established in many countries where
research in statistical mechanics is carried out. He has published over 400
papers in this area. In addition, he has won numerous awards for his scientic
work, the most recent being the Hildebrand Award of the American Chemical
Society in 1999 for his work on the structure of liquids.

2.1 What Is a Liquid?


It is well known from studies of the properties of matter that the liquid state is
much more complex than either the gaseous or solid states. Studies of the properties of gases quickly lead to the ideal gas law, which describes the properties of
real gases at low pressures and high temperatures. This success is clearly due to
45

46

LIQUIDS, SOLUTIONS, AND INTERFACES

the fact that the molecules in a dilute gas are far from one another so that the
eects of intermolecular forces and of the nite volume occupied by the gas
molecules are negligible. As the pressure of a gas is increased and its temperature
lowered, the eects of non-ideality become apparent, and the equation of state
becomes more complex. These changes are those required to convert the gas to a
liquid. As the molecules come closer together, the inuence of intermolecular
forces becomes greater and the free volume available for the gas molecules is
signicantly reduced because of the space occupied by the molecules themselves.
The statistical mechanical description of a gas relies upon the concept that the
molecules are in constant movement with trajectories determined by collisions
with the walls of the container and with other molecules. The probability of
nding another molecule in the immediate vicinity of a given molecule is extremely low and does not vary signicantly with distance from the reference
molecule.
On the other hand, solids are characterized by a very ordered structure in
which each ion or molecule is surrounded by a xed number of neighbors
whose nature and orientation are determined by the interparticle forces in the
crystal. These may be chiey ionion interactions, as in an ionic crystal, or intermolecular forces, as in a molecular crystal. Because of the high state of order in
crystals it is a reasonably straightforward problem to calculate their thermodynamic properties on the basis of quite simple statistical mechanical models.
One way of conceptualizing a liquid is as a very disordered solid. If one disrupts the structure of the nearest neighbors around a reference molecule in a
molecular crystal, the eect of the disruption extends quite far. As a result,
there is some local order around the reference point but the extent of order
falls o rapidly with distance so that at distances equivalent to four or ve
molecular diameters the system does not possess order with respect to the reference point. Theories of the liquid state based on an approach involving disordered
solids were pursued from the 1930s to the 1960s but did not meet with much
success. On the other hand, the liquid may be regarded as an extremely imperfect
gas. In this approach, which has been quite successful, the statistical mechanical
techniques used to describe the properties of non-ideal gases are extended to
liquids.
Considerable advances have been made since the 1950s in developing the
theory of liquids [G1, G2]. The purpose of this chapter is to give an introduction
to this subject, outlining the main theoretical and experimental topics. Rigorous
development of the theory is not possible without appealing to more sophisticated
mathematics. However, an understanding of the basic concepts involved in this
subject is helpful, not only in reading further in the area of liquid structure, but
also in developing the other topics considered in this monograph.
Liquids may be classied according to the intermolecular (or interatomic)
forces existing between the components. In this way, seven dierent kinds of
liquids may be identied:
1. The simplest liquids are those formed by the inert gases, He, Ne, Ar, etc.
These atoms interact via van der Waals forces and strongly repel each other
at short interatomic distances.

THE STRUCTURE OF LIQUIDS

47

2. Homonuclear diatomic molecules such as H2, N2, and Cl2 form the second
group. They are similar to the rst in that they do not possess a dipole
moment but have electrical quadrupole moments and are not spherical.
3. Liquid metals such as Hg make up the third group. Because of the mobility of
electrons in metals, these systems have long-range coulombic forces, and are
softer with respect to short-range repulsive forces. In addition, electrical
screening eects are important in liquid metals.
4. Molten salts are systems in which the components are ions but which are
electrically neutral on a local scale. Coulombic forces are long range in molten salts and electrical screening is important. The complexity of these systems depends on the nature of the ions, that is, whether they are monoatomic
or polyatomic. For polyatomic ions, other electrostatic forces may be
involved.
5. Aprotic polar liquids such as dimethyl sulfoxide and acetonitrile make up
another group. These molecules have high dipole moments, so that dipole
dipole interactions are an important part of the description of intermolecular
forces.
6. Another group is composed of protic polar liquids such as water and the
alcohols. In these systems, hydrogen bonding adds a further complication to
the description of intermolecular forces.
7. Finally, non-polar molecular liquids, such as carbon tetrachloride and the
hydrocarbons, form a group. Many of these systems possess no permanent
dipole moment so that the intermolecular forces are similar to those existing
in simple atomic liquids such as liquid argon. However, internal modes of
motion are important in describing the properties of the molecular liquid.

Chemists are obviously concerned mainly with liquids in the last three groups.
However, they are the most dicult to model from the point of view of theory.
Much of the theoretical eort has been directed to understanding the properties of
the simplest liquids, namely, the inert gases. In the following sections, the statistical mechanical approach developed to understand liquid properties is outlined.
The purpose of this subject is to establish a connection between the properties of
the individual atoms or molecules in the liquid and the bulk properties of the
system. An important part of this development is the experimental study of liquid
structure which is also outlined in the following discussion.

2.2 The Statistical Thermodynamics of Liquids


Statistical thermodynamics uses statistical arguments to develop a connection
between the properties of individual molecules in a system and its bulk thermodynamic properties. For instance, consider a mole of water molecules at 25 C and
standard pressure (1 bar). The thermodynamic state of the system has been
dened on the basis of the number of molecules, the temperature, and the pressure. In order to relate the macroscopic thermodynamic properties such as U, G,
H and A to the properties of the individual molecules, one would have to solve the
Schrodinger wave equation (SWE) for a system composed of 6  1023 interacting
water molecules. This is an impossible task at present but if it were possible, one
would obtain a wave function, j , and an energy, j , for the system. Moreover,

48

LIQUIDS, SOLUTIONS, AND INTERFACES

the values of j and j would uctuate with time because of the changing positions of the molecules and their interactions. The task of statistical thermodynamics is to relate the time average properties of the many microstates which arise
in the uctuating system to its macrostate. In the following section the basic
principles of statistical thermodynamics are outlined, rst for non-interacting
systems, such as ideal gases, and then for interacting systems, that is, non-ideal
gases and liquids.
The present discussion concerns the canonical ensemble. An ensemble is a
hypothetical collection of an large number of non-interacting systems, each of
which is in the same thermodynamic state (macrostate) but in a dierent microstate. A fundamental postulate of statistical thermodynamics is that the measured
time average of a macroscopic property of the system is equal to the average value of
that property in the ensemble. Thus, time averaging can be replaced by averaging
over the systems in the ensemble. The fact that the ensemble is canonical means
that each system in the ensemble has the same volume, temperature, and composition (number of molecules). This means that each system is rigid (constant
volume), and has impermeable walls (constant composition), but walls which
are thermally conductive. All of the systems can be imagined as being immersed
in constant temperature bath.
The internal energy of the macrosystem, U, is found by averaging the energy j
for each microsystem in the ensemble. The averaging is carried out over all
possible quantum states of the microsystem, taking into account the probability
that the total energy is equal to j . A second postulate used in this process is that
for a thermodynamic system of xed volume, composition, and temperature, all
quantum states that have equal energy have equal probability of occurring.
Estimation of the probability for a given quantum state leads to the denition
of the canonical partition function of the macrosystem:
X
ebj
2:2:1
Q
j

where b 1=kB T and kB is the Boltzmann constant. The partition function is of


central importance in determining the thermodynamic properties of the macrosystem given its microscopic properties. Sometimes the summation is dened in terms
of available energy levels rather than quantum states. In this case, each term in the
summation must be multiplied by the degeneracy of the corresponding energy level.
On the basis of the denition of the partition function, the probability that the
microsystem is in quantum state j is given by
fj

ebj
Q

Since the internal energy, U, is given by


X
U
fj j
it is easily shown that
U





@ ln Q
@ ln Q
kB T2
@b V;N
@T V;N

2:2:2

2:2:3

2:2:4

49

THE STRUCTURE OF LIQUIDS

In the same way, one may estimate the systems pressure P by noting that
X
P
fj Pj
2:2:5
where Pj is the pressure for the microsystem in microstate j. It follows that


1 @ ln Q
P
2:2:6
b @V T;N
An expression for the entropy S of the ensemble can be found by relating the
temperature derivative of the entropy to the heat capacity at constant volume
using equation (1.3.9). Accordingly,
 
 
@U
@S
CV
T
2:2:7
@T V;N
@T V;N
Since
CV
it follows that




@
@ ln Q
kB T2
@T
@T V;N

2:2:8

!



@S
@ ln Q
@2 ln Q
2kB
k T
@T V
@T V;N B
@T2

2:2:9
V;N

The corresponding dierential equation to obtain the entropy is


!


@ ln Q
@2 ln Q
dS 2kB
dT kB T
dT
@T V;N
@T2
V;N




@ ln Q
@ ln Q
kB
dT kB d T
@T V;N
@T V;N

2:2:10

Integrating with respect to temperature from 0 K, one obtains the expression


S  S0 kB ln Q  kB ln Q0 kB T

@ ln Q
@T

2:2:11

where S0 and Q0 are the entropy and partition function at 0 K. The partition
function Q0 is simply the degeneracy of the lowest available energy state of the
system and is a temperature-independent quantity. Equating S0 and kB ln Q0 , the
resulting expression for the entropy is
S

U
kB ln Q
T

2:2:12

On the basis of these denitions, one easily obtains expressions for the Helmholtz
energy
A U  TS kB T ln Q
and for the Gibbs energy

2:2:13

50

LIQUIDS, SOLUTIONS, AND INTERFACES



@ ln Q
G U  TS PV kB T ln Q kB TV
@V T;N

2:2:14

The thermodynamic functions are introduced here for a one-component system,


but are easily extended to multicomponent systems [G3, G4].
Two other ensembles are commonly dened in statistical thermodynamics,
namely, the microcanonical ensemble and the grand canonical ensemble. In the
microcanonical ensemble, the number of moles, volume, and internal energy, U,
are xed in each system. This means that each system is totally isolated, being
unable to exchange either energy or matter with the surroundings. In the case of
the grand canonical ensemble, the volume, temperature, and chemical potential of
the single component in each system are held constant. Thus, for such an ensemble, both energy and matter can be exchanged with the surroundings. Further
details regarding these ensembles and the relationships between the three types
introduced can be found elsewhere [G3, G4].
The treatment of the canonical ensemble for the special case of an ideal gas is
now outlined. First of all the partition function for the macrosystem is related to
the properties of the individual molecules. At the same time, the energy of a given
state in the ensemble j can be related to the energy of an individual molecule i .
In the case of a gas or a liquid the particles in the system are indistinguishable
because of random motion. Furthermore, if the particles do not interact with one
another as in an ideal gas, it is easily shown that
qN
2:2:15
N!
where q is the partition function for a given molecule, which is given by
X b
q
e i
2:2:16
Q

The summation for q is made over the available quantum states for the molecule
as determined by solution of the SWE.
In order to proceed further one must write down the Hamiltonian for the
molecule, that is, the expression for its kinetic and potential energy. The former
contains up to ve contributions, namely, for its translational, rotational, vibrational, electronic, and nuclear energies. Since the molecules do not interact with
one another the potential energy is zero. Thus, one may write
H Htrans Hrot Hvib Helec Hnuc

2:2:17

For present purpose this is more conveniently written as


H Htrans Hint

2:2:18

where Hint represents all of the internal modes of possessing energy. With the
Hamiltonian operator H one obtains the SWE whose solution gives the energy of
an individual molecule, :
 trans int

2:2:19

where trans and int are the contributions of the translational and internal modes
to the energy, respectively. These may then be used to estimate the molecular
partition function, q:

THE STRUCTURE OF LIQUIDS

q qtrans qint

51

2:2:20

Expressions for the individual partition functions have also been developed.
From the solution of the SWE for a particle in a box it is well known that


2pmkB T 3=2
V
qtrans
V 3
2:2:21

h2
where m is the mass of the particle, V, the volume of the box and h, the Planck
constant and


h
2pmkB T1=2

2:2:22

The expression for the canonical partition function of an ideal gas thus becomes
Q

N
qN
qN V N
trans Qint
int 3N
N!
N!

2:2:23

Another way of writing the molecular partition function is to use the classical
expression for Htrans in an integral form. By classical mechanics, Htrans for each
molecule is given by
1
P2 P2y P2z
2:2:24
Htrans
2m x
where Pi is the linear momentum in the ith direction. Then,

1
qtrans 3
expbHtrans dPdr
2:2:25
h
where dP dPx dPy dPz and dr dxdydz. The factor 1/h3 appears in this expression in order to keep the classical result the same as that from the quantummechanical summation. Integration with respect to the volume element dr yields
the volume V of the container. Substituting equation (2.2.24) into equation
(2.2.25), one may write
21
33

V4
2pmkB T3=2
qtrans 3
expbP2 =2mdp5
V
2:2:26
h
h3
1

Thus, the classical expression for qtrans yields the same result as that obtained
from the SWE (equation (2.2.21)).
It is useful to keep the classical way of expressing the partition function and
extend its application to more complex situations. First of all, one may write an
expression for the canonical partition function of an ideal gas in terms of the
partition function for each molecule. On the basis of the total Hamiltonian for
each molecule (equation (2.2.18)), Hj , the canonical partition function is

N
1
expbHj dPj drj
Q
2:2:27
N!h3N
Each integral within the brackets is sixfold with three directional and three
momentum coordinates involved in the integration process. Alternatively, the
partition function may be expressed as

52

LIQUIDS, SOLUTIONS, AND INTERFACES

1
.
.
.
expbHdP1 . . . dPN dr1 . . . drN
N!h3N

where
H

Hj

2:2:28

2:2:29

is the Hamiltonian of the entire system. In the notation used, particle 1 at position
r1 (a vector) is located in volume element dr1, and so on. Now the partition
function is expressed in terms of one 6N-fold integral.
The above treatment of an ideal gas is easily extended to a non-ideal system, at
least, in a conceptual fashion. In the non-ideal system the molecules interact with
each other so that the system has a potential energy, U, which depends on the
coordinates of each molecule in the system. In the real system in which molecular
positions change with time, the potential energy also uctuates. This is reected in
the canonical ensemble by variation in the potential energy with the molecular
conguration in a given microstate. The Hamiltonian for such a system containing N molecules is
H

N
N
X
1 X
P2xj P2yj P2zj
Hintj Ur1 ; r2 ; . . . ; rN
2m j1
j1

2:2:30

Performing the integration in equation (2.2.27), one obtains the following expression for the canonical partition function Q:
Q

qN
int
Z
N!3N

where Z is the congurational partition function, that is,

Z . . . expbUdr1 dr2 . . . drN

2:2:31

2:2:32

It should be noted that it is assumed that the intermolecular forces do not aect
the internal degrees of freedom so that qint is independent of whether these forces
are present or not. When they are absent (U 0), the integral Z collapses to VN
and equation (2.2.31) becomes the same as equation (2.2.23). The important task
of the statistical thermodynamics of imperfect gases and liquids is to evaluate Z.
This subject is discussed in detail later in this chapter. However, the nature of the
intermolecular forces which give rise to the potential energy U is considered next.

2.3 Intermolecular Forces


Molecules exhibit relatively long-range attractive forces between themselves which
give rise to the cohesive forces in liquids. These forces arise because the electronic
distribution in the molecule or atom making up the liquid is not uniform either on
a time-averaged basis or with respect to its instantaneous value. Non-uniformity
in the time-averaged electronic distribution in a molecule is a well-known
phenomenon, and is discussed in terms of the experimentally measured dipole

THE STRUCTURE OF LIQUIDS

53

moment, and higher-order moments such as the quadrupole and octapole


moments. The major attractive component of intermolecular forces is due to
dipoledipole interactions, of which there are three principle contributions,
namely, that due to permanent dipole interactions, that due to induced dipole
permanent dipole interactions, and the dispersion contribution arising from interactions between the instantaneous dipole moments. These are collectively called
van der Waals forces and give rise to an attractive potential between two molecules which is inversely proportional to the distance between them to the sixth
power. The nature of van der Waals forces is now examined in more detail.
van der Waals forces are usually treated using the physics of ideal dipoles. A
real dipole consists of equal and opposite charges separated by a nite distance d.
This concept is easily applied to molecules where dierences in atomic electronegativities leads to polar molecules in which the equal and opposite charges are
separated by distances the order of a typical bond length. A simple example is
carbon monoxide, which has a dipole moment of 0.12 debye because of the
polarity associated with the CO bond. An ideal dipole is one in which the nite
distance separating the charges shrinks to zero but the charge separation is maintained. Thus, the ideal dipole is a point with a vector character associated with the
charge separation. The dipole moment is measured in coulomb meters in SI units
and in debyes in traditional units.* The dipole vector points along the axis of the
dipole from the negative to the positive charge. Because of the vector character of
the dipole moment, the electrostatic equations describing its properties are much
more complex than those for a point charge.
The potential due to an ideal dipole p at a distance r from its center is
p

pr
p cos y

3
4pe0 r
4pe0 r2

2:3:1

where y is the angle between the dipole vector and the line from the dipole to the
point where the potential is measured, and "0, the permittivity of free space. The
maximum potential is obtained in the direction of the dipole vector where cos y is
equal to one. On the other hand the potential perpendicular to the dipole is zero
(cos 90 0). The corresponding equation for a point charge q is
q
2:3:2
q
4pe0 r
In this case the potential is independent of the direction from the charge at which
it is measured. The dipole potential in a given direction falls o as 1=r2 , whereas
that due to a point charge, as 1=r.
The eld due to the ideal dipole is found by taking the gradient of the potential.
Thus,

*All electrical equations in this monograph are written in SI units. As a result, the dipole moment
must be given in C m, not in its usual units of debyes (1 debye 3.336  1030 C m). In addition, the
molecular polarizability, which is usually tabulated in m3, has units of C2 m N1 in the SI system
a 0 cgs aSI=4pe0 . Thus, a polarizability of 1030 m3 in traditional units is equivalent to 1.113 
1040 C m2 V1 in SI units. Although the equations are written for SI units, dipole moments and
polarizabilities are recorded in the tables in this monograph in the traditional units of debyes and m3.

54

LIQUIDS, SOLUTIONS, AND INTERFACES

Ep gradq

3p  r
p
r
4pe0 r5
4pe0 r3

2:3:3

The rst term on the right-hand side gives the component of the eld in the
direction r dened by the vector from the ideal dipole to the point of measurement. The second term gives the component in the direction dened by the dipole.
The net eld, Ep , which is also a vector, points in a direction between p and r
dened by their vector sum. When the eld is measured along the direction of the
ideal dipole, the expression simplies to
Ep y 0

p
2pe0 r3

2:3:4

Now one may estimate the energy of two dipoles on the basis of the work done to
bring dipole p2 from innity to a point located at distance r from dipole p1. This is
u12 p2  E 

3p1  r
p p
p  r 1 2 3
4pe0 r5 2
4pe0 r

2:3:5

In polar coordinates, equation (2.3.5) becomes


u12 r 

p1 p2
 2 cos y1 cos y2  sin y1 sin y2 cosf1  f2 
4pe0 r3

2:3:6

where yi is the angle that dipole i makes with the z-axis, chosen as the direction
dened by the line between the dipoles, and fi is the angle that dipole i makes
with the x-axis (see g. 2.1). There are several important congurations that are
among all possible congurations of two dipoles. The rst corresponds to the case
that the two dipoles point along the z-axis with the head of one dipole pointing to
the tail of the other (g. 2.1). In this case
y1 y 2 0

2:3:7

and
u12 r 

2p1 p2
4pe0 r3

2:3:8

Fig. 2.1 Schematic diagram showing two


dipoles pa and pb separated by a distance r
along the z-axis with orientations dened by
the angles ya, fa and yb, fb. The four simple
congurations for two dipoles and their
interaction energies are also illustrated with
ur pa pb =4pe0 r3 :

THE STRUCTURE OF LIQUIDS

55

On the basis of equation (2.3.6), this is the conguration of minimum energy. The
conguration of maximum energy occurs when the two dipoles are oriented with
their heads or tails pointing to one another. This occurs when
y1 0

y2 1808

and

2:3:9

and gives an energy


u12 r

2p1 p2
4pe0 r3

2:3:10

Two other congurations are important in assessing dipoledipole interactions.


The rst occurs when the two dipoles are parallel to each other but point in
opposite directions. This is obtained when
y1 908;

y2 2708;

f1 f2

and

2:3:11

with the result that


u12 r 

p1 p2
4pe0 r3

2:3:12

Finally, when the two dipoles are parallel and point in the same direction
y1 908;

y2 908;

and

f1 f2

2:3:13

so that
u12 r

p1 p2
4pe0 r3

2:3:14

The important result from this analysis is that the dipoledipole interaction
energy depends on the product of the two dipole moments and decreases with
distance as 1=r3 .
In order to estimate the contribution of interactions between permanent
dipoles to intermolecular forces, one must consider all possible relative orientations at a given separation distance r. The interaction energy is then averaged,
taking into account the probability of a given orientation on the basis of a
Boltzmann factor. In this way, orientations with attractive interaction are
weighted in favor of those resulting in repulsive interaction. The expression giving
the net average interaction energy between two dipoles is

u r expu12 r=kB Tdo1 do2


12

2:3:15
udd r
expu12 r=kB Tdo1 do2
where
doi sin yi dydf

2:3:16

Integration over all possible values of y and f for the case that u12 r is small with
respect to kB T gives the following result for the average dipoledipole interaction
energy:
udd r

2p21 p22
34pe0 2 kB Tr6

2:3:17

56

LIQUIDS, SOLUTIONS, AND INTERFACES

In the averaging process, the factor p1 p2 =4pe0 r3 ; which appears in the expression
for the energy of a specic orientation, is squared, so that the average attractive
interaction depends on 1/r6. Thus it is important to distinguish between the interaction energy of two isolated dipoles, xed with respect to their relative orientations, which depends on the distance separating them as 1=r3 , and the interaction
energy between the same two dipoles, when it is averaged over all possible mutual
orientations, which depends on 1=r6 .
As an example, consider the case of two water molecules in contact, each with a
dipole moment equal to 1.85 debyes (6.17  1030 C m) and represented as
spheres with diameters of 274 pm. The attractive energy between these molecules
when they are oriented in the conguration of maximum attraction is 3:25 
1020 J, that is, 7:9kB T at room temperature. On the other hand, when the
attractive energy is estimated using Boltzmann averaging, it is 4:30  1020 J
or 10:4kB T. The Boltzmann-averaged value is more than 50% of the maximum
attractive energy. It follows that dipoledipole interactions represent a major
component of the cohesive energy which leads to formation of the liquid state
in water.
A second component of van der Waals forces is that resulting from the induced
dipole moment formed in one molecule in the presence of another molecule
possessing a permanent dipole moment. If a1 and a2 are the polarizabilities of
the two molecules, the potential energy due to dipoleinduced dipole interactions
is
uid r

p21 a2 p22 a1
4pe0 2 r6

2:3:18

This is derived by considering the interaction of two polarizable dipoles in a


general orientation and then averaging over all possible orientations. Assuming
a molecular polarizability equal to 1.46  1030 m3 (1.62  1040 C m2 V1) for
water, the value of uid r for water molecules in contact is 2:3  1021 J, or
0:6kB T at room temperature. As expected, this contribution is much smaller
than that due to the interaction of the permanent dipole moments.
The third contribution to the attractive forces comes from London dispersion
forces. These arise from the instantaneous dipoles on the molecules formed by the
moving electrons. Thus, inert gas atoms such as helium and argon possess instantaneous dipole moments formed by the electron cloud, which is constantly in
motion. Dispersion forces were analyzed using quantum mechanics by London
[2] who derived the following expression for the attractive potential:
udis 

3I1 I2 a1 a2
2I1 I2 4pe0 2 r6

2:3:19

where I1 is the ionization potential of molecule 1, and I2 , that of molecule 2. For


two water molecules in contact, the dispersion energy is 1:85kB T at room temperature given that the ionization potential of a water molecule is 12.6 eV or 2.02
 1018 J molec1 .

THE STRUCTURE OF LIQUIDS

57

EXAMPLE

Estimate the contributions to the van der Waals energy in dimethylsulfoxide at


25 C by considering two molecules in contact as hard spheres with diameters of
491 pm. The dipole moment of dimethyl sulfoxide is 3.96 debyes, its polarizability, 7.99  103 nm3, and its ionization potential, 9.01 eV.
The dipoledipole attractive potential energy for two identical spherical
molecules in contact is
udd

2p4
34pe0 2 kB Ts6

2:3:20

where s is the molecular diameter. For dimethyl sulfoxide,


udd

23:96  3:336  1930 4


31:113  1010 2  1:38  1023  298:2  4:91  1010 6

2:3:21

2:84  1020 J molec1 ; or  6:91kB T


Similarly, for the dipoleinduced dipole interactions,
uid

2p2 a
4pe0 2 s6
23:96  3:336  1030 2  7:99  1030  1:113  1010
1:113  1010 2  4:91  1010 6

2:3:22

1:79  1021 J molec1 ; or  0:43kB T


For the London dispersion energy,
udis

3Ia2
44pe0 2 s6
39:01  1:602  1019 7:99  1030 2
4  4:91  1010 6

2:3:23

4:93  1021 J molec1 ; or  1:20kB T


Note that the calculations of uid and udis in which the polarizability is involved
are simpler when the SI polarizability a is replaced by a 0 =4pe0 , which has
units of m3. Then equations (2.3.22) and (2.3.23) may be written as
uid

2p2 a 0
4pe0 s6

2:3:24

udis

3Ia 02
4s6

2:3:25

and

Values of the dipoledipole, dipoleinduced dipole, and London dispersion


contributions for two molecules in contact are summarized for a range of liquids

58

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 2.1 Estimation of van der Waals Interaction Energies for Two Molecules at
Contact Using a Spherical Representation of the Molecules
Atom or
Molecule
Argon
Nitrogen
Hexane
Benzene
Water
Acetone
Acetonitrile
Dimethyl sulfoxide

Molecular Dipole
Molecular Ionization van der Waals Energy*
Diameter Moment Polarizability Potential
s=pm
p=debye
a=nm3
I=eV
udd =kB T uid kB T udis =kB T
370
400
592
563
274
476
427
491

0
0
0.09
0
1.82
2.88
3.92
3.96

1:63  103
1:76  103
0:0118
0:0103
1:46  103
6:41  103
4:41  103
7:99  103

15.8
15.6
10.1
9.25
12.6
9.71
12.2
9.01

0.0
0.0
0.0
0.0
10.38
2.33
15.34
6.91

0.0
0.0
0.0
0.0
0.55
0.22
0.54
0.43

0.48
0.34
0.95
0.90
1.85
1.00
1.14
1.20

Estimated at 25 C.

in table 2.1. It should be kept in mind that equations (2.3.17)(2.3.19) are generally not applicable at such short distances, since they were derived on the basis
of point dipole models. However, they give a good idea of the relative magnitude
of the three components and how they change when one goes from an inert gas
like argon to very polar molecules like water and dimethyl sulfoxide. It is also
easily seen from these equations that the intermolecular potential energy falls o
rapidly with increase in distance between the molecules. Thus, if the separation is
two molecular diameters, the value of the potential energy drops by a factor of
1/26, that is, 1/64; for three molecular diameters this decreases to 1/36, or 1/729,
and so on.
The above simple picture of the attractive component of intermolecular forces
is certainly not complete. Since a complete electrostatic description of a molecule
usually requires the introduction of higher-order moments, one must also consider the potential energy due to dipolequadrupole interactions, quadrupole
quadrupole interactions, and interactions of moments of higher order. These
lead to terms proportional to r8 , r10 , and so on. Obviously, the potential energy
due to these components falls o much more rapidly than those due to dipole
dipole interactions, and therefore, is less important. Another factor not considered in the above discussion is the role of hydrogen bonding, which is very
important for protic molecules such as water and the alcohols. It is well recognized that hydrogen atoms bonded to more electronegative atoms such as oxygen
and nitrogen can form a bond with another electron-rich atom in an adjacent
molecule. The best-known example of hydrogen bonding is that in water, where
the hydrogen atom on one molecule bonds with the oxygen atom on an adjacent
molecule. Other well-known examples are the alcohols, certain amides like formamide and acetamide, and carboxylic acids. In order to estimate the strength of
hydrogen bonding, one must develop a quantum-mechanical model of the system.
This is a complex topic and is not considered further here. It is sucient to point
out that hydrogen bonding accounts for an important fraction of the cohesive
energy in liquids when it is present.

THE STRUCTURE OF LIQUIDS

59

Hydrogen bonding is an example of a relatively short-range attractive force


between specic types of molecules. In general, one must consider another shortrange force which is experienced by all atoms and molecules and which is repulsive. This repulsive interaction arises when the electronic clouds in two molecules
are so close that they repel one another. It may be treated quantum mechanically
in the adiabatic approximation in which the nuclei in the molecules are assumed
to be motionless, and the wave functions for the electrons calculated. An approximate form for the repulsive energy between two molecules is
urep AR ear

2:3:26

where AR and a are constants depending on the properties of the individual


molecules. This is more conveniently approximated by a function of the twelfth
power of the intermolecular distance, r, so that equation (2.3.26) becomes
urep

AR
r12

2:3:27

When one compares this term with the attractive van der Waals forces considered
above it is clear that the repulsive energy falls o much more rapidly with distance
than the attractive one.
When one adds the attractive van der Waals potential terms to the repulsive
term, one obtains the LennardJones expression for the intermolecular potential
energy for a simple uid such as an inert gas like argon. On the basis of the above,
the LennardJones potential function may be written
ur

ALJ BLJ
 6
r12
r

2:3:28

where the second term represents the attractive van der Waals component.
Obviously, there is a minimum potential energy, LJ , corresponding to the optimum distance between any two molecules. In addition, one may identify the
molecular diameter s as corresponding to the distance at which the intermolecular potential energy is zero. As a result, the constants ALJ and BLJ are
connected by the equation
ALJ =BLJ s6

2:3:29

dur
ALJ
B
12 13
6 LJ
0
dr
r7e
re

2:3:30

At the optimum separation re

so that
r6e

2ALJ
BLJ

2:3:31

It follows that at the minimum


LJ

ALJ BLJ
B2
B2
B2
 6 LJ  LJ  LJ
12
4ALJ 2ALJ
4ALJ
re
re

2:3:32

Solving equations (2.3.29) and (2.3.32) for the constants ALJ and BLJ , one obtains

60

LIQUIDS, SOLUTIONS, AND INTERFACES

ALJ 4s12 LJ

2:3:33

BLJ 4s6 LJ

2:3:34

and

It follows that the LennardJones equation is





s 12
s 6
ur 4LJ

r
r

2:3:35

It is easily seen that the function r12 was chosen to replace ear for the repulsive
component in order that a simple mathematical result could be obtained.
EXAMPLE

Estimate the LennardJones energy of molecular nitrogen at the optimum


separation re and at twice this value. Use the parameters given in table 2.2.
From the table,
LJ 95:2  1:381  1023 1:245  1021 J molec1

2:3:36

When r is equal to re , ur is equal to LJ . The relationship between re and s is


r6e 2s6

2:3:37

so that re is 420.4 pm, given that s is 374.5 pm.


When r is equal to 2re
"
#


s12
s6
1
1
ur 4LJ

LJ 12  5
2
2
221=6 s12 221=6 s6

2:3:38

0:031  1:245  1021 3:86  1023 J molec1


Thus, the LennardJones energy at 2re is 3:86  1023 J molec1 :
A plot of the LennardJones potential against distance between two molecules
is shown in g. 2.2. It is clear that the repulsive component dominates for values
of r less than the molecular diameter, where it rises to values over 5LJ for
r 0:9s. The stable minimum occurs at r 1:12s. By the time the separation between the two molecules is equal to three times their diameter, the intermolecular

Table 2.2 LennardJones


Parameters for Simple Molecules
Atom or Molecule
Ar
Xe
N2
CO2

s=pm

LJ k1
B =K

350
410
374.5
433

117.7
222.3
95.2
198.2

*kB is the Boltzmann constant, so that LJ k1


B
has units of temperature.

THE STRUCTURE OF LIQUIDS

61

Fig. 2.2 Plot of the


LennardJones potential
ur in units of the attractive
potential energy LJ against
intermolecular distance, r, in
units of the molecular
diameter s. The vertical and
horizontal straight lines at r
s show the potential
energy for a hard-sphere
representation of the system.

potential is negligible. This potential energy function has often been used in the
development of the theory of simple liquids such as the noble gases at low temperature. For many liquids that chemists use, a much more complex expression for the
intermolecular potential is required. However, the properties of a Lennard
Jones liquid are reasonably easily derived and form a convenient point of reference with respect to which the properties of more complex systems can be
considered.

2.4 Distribution and Correlation Functions


The experimental and theoretical descriptions of liquid structure are most conveniently achieved in terms of distribution functions. This is because there is
short-range structure in the liquid, but at large distances from the point of reference, the distribution of molecules is random. In this section, the fundamental
aspects of distribution and correlation functions, especially, the pair correlation
function, are outlined.
Using the congurational partition function derived earlier (equation (2.2.32)),
one may write an expression for the probability of any given conguration in
which the particle located at r1 is in volume element dr1, that at r2 in dr2, and so on
(g. 2.3). This probability is given by
f N r1 ; . . . rN dr1 . . . drN

expbU
dr1 . . . dN
Z

2:4:1

The ratio exp(bU=Z is the important part of this expression, giving the fraction
of the conguration integral associated with a given potential energy U.
Otherwise, the expression is of little practical use other than as a starting point
for deriving simpler distribution functions. The most elementary of these is the
single-particle distribution function f 1 r1 , which gives the probability of nding
a particle or molecule at position r1 . It is found by integrating the N-particle
density function f N over the remaining coordinates r2 ; . . . rN and multiplying
by the number of ways of choosing particle 1, namely N. The result is

62

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 2.3 Coordinate system in


which the location of each
particle is designated by a vector
ri with its associated volume
element dri. Three particles are
shown at r1, r2, and r3. The scalar
distances between them are r12
jr1  r2 j and r13 jr1  r3 j.

f 1 r1

N
. . . expbUdr2 . . . drN
Z

2:4:2

Since the system is uniform, the potential energy is a function of relative coordinates only so that Z can be written as the product of the integral in the numerator
times the volume of the system V. It follows that the singlet distribution function
is simply the number of particles or molecules in the uid N per unit volume V,
that is,
f 1 r1

N
V

2:4:3

One may also dene the pair distribution function f 2 r1 ; r2 as the probability of
nding a particle in the volume element dr2 at r2 given that there already is a
particle in the volume element dr1 at position r1 . By analogy with equation (2.4.2),
the pair distribution function is given by

NN  1
2
. . . expbUdr3 . . . drN
f r1 ; r2
2:4:4
Z
By integrating f 2 r1 ; r2 over dr2 , that is, over the volume of the system, one
obtains the singlet distribution function:

NN  1
2:4:5
f 2 r1 ; r2 dr2 N  1f 1 r1
V
In the same way, one may dene higher-order distribution functions. For
instance, f 3 r1 ; r2 ; r3 is the probability of nding a particle at r3 given that
there are already particles at r1 and r2 . A dening relationship for this function is

f 3 r1 ; r2 ; r3 dr3 N  2f 2 r1 ; r2
2:4:6
The pair distribution function leads to the pair correlation function, which
illustrates how the local order found near a given molecule is lost as distance
from the molecule increases. This quantity is of fundamental theoretical interest
and may be determined in X-ray and neutron scattering experiments, as discussed
below. The denition of the pair correlation function gr12 is

THE STRUCTURE OF LIQUIDS

gr12

N2 f 2 r1 ; r2
V2

63

2:4:7

This function gives the normalized probability for nding a molecule at r2 when
another molecule is at r1 . Usually, the reference molecule is assumed to be at the
origin of the coordinate system and the subscript 12 is dropped so that the pair
correlation function becomes simply gr. In the limit that r goes to innity, gr
goes to unity, demonstrating that there is no correlation between the molecule at
the origin and one innitely far away. Another way of thinking about this function is to consider gr as a factor which multiplies the average bulk density, N=V,
to give the local density, Ngr=V, about a central molecule. The correlation
function for a uid obeying the LennardJones potential as calculated by
Verlet [3] is shown in g. 2.4. At the optimum distance from the central molecule
or particle, which is slightly larger than the molecular diameter s, gr is close to
three because of attractive intermolecular forces. As distance increases, the correlation function oscillates, reecting the nite size of the particles in the system.
A second maximum is found at twice the optimum distance but its height is
signicantly reduced with respect to that of the rst. Eventually, the oscillations
die away so that, at a distance equal to four or ve particle diameters, the eect of
the central molecule is scarcely felt.
Several important quantities may be obtained from gr. One is the potential of
mean force Wr. This is dened by the equation
Wr kB T ln gr

2:4:8

The problem of obtaining a relationship between Wr and the intermolecular


potential ur is central to the statistical mechanics of non-ideal gases and liquids.
Various methods have been described for making this connection as discussed in
the statistical mechanical literature [G1G4]. As with any potential energy, one
may obtain the force acting on the central particle in the direction of any other
particle by dierentiation with respect to the distance vector r1 . Thus, the mean
force acting on the central particle due to a molecule at r1 is

Fig. 2.4 The correlation


function gr for a uid
obeying the LennardJones
potential with LJ 1:69kB T
and a molecular density N=V
0:88s3 [3].

64

LIQUIDS, SOLUTIONS, AND INTERFACES

Fr1 

@Wr kB T @gr

@r1
gr @r1

2:4:9

Another function commonly used in discussing the structure of liquids is the


total correlation function hr. It is simply related to gr by the equation
hr gr  1

2:4:10

Clearly, when the separation between two molecules is suciently large, hr is


zero (see g. 2.4).
From the total correlation function, one obtains the structure factor SkD by
Fourier transformation. Thus,

SkD 1 N=V hreikD r dr


2:4:11
where kD is the reciprocal distance. The structure factor may be determined
experimentally from X-ray and neutron diraction experiments, and thus provides a direct route to information about the pair correlation function in liquids.
A plot of SkD against reciprocal distance kD based on the data obtained by
Yarnell et al. [4] for liquid argon near its triple point is shown in g. 2.5. Damped
oscillations of the same kind are found for the structure factor as are seen for gr.
More information about Fourier transforms is found in appendix A.
One still has the problem of relating the potential energy of the system U, which
appears in the congurational integral (equation (2.2.32)) and in the pair correlation function (equations (2.4.4) and (2.4.7)) to the intermolecular potential energy
between any two molecules, uij . The potential energy can be expanded in terms of

Fig. 2.5 An example of an experimentally determined structure factor, namely, that for
liquid argon near its triple point [4]. (Reproduced from Physical Review A, by permission.)

THE STRUCTURE OF LIQUIDS

65

a sum of interactions between pairs of molecules, triplets of molecules, and so on.


It follows that
Ur1 ; . . . ; rN

N
X
i<j1

urij

N
X

vrij ; rik ; rjk . . .

2:4:12

i<j<k1

where urij is the pair interaction energy already discussed, and vrij ; rik ; rjk the
triplet interaction energy. The contributions of the triplet and higher-order terms
given by the second and higher sums in equation (2.4.12) constitute about 5% of
the total potential energy. Estimation of eects beyond the pair potential contribution represents an important problem in the statistical thermodynamics of
liquids and several strategies have been developed to solve this problem. More
detailed discussion of this topic, including the use of cluster diagrams, can be
found elsewhere [G1, G2, G4]. In this chapter, only the integral equation
approach is considered and is presented later.

2.5 The Experimental Study of Liquid Structure


The structure of pure liquids and liquid solutions is conveniently studied using
diraction techniques [5]. The most common of these is X-ray diraction. Two
other useful techniques are neutron and electron diraction. In these experiments,
radiation, which is usually monoenergetic, penetrates the liquid sample and is
scattered through an angle y (see g. 2.6). The analytical information is obtained
by studying the intensity of the scattered radiation as a function of this angle. In

Fig. 2.6 Schematic representation of a scattering experiment in which the intensity of


scattered radiation is measured as a function of the scattering angle y (From P. A.
Egelsta, An Introduction to the Liquid State, 2nd edition, Oxford University Press, New
York (1992), by permission.)

66

LIQUIDS, SOLUTIONS, AND INTERFACES

X-ray diraction, the X-rays are scattered by the electron clouds around individual atoms. Since the atoms and molecules of the liquid sample are not xed in
space, the information resulting from the diraction experiment must be interpreted in terms of statistical averages. The neutrons used in a neutron diraction
experiment are scattered by the nuclei of the atoms in the liquid sample so that the
scattering pattern is quite dierent from that for X-rays. In electron diraction,
the electrical potential, which depends on the spatial conguration of the nuclei
and electronic density distribution, determines the diraction pattern. Early
experiments involved simple monoatomic liquids such as the inert gases and liquid
metals. However, many molecular liquids have also been studied, including polar
liquids such as water, the alcohols, and amides [5]. In this section, attention is
focused on two of these techniques, namely, X-ray and neutron diraction.
The incoming radiation in the experiment is characterized by its wavelength, l,
or its frequency n, and by its intensity I0 . Special eorts must be made to achieve
monochromatic radiation. The wavelength is chosen so that it is commensurate
with the average distance between atoms, but much smaller than the sample
dimensions. A typical wavelength for neutrons is the order of 100 pm, which
corresponds to a kinetic energy of 0.08 eV; the wavelength and the linear momentum are connected through the de Broglie equation:
l

h
P

2:5:1

where P is the momentum of the neutrons. The scattering results are presented as
a function of the variable kD , which has the dimensions of reciprocal distance:
kD

4p siny=2
l

2:5:2

Consider rst of all the scattering of neutrons by the nuclei in a monoatomic


liquid. This process is characterized by a scattering cross-section, sD , which, in
turn, is related to bD , the bound atom scattering length. For slow neutrons,
sD 4pbD 2

2:5:3

Two types of scattering are observed in these experiments, namely, coherent and
incoherent scattering. The former is directly related to the structure of the sample
and can be used to determine the structure factor SkD of a simple monoatomic
liquid. Incoherent scattering arises due to isotope or spin eects. The presence of
dierent isotopes in a sample leads to dierent values of scattering length bD ,
which depends in a complex way on the number of nucleons in the nucleus from
which it is scattered. In addition, a given nucleus may possess a spin which is
randomly oriented in the sample. This characteristic of the system contributes to
incoherent scattering. The incoherence only gives information about an individual
atom and no information about the collective motion of atoms.
The relationship between the scattered intensity and the structure factor for a
monoatomic liquid is
Iy aD yhbD i2 SkD D

2:5:4

THE STRUCTURE OF LIQUIDS

67

where aD y is a factor which depends on the properties of the instrument used for
the experiments and inelastic scattering from the sample, and D gives the contribution from incoherent scattering. hbD i denotes the value of the atomic scattering length averaged with respect to isotopic composition and spin state. The two
unknown quantities in equation (2.5.4), namely, aD y and D are determined by
measuring the intensity at y 0 and y 1. The structure factor of undeected
neutrons is related to the sample atomic density NA and isothermal compressibility, T by the following equation:
S0 NA T kB T

2:5:5

At very large angles, the structure factor goes to unity (see g. 2.6)
S1 1

2:5:6

As a result, one may show for monoatomic liquids that


SkD

IkD  I0
I1  I0

2:5:7

In the case of X-rays, scattering occurs from electrons in the atoms of the liquid
sample, and depends on the electron density of the isolated atom, Ne r=V, where
Ne r is the number of electrons at distance r. The quantity corresponding to hbD i2
in the neutron diraction experiment is the atomic scattering intensity for isolated
atoms, fD 2 kD , where
ra
Ne r
sin kD r
4pr2
dr
2:5:8
fD kD
V
kD r
0

In contrast to hbD i
depends on the angle of scattering y as expressed
through the parameter kD . The structure factor SkD is simply the ratio of the
scattered intensity IkD to the incident intensity I0 divided by the intensity ratio
that would be observed for the same number of atoms of the same atomic mass as
individuals. The resulting expression for SkD is
2

; f 2D kD

SkD

IkD
Z2
I0 NZ f 2D kD

2:5:9

where NZ is the number of atoms of atomic number Z.


Both the X-ray and neutron diraction techniques are subject to experimental
diculties. It is important to be able to carry out the experiments to high values of
kD so that Fourier transformation can be performed accurately. A practical limitation for the value of kD in X-ray and classical neutron diraction experiments is
180 nm1 . It is also dicult to measure SkD for very small values of kD .
Problems due to incoherent scattering with neutrons and with absorption of
radiation also have to be dealt with. However, it is apparent from g. 2.5 that
data of high precision can be obtained for simple systems such as the rare gases in
the liquid state.
Initially, diraction experiments were performed on monoatomic liquids such
as argon and neon, or on liquid metals such as mercury. The analysis of scattering
data from molecular liquids is more dicult. Nuclei with dierent atomic masses
are present, and the incident radiation is scattered by dierent amounts by each

68

LIQUIDS, SOLUTIONS, AND INTERFACES

type of nucleus. In the case of symmetrical molecules such as methane or carbon


tetrachloride, the scattering data can be interpreted in a reasonably straightforward fashion. However, in the case of molecules like water, the resulting spectra
are much more complex.
For liquids with molecules containing dierent atoms, the change in intensity
with angle y is given by
"
#
X
dI
2
nA
ci f i kD FT kD
2:5:10
dy
i
where nA is the number of dierent atoms (nuclei) in the sample, ci , the molar
concentration of atom i; fi kD , the inherent scattering amplitude of the same
atom, and FT kD , the structure function for the liquid being studied. For example, in the case of water there are two atoms, the H atom and the O atom. In
neutron diraction, the scattering amplitude fi kD is an inherent property of the
atom and is tabulated for each atom on the basis of its nuclear composition. That
means that it is dierent for normal hydrogen, 1 H, and heavy hydrogen (deuterium), 2 H. Since ordinary water contains some heavy water, an ordinary water
sample actually contains three dierent atoms. In the above discussion of scattering from monoatomic liquids, fi kD was referred to as bD ; the simpler notation
was used because the scattering fraction is independent of kD in neutron experiments.
The structural information from the scattering experiment is contained in the
structure function FT kD which is dened as follows for both X-ray and neutron
experiments:
!2
XX
X
FT kD
2  dij ci cj fi kD fj kD S ij kD  1=
ci fi kD
2:5:11
ij

where S ij kD is the partial structure factor for atoms i and j, and dij is the
Kronecker delta. In the case of a monoatomic uid such as liquid argon, there
is only one kind of atom i j and the structure factor S Ar is easily extracted
from the structure function. In the case of liquid water, ignoring minor isotopic
components, there are three partial structure factors, namely, S OO ; S OH , and S HH .
The individual structure factors must be separated in the structure function in
order to obtain the corresponding pair correlation functions. This separation is
usually achieved using isotopic substitution techniques as described below. It
should be noted that the partial structure factors S OH and S HO are the same
because of the nature of the experiment. It follows that there are six independent
partial structure factors for a triatomic molecule such as HOD, namely,
S OO ; S OD ; S OH ; S DD ; S DH , and S HH .
If the individual partial structure factors S ij kD can be determined, one can
calculate the individual partial pair correlation function gij r on the basis of a
Fourier transformation:

1

V
gij r 1
S ij kD  1kD sinkD r dkD
2:5:12
2p2 Nr
0

THE STRUCTURE OF LIQUIDS

69

However, if this is not possible, one is forced to Fourier transform the whole
structure function FT kD to obtain the overall correlation function Gr, which is
dened as
1


V
Gr
FT kD sinkD r dkD
2:5:13
2p2 Nr
0

Because the fractions fi kD and fj kD depend on the nature of the atom, Gr is


not a linear combination of the individual gij r functions, so that their separate
determination is quite dicult in general.
As pointed out above, X-radiation is scattered by the electrons around each
atom, and the scattering amplitude increases monotonically with the atomic number Z of the atom [G2]. The value of fi kD for the hydrogen atom is so small that
the contribution of partial structure factors involving this atom to FT kD can be
neglected. As a result, in an X-ray scattering experiment in pure water, the only
signicant contribution to FT kD is from S OO kD . The overall correlation function Gr obtained from these experiments shows a single sharp maximum at 285
pm [6, 7]. More detailed analysis of the data indicates that each water molecule is
surrounded on the average by four nearest neighbors.
In the case of neutron diraction, the radiation is scattered by the atomic
nuclei, not by the electrons. It turns out that nucleons such as 1 H and 2 H have
very dierent scattering amplitudes. This means that isotope eects are very
important in developing experimental strategies. Soper and Phillips [8] used
data for the structure function obtained in mixtures of normal and heavy water
to extract values of the partial structure factors for water. In this way they were
able to determine all of the pair distribution functions for water from their diffraction data. These are gHH r; gOH r, and gOO r. More details of their experimental results are given in section 2.10.
X-ray and neutron diraction studies have also been carried out in other
liquids with hydrogen bonding. Results with three or more dierent atoms
become quite complex. A good example is methanol, which has three dierent
atoms, namely, C, O, and H. Moreover, there are two dierent types of H atom,
that on oxygen, which is involved in hydrogen bonding, and those in the methyl
group, which are not. On this basis there are ten distinct contributions to the
structure function, that is, S CC ; S CO ; S CH ; S CM ; S OO ; S OH ; S OM ; S HH ; S HM ; and
S MM , where M designates a hydrogen atom in the methyl group, and H, the
hydrogen atom of the hydroxyl group. In an X-ray experiment, only three of
these are signicant, namely, S CC ; S CO , and S OO . Fourier transformation of the
structure function FT kD for methanol gives a correlation function Gr with one
sharp peak at 280 pm [9]. This corresponds to the distance between two oxygen
atoms in adjacent methanol molecules. The peak is sharp because hydrogen
bonding results in a strong correlation between oxygen atoms in liquid methanol.
Further analysis of the data demonstrates that there are, on the average, two
other molecules associated with the central one. This result is interesting because
it demonstrates the importance of hydrogen bonding in the structure of protic
solvents. Water, which has two sites for hydrogen bonding per molecule, has
approximately four nearest neighbors associated by hydrogen bonding, whereas

70

LIQUIDS, SOLUTIONS, AND INTERFACES

methanol, which can form one hydrogen bond per molecule, has two. More
recently, a complete description of the ten pair correlation functions in methanol
has appeared [10]. The experimental data were obtained using neutron diraction
and involved the use of isotope techniques to separate the component structure
factors. These were then Fourier transformed to give the individual pair correlation functions.
Other polar liquids which have been studied using X-ray and neutron diraction are acetonitrile [11, 12], formamide [13, 14], and dimethyl sulfoxide [15]. The
analysis of X-ray data for molecules containing the methyl group is simpler
because this group can be treated as a simple atom. On this basis, acetonitrile
contains only three distinguishable atoms, namely, CH3, C, and N. As a result
there are only six partial structure factors to be considered in analyzing the X-ray
diraction data. Studies of protic solvents such as formamide show that there are
hydrogen-bonded chains in this liquid. On the other hand, aprotic solvents like
acetonitrile and dimethyl sulfoxide show evidence of dimerization due to strong
dipoledipole interactions.
Diraction studies of liquid structure constitute an active area of contemporary research. When suitable isotopes are available the data may be resolved to
give the individual structure factors and pair correlation functions. These studies
help elucidate the role of intermolecular forces in determining liquid structure,
and hence bulk properties.

2.6 The Direct Correlation Function and the Mean


Spherical Approximation
One of the important methods of developing a model for the potential energy of
the liquid system is that based on integral equations. These include the Kirkwood
integral equation, the BornGreenYvon equation, and the OrnsteinZernike
equation. The last approach leads to the denition of the direct correlation function cr12 . It is the approach which is most frequently used and is the one which is
considered here.
In earlier discussion, the total correlation function hr12 was dened to be
gr12  1. This quantity is a measure of the total inuence molecule 1 has on
molecule 2 at a distance r12 . Ornstein and Zernike [16] proposed that this inuence
could be considered as composed of two parts, a direct part and an indirect part.
The direct part, which measures the direct inuence of molecule 1 on molecule 2,
is given by cr12 . The indirect part is the inuence propagated by molecule 1 on
molecule 3, which then aects molecule 2 either directly or indirectly through
other molecules. The indirect eect is weighted by the density and averaged
over all positions of molecule 3. As a result one may write

N
hr12 cr12
cr13 hr23 dr3
2:6:1
V
v

This equation is the OrnsteinZernike (OZ) equation and gives the mathematical
denition of cr12 with the indirect eect being expressed as a convolution
integral of h and c. By Fourier transformation, one obtains

THE STRUCTURE OF LIQUIDS

Nc~kD h~kD
h~kD c~kD
V

71

2:6:2

where c~ and h~ are the Fourier transforms of cr and hr, respectively. Using the
denition of the structure factor, one may also write
Nc~kD SkD  1

V
SkD

2:6:3

It follows that the direct correlation function may be calculated from the experimental structure factor after Fourier transformation of the expression on the
right-hand side of this equation.
Three other important equations in the statistical thermodynamics of liquids
involve the direct correlation function and provide a connection between the
intermolecular potential ur for two molecules and the potential of mean force
Wr. One way of deriving these equations is by writing an approximate expression for the indirect contribution to the pair correlation function gr. Keeping in
mind that Wr is dened as  ln gr=b, and dening gind r as the contribution to
gr from indirect interactions, an approximate expression for cr is
cr gr  gind r gr  expfbWr  urg

2:6:4

The approximation consists of assuming that the potential of mean force Wr less
the direct interaction energy ur gives a correct estimate of the indirect eect of
the other molecules in the system. Equation (2.6.4) may also be written as
cr grf1  expburg

2:6:5

This result is known as the PercusYevick (PY) approximation [17]. It has been
applied with considerable success to the evaluation of the properties of a liquid
composed of hard spheres. In this case, the interaction energy ur is zero so that
cr 0;

r>s

2:6:6

Another approximation for cr is obtained by expanding the exponential in


equation (2.6.4). Assuming that the rst two terms in the expansion suce, one
obtains
cr gr  1 bWr  bur hr  ln gr  bur

2:6:7

This expression for cr is called the hypernetted chain (HNC) approximation [18].
On the basis of cluster diagrams [G4] it has been shown that the HNC equation
provides a better description of most systems than the PY equation. It has been
applied extensively in the development of the theory of liquids and electrolyte
solutions. Its drawback is that the OZ equation can only be solved numerically
using this approximation.
Values of the direct correlation function estimated for the LennardJones uid
described earlier (g. 2.4) using the PY equation are shown in g. 2.7. It is
apparent that cr rises to a maximum close to the rst maximum in the total
correlation function hr and then rapidly dies away, reaching a value of zero close
to r 2:5s. When cr is estimated by the HNC equation, qualitatively similar
results are obtained but the exact values of cr dier by a few percent.

72

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 2.7 Total correlation function hr () and the direct correlation function cr () for a
liquid obeying the LennardJones potential with the same parameters as in g. 2.4.

Since cr is short ranged, an even simpler approximation can often be applied


to estimate it in the region outside of a hard sphere. The logarithmic term in
equation (2.6.7) can be written as ln[1 hr]. Expanding this using only the rst
two terms, the expression for cr becomes
cr bur;

r>s

2:6:8

This approximation is known as the mean spherical approximation (MSA). For the
case of a hard-sphere uid for which ur 0, the MSA is equivalent to the PY
approximation. For the case that the hard spheres have embedded point charges,
the function ur is simply Coulombs law. Although the MSA provides the least
detailed expression for cr, it is popular because the OZ equation can often be
solved using this approximation to yield an analytical expression for gr. The
equation for gr within a hard sphere is
gr 0;

r<s

2:6:9

Equations (2.6.8) and (2.6.9) give what is known in statistical mechanics as the
closure conditions. To solve a particular problem given ur, one must rst determine cr for r < s. After Fourier transformation, one can calculate the total
correlation function in Fourier space, namely, h~k, using equation (2.6.2).
Inverse Fourier transformation then gives hr and gr.
Wertheim [19] showed that cr within a non-interacting hard sphere on the
basis of the MSA is given by
cr l1 
where

62 zr zl1 r3

;
s
2s3

r<s

2:6:10

THE STRUCTURE OF LIQUIDS

73

Fig. 2.8 The pair correlation function gr for a uid composed of hard spheres at a
packing fraction of z 0:49 calculated as a function of distance, r, using the Ornstein
Zernike equation with the direct correlation function given by equations (2.6.6) and
(2.6.10). The data shown as () are from a Monte Carlo calculation.

l1

1 2z2
1  z4

2:6:11

1 z=22
1  z4

2:6:12

and
l2 

The parameter z is the packing fraction given by


z

Nps3
6V

2:6:13

The radial distribution function is now obtained using the OZ equation. The
resulting expressions for gr are rather lengthy and are not written out here.
However, it is clear that the calculated gr is very close to the value that one
obtains on the basis of a computer simulation (g. 2.8). A brief description of
computer calculations is given in the following section.
As will be seen in later chapters, the integral equation approach has been
applied to other important problems relating to liquids and solutions. The
MSA used to dene cr in the region outside of a given sphere has proven to
be especially useful because of its simplicity.

2.7 Computer Simulations of Simple Liquids


Two types of reference uids have been studied extensively by computer experiments. One system is composed of the non-interacting hard spheres discussed

74

LIQUIDS, SOLUTIONS, AND INTERFACES

above and is often referred to as PercusYevick (PY) uid. The other system is
made up of spheres which interact by van der Waals forces according to a
LennardJones potential. Such a uid corresponds to a good approximation
to a noble gas in the liquid state, for example, liquid argon. In a computer
experiment, the uid is imagined to consist of a cell with a known number of
particles N and volume V. The value of N is usually chosen to be between 100
and 1000, its exact magnitude depending on the speed and memory capabilities
of the computer. The real liquid is imagined to be made up of many such cells,
all being identical (see g. 2.9). Surface eects in the experiment are minimized
by assuming that, if a particle leaves the cell on one side, it re-enters from an
image cell on the opposite side. In this way, surface eects are minimized and
calculations based on a relatively small number of particles are capable of
estimating accurately the properties of a macroscopic system containing the
order of 1023 molecules.
The two simulation techniques commonly used are the Monte Carlo method
[20, 21] and the method of molecular dynamics [22, 23]. In Monte Carlo experiments, an initial conguration for the N particles is chosen and the corresponding
potential energy Ur1 ; r2 ; . . . ; rN is calculated. This conguration, chosen by the
programmer, is usually something simple, for instance, a face-centered cubic
arrangement of the particles. Then, the position of one particle is changed at
random, generating a new conguration. The potential energy U is calculated
and compared with that of the previous conguration. If it is smaller, the new
conguration is accepted as a contribution to the estimation of the congurational partition function for the ensemble, Z. However, if U is greater than that
for the previous conguration, a choice is made on the basis of the increment in
the potential energy, U. The fraction expbU is calculated and compared
with a random number r in the interval 0 to 1 generated by the computer. If the
fraction is greater than r, the new conguration is accepted and added to the chain
of congurations describing the system. If the fraction is less than the random
number r, the new conguration is rejected and the previous conguration is
added again into the chain of congurations describing the system. This process
is repeated many times, thereby generating a chain of congurations. The overall
properties of the system then converge to those of a canonical ensemble for which

Fig. 2.9 Schematic diagram


illustrating the periodic boundary
conditions used in computer
simulations. The lines represent
cell boundaries. The positions of
the particles in each cell, assumed
to be ve in this example, are
identical so that surrounding cells
may be considered images of a
central one. Each particle is given
a dierent symbol to clarify the
imaging eects.

THE STRUCTURE OF LIQUIDS

75

V, N, and T are held constant. In this way, the congurational integral Z is


calculated. This immediately allows one to calculate the partition function Q
for the ensemble (equation (2.2.31)) and thus the thermodynamic functions for
the system. In addition, the pair correlation function for the uid is obtained in
this calculation.
The acceptance or rejection of congurations with high potential energy is a
special feature of modern Monte Carlo techniques [20, 21]. In the case of hardsphere systems, this choice is particularly simple because U is equal to zero when
spheres do not overlap, and innity when they do. Details about application of
this technique to more complex systems such as molecular uids involve some
variations which are described in the original literature.
In a molecular dynamics calculation, both the position and velocity of the
particles in the cell are specied. The movement of the particles is governed by
Newtons laws of motion, and the initial velocities are chosen from a Maxwell
distribution. This computer experiment is particularly easy for non-interacting
hard spheres because the molecules move in straight lines and undergo elastic
collisions. The velocity after the collision is found through the laws of conservation of momentum and energy. Since the total energy of the system is constant, it
corresponds to a microcanonical ensemble with constant U, V, and N. The temperature is found from the time average of the molecular kinetic energy. Since
velocity is included in the description of the system both equilibrium and transport properties can be obtained from this type of computer calculation. When
these calculations are performed for systems with continuous functions for the
potential energy U, nite dierence techniques are used. This type of calculation is
more complex and takes more computer time. In the end one obtains the same
information as in the Monte Carlo experiment, namely, the pair correlation function and the thermodynamic properties of the uid. The additional information
from molecular dynamics allows one to calculate velocity correlation functions,
and ow properties such as viscosity and diusion coecients.
The results of computer experiments are often used to test approximate
theories of liquids such as those based on the OZ equation discussed above.
For this reason they are an important part of understanding the structure of
liquids and how structure aects liquid properties.

2.8 Estimation of Thermodynamic Properties from the


Pair Correlation Function
In section 2.2 it was shown that the thermodynamic properties of a system may be
estimated from its partition function, Q. In a liquid, estimation of Q requires
knowledge of the congurational partition function, Z. In the following section
the relationship between Z and the pair correlation function gr is examined. In
principle, gr may be determined from experiment. Therefore, it is important to
understand the connection between gr and the thermodynamic properties of the
system.
The starting point in the derivation is the partition function Q (equation
(2.2.31)), which is written in terms of logarithms:

76

LIQUIDS, SOLUTIONS, AND INTERFACES

ln Q N ln qint ln Z  ln N!  3N ln l

2:8:1

Now the internal energy U can be found by taking the derivative with respect to b,








@ ln Q
@ ln qint
@ ln Z
@ ln l
U
N

3N
2:8:2
@b V;N
@b V;N
@b V;N
@b
V;N
On the basis of the denition of l (equation (2.2.22)) and qint , this may be
rewritten as


3NkB T
@ ln Z
Neint 
2:8:3
U
2
@b V;N
where the rst term on the right-hand side gives the average kinetic energy of the
system, the second, the contribution from the internal energy of the molecules,
and the last, the average potential energy of the system due to intermolecular
interactions. Dierentiating equation (2.2.32) with respect to b, the following
expression is obtained for the average potential energy:

@ ln Z 1

. . . U expbUdr1 dr2 . . . drN


hUi 
2:8:4
@b
Z
The multiple integral in this equation expresses the fact that the averaging process
is carried out by multiplying the potential energy of each conguration U by its
probability given by the factor expbU=Z. In order to proceed further, the
important assumption is made that U is made up of the sum of potentials between
pairs of molecules:
X
NN  1
ur12
U
urij
2:8:5
2
1 i j N
where ur12 is the pair potential energy. After substitution of equation (2.8.5) into
equation (2.8.4), one obtains

NN  1
hUi
. . . ur12 expbUdr1 dr2 . . . drN
2Z

2:8:6
NN  1

ur12 . . . expbU dr3 . . . drN dr1 dr2


2Z
Comparing the inner integral with the denition of the pair distribution function
given by equations (2.4.4) and (2.4.7), one may now write

1
hUi
ur12 f 2 r1 r2 dr1 dr2
2
2:8:7

N2

ur12 gr12 dr1 dr2


2V 2
Integrating over the coordinates of particle 1, the following result is obtained for
the average potential energy:
N2
hUi
2V

urgr4pr2 dr
0

2:8:8

THE STRUCTURE OF LIQUIDS

77

The integral in this equation gives the total intermolecular potential energy
between a central molecule and other molecules in the uid located between r
and r dr. Thus, evaluation of hUi involves adding up contributions for all values
of r and multiplying by the factor N=2, since any one of the N molecules can be
considered as central. The factor of two arises so that each pair interaction is not
counted twice. The nal expression for the internal energy is
3NkB T
N2
Neint
U
2
2V

urgr4pr2 dr

2:8:9

It should be remembered that the approximation involved in equation (2.8.5)


may not always be valid. When three-body interactions are important they must
be included in the estimation of U. Under most circumstances higher-order interactions account for approximately 5% of the potential energy so that equation
(2.8.5) represents a reasonable approximation.
The next quantity calculated from the radial distribution function is the
pressure. On the basis of equations (2.2.6) and (2.2.31), one may write


1 @ ln Z
2:8:10
P
b @V T;N
where it is assumed that the partition function due to internal degrees of freedom
is independent of volume. Derivation of the relationship between the volume
derivative of ln Z and the radial distribution function gr is presented elsewhere
[G3, G4] and is not reproduced here. The result expressed as the equation of state
is
PV
N
1
NkB T
6VkB T

gr

dur
4pr3 dr
dr

2:8:11

Estimation of the pressure requires that the derivative of the pairwise interaction
energy with respect to distance be known. This is certainly not a problem for
simple systems. Equation (2.8.11) was also derived on the basis of the assumption
that the potential energy U can be written as a sum of two-body interactions. To
this extent the result is approximate.
In order to complete the thermodynamic description, the Helmholtz energy A
is now calculated. On the basis of equation (1.3.15), one may write

so that

A U
S
T T

2:8:12

 
 
A
dU
1
Ud
d

 dS
T
T
T

2:8:13

dU
P dV
dS 
T
T

2:8:14

Since

78

LIQUIDS, SOLUTIONS, AND INTERFACES

it follows that


@A=T
U
@1=T V

2:8:15

Thus, integration of equation (2.8.9) with respect to 1=T yields the Helmholtz
energy A. This in turn requires that the radial distribution function gr be known
as a function of temperature. Since gr is generally not available as a function of
temperature, equation (2.8.15) is not a convenient route to obtain A. On the basis
of equation (1.3.19), one obtains the relationship
 
@A
P
2:8:16
@V T
Thus, another route to estimating A is by integration of the pressure equation
(equation (2.8.11)) with respect to volume. This calculation requires that the
dependence of gr on volume or density be known. Since this is usually not
known, this method of estimating A is also not convenient in most cases.
Another method used to estimate the Helmholtz energy in a uid with intermolecular forces is to introduce a coupling parameter, x. This quantity, which
varies between 0 and 1, measures the extent to which a central reference molecule
is coupled to all other molecules in the system. Thus, when x 0, one imagines
that the reference molecule experiences no intermolecular interactions, whereas all
other molecules interact with each other in the normal fashion. In the case of van
der Waals interactions, this is equivalent to setting the central molecules dipole
moment equal to zero at all moments of time. As the parameter x increases from 0
the dipolar characteristics of the central molecule are gradually turned on until
when x 1, the system returns to its normal state. In order to evaluate the eects
of this imaginary process, one needs to evaluate the pair correlation function for
dierent values of x. This quantity is designated gr; x where gr; 1 is equal to
gr. Of course, the value of the pair correlation function during this imaginary
process cannot be determined experimentally, but it can be estimated using
various theoretical models, for instance, the MSA model discussed earlier.
When the number of molecules is very large, the chemical potential m can be
calculated from the increase in Helmholtz energy obtained by adding molecules,
one by one, to the system. Thus,
 
@A
AN; V; T  AN  1; V; T
2:8:17
m
@N V;T
From equations (2.2.13) and (2.2.31), one may write
AN; V; T NkB T ln qint  kB T ln ZN kB T ln N! 3NkB T ln 

2:8:18

where ZN is the conguration integral for the system with N molecules. It follows
that


ZN
m kB T ln qint  kB T ln
2:8:19
kB T ln N 3kB T ln l
ZN1
On the basis of the denition of the conguration integral (equation (2.2.32)) it
can be shown that

THE STRUCTURE OF LIQUIDS



1
ZN
@ ln ZN
dx
ln
ln V
ZN1
@x

79

2:8:20

Now making use of the relationship between the average potential energy hUi and
the pair correlation function (equation 2.8.8), one obtains


1 1
ZN
N
ln
urgr; x4pr2 drdx
ln V 
ZN1
VkB T

2:8:21

0 0

The resulting expression for the chemical potential is


!

1 1
Nl3
N
urgr; x4pr2 drdx
m kB T ln

Vqint
VkB T

2:8:22

0 0

If one has a model for gr; x) one may estimate the chemical potential m, and
hence, all of the other thermodynamic functions.
The above analysis demonstrates the importance of the pair correlation function in estimation of the thermodynamic properties of simple liquids. In the
following section, the properties of the simplest uid, namely, one based on
non-interacting hard spheres, are developed on the basis of the relationships
presented in this section.

2.9 The Properties of a Hard-Sphere Fluid


It is useful to examine the properties of a uid made up of non-interacting hard
spheres. Such a system may be regarded as an important reference liquid, albeit
ctitious, with respect to which the properties of real systems can be compared. Its
properties are most easily obtained on the basis of the PercusYevick (PY)
approximation. Since the spheres do not interact, the interaction energy ur is
zero outside any sphere:
ur 0;

r>s

2:9:1

Since the spheres are hard, that is, they do not penetrate one another,
ur 1;

r<s

2:9:2

It is apparent that the interaction energy is discontinuous at the boundary of a


sphere. From the discussion in section 2.6, discontinuities are also possessed by
the pair correlation function gr and the direct correlation function cr at the
boundary of a sphere. In order to remove problems associated with these discontinuities, one introduces a new function, yr dened as follows:
yr gr expbur

2:9:3

Outside of a sphere where ur is zero, one nds that


yr gr;

rs

2:9:4

80

LIQUIDS, SOLUTIONS, AND INTERFACES

Referring to the PY approximation (equation (2.6.5)), inside a sphere where gr is


zero,
yr cr;

r s

2:9:5

Although cr and gr are discontinuous at r s; yr is continuous.


The rst step in obtaining the properties of the hard-sphere system is to calculate its equation of state on the basis of equation (2.8.11). From equations (2.9.1)
and (2.9.2), the derivative dur=dr is zero for all values of r except r s where it
is a negative-going delta function. This follows from the fact that ur drops from
1 to 0 at the boundary of a hard sphere. It can be shown that the integral in the
equation of state (equation (2.8.11)) simplies to the value of the integral at r s
multiplied by kB T so that one obtains
PV
2pNs3
1
gs 1 4zys
NkB T
3V

2:9:6

where the packing fraction z is introduced to simplify the result (see equation
(2.6.13)). On the basis of equations (2.9.4) and (2.9.5), one may write
gs ys cs

2:9:7

where s and s indicate that the function is evaluated at the positive and
negative side of the discontinuity at s, respectively. Thus, gs may be calculated
on the basis of equations (2.6.10)(2.6.12), giving the result that
gs

1 z=2
1  z2

2:9:8

Substituting equation (2.9.8) into equation (2.9.6) one obtains the following equation of state:
PV
1 2z 3z2

NkB T
1  z3

2:9:9

In the limit of very low densities, the parameter z goes to zero and the ratio
PV=NkB T approaches one. This is the expected ideal gas limit. At higher densities, the ratio PV=NkB T is greater than unity and goes to innity when z 1.
In fact, for a real system, the value
p of 3z is limited by the density of hard spheres in
a close-packed
system,
which
is
2=s . The corresponding value of the parameter
p
z is 2p=6, or 0.74, and that of PV=NkB T, 61.
The equation of state may also be calculated from an equation relating the
compressibility of the system to the pair correlation function gr. The result is
PV
1 z z2

NkB T
1  z3

2:9:10

For low densities, this equation gives the same value of PV=NkB T as that
estimated from the pressure equation (equation (2.9.9)). However, at high densities, the estimate from the compressibility equation is much higher (see g. 2.10).
The disagreement between the equations of state obtained by the two dierent
methods clearly is a result of the approximation made in deriving the PY
equation.

THE STRUCTURE OF LIQUIDS

81

Values of PV=NkB T have been calculated for the hard-sphere system by


computer simulation. At high densities, the results obtained in this way fall
between those estimated by the pressure and compressibility equations. This led
Carnahan and Starling [24] to propose an equation of state obtained by combining one-third of the result from the pressure equation (equation (2.9.9)) together
with two-thirds of the compressibility result (equation (2.9.10)). The result is
PV
1 z z2  z3

NkB T
1  z3

2:9:11

The CarnahanStarling equation of state agrees well with the result of computer
simulations over the range shown in g. 2.10 and is used in all further calculations
presented here.
EXAMPLE

Estimate the value of PV=NkB T for a hard-sphere uid using the Carnahan
and Starling equation of state assuming a concentration of 10 M and a hardsphere diameter of 300 pm.
The concentration 10 M corresponds to
10  6:023  1023
6:023  1027 molec m3
103

2:9:12

The packing fraction z is equal to


z

3:1416  6:023  1027  3  1010 3


8:514  102
6

2:9:13

Thus,
PV
1 8:514102 8:514102 2 8:514 102 3

1:427
NkB T
1  8:514102 3

2:9:14

At this concentration the hard-sphere uid has properties which are signicantly dierent from those of an ideal uid (PV=NkB T 1).

Fig. 2.10 Plot of PV=NkB T


for a hard sphere uid
against the ratio of its
density N=V to the
p closepacked density 2=s3 .
The data designated () were
obtained using the pressure
equation (2.9.9), those
designated (^) using the
compressibility equation
(2.9.10), and the smooth
curve, using the Carnahan
Starling equation (2.9.11).

82

LIQUIDS, SOLUTIONS, AND INTERFACES

The Helmholtz energy of the system is now calculated using equations (2.8.16)
and (2.9.11).
Accordingly,

A
P
1 z z2 z3
dV
2:9:15

dV 
NkB T
NkB T
V1  z3
Recalling that
z

pNs3
6V

2:9:16

it follows that
dV 

pNs3
dz
6z2

2:9:17

so that the integral in equation (2.9.15) can be written in terms of z. The result is

A
1 z z2  z3

dz
2:9:18
NkB T
z1  z3
This integral can be broken up into four integrals, all of which can be found in
standard tables. The integration is carried out from a nite but very low density
where the parameter z is z0 , and the properties of the system are those of an ideal
gas, to any higher value of z. The result is
 
A
A0
z
3 2z  3z2 3
2:9:19

ln


NkB T NkB T
z0
2
21  z2
where A0 is the Helmholtz energy of an ideal gas. On the basis of equations
(2.2.13) and (2.2.23) this contribution is
A0
 ln V0 ln N  1 3 ln l
NkB T

2:9:20

where V0 is the volume of the ideal gas. Noting that


z
V
0
V
z0
the expression for the Helmholtz energy becomes
 
A
N
3 2z  3z2 3

3 ln l ln

NkB T
V
2
21  z2

2:9:21

2:9:22

One may now derive the remaining thermodynamic functions. First of all, the
internal energy is obtained by dierentiation of A=T with respect to the reciprocal
temperature:


@A=T
@ ln l
3NkB T
U

2:9:23
3NkB
@1=T V
@1=T
2

THE STRUCTURE OF LIQUIDS

83

The internal energy is simply the kinetic energy of the system and therefore does
not dier from the result for an ideal gas containing the same number of molecules. One may now write an expression for the entropy of the system:
 
S
UA
N
3 2z  3z2
3 ln l  ln

3
2:9:24

NkB NkB T
V
21  z2
Finally, the Gibbs energy is obtained by adding PV to the Helmholtz energy:
 
G
A PV
N
3 2z  3z2 1 z z2  z3 3

3 ln l ln



NkB T
NkB T
V
2
21  z2
1  z3
2:9:25
For an ideal monoatomic gas, the Gibbs energy at constant temperature and
pressure varies with the logarithm of the molecular density. The additional
terms in z in equation (2.9.25) give the contribution to G due to the non-ideality
of the hard-sphere system with respect to an ideal gas.
EXAMPLE

Estimate the internal energy, Helmholtz energy, and entropy of a hard-sphere


uid in units of NkB T assuming a concentration of 10 M, a diameter of 300 pm,
a molecular mass of 30 g, and a temperature of 258C.
The concentration of hard spheres is 6:023  1027 m3:
The mass of each sphere is
30  103
4:98  1026 kg
6:022  1023
The parameter l (equation (2.2.22)) is
l

6:626  1034
2  3:1416  4:98  1026  1:38  1023  298:21=2

1:847  1011 m

2:9:26

3 ln l 74:14
 
N
ln
63:97
V

2:9:27
2:9:28

From the previous example, z is equal to 8:514  102 :


Thus,
3 2z  3z2
7:52
21  z2

2:9:29

A
74:14 63:97 7:52  1:5 4:15
NkB T

2:9:30

and

The internal energy in units of NkB T is 1.5.


The entropy is given by

84

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 2.11 Plots of the Helmholtz energy for a hard-sphere uid (s 0:37 nm) against the
logarithm of the pressure at constant temperature as indicated.

S
UA
1:5  4:15 2:65

NkB NkB T

2:9:31

Values of the Helmholtz energy estimated as a function of pressure at constant


temperature on the basis of equation (2.9.22) are shown in g. 2.11. These plots
are reasonably linear in the logarithm of the pressure at low pressures. This is to
be expected, since the density is proportional to the pressure under these conditions, and the eects of non-ideality are relatively unimportant. However, at
higher pressures the value of A, starts to rise sharply due to non-ideality.
Eventually, one reaches positive values of A, indicating that the uid is not stable.
It has been shown that the hard-sphere system undergoes a phase transition from
uid to solid when Ns3 =V 0:943. For the system considered in g. 2.11, this
corresponds to a pressure of 760 bars at 300 K. Many interesting calculations
relating to phase transitions and critical phenomena in hard-sphere and
LennardJones uids have been carried out.
Just as the ideal gas forms a convenient point of reference in discussing the
properties of real gases, so does the hard-sphere uid in discussing the properties
of liquids. This is especially true at low densities, where the role of intermolecular
forces in real systems is not so important. In this limit, the hard-sphere model is
useful in developing the theory of solutions, as will be seen in chapter 3.

2.10 The Structure of Water


The discussion in this chapter has largely concerned very simple liquids such as a
hypothetical uid composed of non-interacting hard spheres, or spheres interacting via the LennardJones potential function. The most common liquid, namely,
water, is much more complex. First, it is a molecule with three atoms, and has a

THE STRUCTURE OF LIQUIDS

85

large permanent dipole moment. Second, it does not possess a center of symmetry,
unlike methane, or carbon tetrachloride. Finally, it is more complex than other
polar solvents because of the strong hydrogen bonding.
In spite of its complexity, the structure of liquid water has been determined
with precision using neutron diraction techniques [8]. The structure factor may
be analyzed to obtain correlation functions for each type of atomatom interaction in the system. For water, the three atomatom distribution functions are
gOO r; measuring the distribution of oxygenoxygen separations, gOH r; measuring the oxygenhydrogen distribution, and gHH r, measuring the hydrogen
hydrogen distribution.
Since the scattering amplitude for oxygen is much smaller than that for hydrogen, the gOO r distribution is the most dicult to determine. The experimental
results are illustrated in g. 2.12. This function rises from a value of zero at
200 pm to a sharp maximum of 3.09 at a distance of 288 pm. This means that
the local density of oxygen atoms is 3.09 times greater than the average value.
However, in order to estimate of the oxygenoxygen coordination number one
must consider the distribution density over the whole region of the maximum in
gOO r. One way of achieving this is to integrate the distribution function up to the
rst minimum, considering shells of volume 4pr2 dr. The coordination number is
then dened as
rmin

ro gOO r 4pr 2 dr

nc

2:10:1

where ro is the density of oxygen atoms in the liquid. When this integration is
carried out to a distance of 330 pm from the central oxygen atom, the result is that
nc 4:3. This suggests that the central water molecule is approximately in a
tetrahedral environment surrounded on the average by four nearest neighbors.

Fig. 2.12 Oxygenoxygen distribution function in liquid water determined at 258C by


neutron diraction [8].

86

LIQUIDS, SOLUTIONS, AND INTERFACES

Beyond the rst minimum, gOO r oscillates with a second maximum at 450 pm. In
order to understand these results in more detail, one needs to carry out a molecular dynamics calculation. However, it is clear that the behavior of water is
roughly similar to that of much more simple liquids if one considers the oxygen
atom alone.
A much dierent pattern is seen for the oxygenhydrogen distribution function
(g. 2.13). These results have been corrected for the intramolecular contribution
to gOH r, and show only the eects of the intermolecular correlation. A fairly
sharp maximum occurs at 185 pm, and a broader but higher one at 330 pm. The
rst maximum is clearly associated with the hydrogen atoms in surrounding
molecules which are hydrogen bonded to the oxygen atom in a central molecule.
Integration out to the rst minimum gives a coordination number of 1.7. The
second maximum occurs at the rst minimum on the gOO r distribution curve. At
this point, the total number of hydrogen atoms around the central oxygen is close
to eight, that is, two times the number of oxygen atoms in the same volume of
solution. These observations all follow what is expected on the basis of the molecular composition of water.
The distribution function for hydrogen atoms with respect to a central hydrogen is shown in g. 2.14. The function gHH is the easiest to determine experimentally because of the large scattering amplitude for hydrogen with respect to that
for oxygen. These results have also been corrected for the intramolecular contribution to gHH r. The rst maximum at 240 pm is followed by one which is less
high at 390 pm. The coordination number estimated by integrating out to the rst
minimum at 310 pm is 5.8. These hydrogen atoms are associated with a central
molecule via hydrogen bonding. Comparing gOH r and gHH r, one sees that the
maxima on the HH distribution function are located further from the central
atom by 60 pm with respect to those on the OH distribution. This is perfectly
reasonable because of the OH bond length in water.
Another method of studying water structure is Raman spectroscopy [25]. Using
this technique, one is able to distinguish spectral features which arise from intra-

Fig. 2.13 Oxygenhydrogen distribution function in liquid water determined at 258C by


neutron diraction [8].

THE STRUCTURE OF LIQUIDS

87

Fig. 2.14 Hydrogenhydrogen distribution function in liquid water determined at 258C by


neutron diraction [8].

molecular and intermolecular vibrational modes of the water molecules.


Interpretation of the data is assisted by comparing spectra obtained in H2O
and D2O, and by changing the temperature. A picture which is consistent with
both the Raman spectra and the neutron diraction data shows considerable
order around a given water molecule. Because of hydrogen bonding, one molecule
is surrounded on the average by four hydrogen-bonded nearest neighbors (see g.
2.15). The orientation of these neighbors can be such that the system has a high
degree of symmetry. However, keeping in mind the dynamic character of liquid
structure, rotation of the molecules hydrogen bonded to the central molecule can
reduce the symmetry. The dynamic character of the system also results in a very

Fig. 2.15 Diagram of a water molecule


surrounded by four nearest neighbors
whose orientation is determined by
hydrogen bonding. Hydrogen bonds are
denoted by broken lines and OH
bonds by solid lines. (Reproduced from
reference 25, with permission.)

88

LIQUIDS, SOLUTIONS, AND INTERFACES

weak correlation between the central molecule and those located further away
than the four nearest neighbors. The vibrational spectra of water are discussed in
more detail in section 5.7A.
It is clear that the physical properties of water are very much inuenced by the
important role played by hydrogen bonding in determining its structure. These
properties include the high dielectric permittivity, which cannot be explained on
the basis of dipoledipole interactions alone. It is also clear that electrolytes have
a very disruptive eect on water structure. Cations are solvated by the lone
electron pairs on the oxygen atom of the water molecule and thus cause considerable disruption in the local water structure. This leads to changes in the bulk
physical properties of water, such as its permittivity.
Many aspects of the structure and properties of aqueous solutions can be
understood in terms of the qualitative structural changes that occur because of
solutesolvent interactions. This subject is discussed in more detail in the following chapters.

2.11 Distribution Functions for Liquid Solutions


The techniques used to describe the properties of pure liquids can be extended in a
fairly straightforward fashion to liquid solutions [26, 27]. This treatment is normally restricted to liquids in which the molecules behave as non-interacting hard
spheres or as dipolar species interacting via a LennardJones potential. The discussion here is limited to two-component mixtures but it is easily extended to
more complex systems.
The energy equation for a liquid mixture or solution is
3NkB T
N2 X
2p
xx
U
2
V ij i j

uij rgij rr2 dr

2:11:1

where x1 is the mole fraction of component 1, x2 , that of component 2, and


N N1 N2 . The summation involves three terms and requires specication of
the interaction energies u11 ; u12 and u22 as well as the pair correlation functions
g11 ; g12 and g22 . In equation (2.11.1), the contribution to U from the internal
degrees of freedom of the two molecules in the solution has not been included.
Several approaches to estimation of the internal energy have been described.
These involve assuming specic relationships between the pair correlation functions gij and the form of the interaction energy uij . The simplest of these is based
on the van der Waals treatment of uids and its application of the law of corresponding states. Examination of typical radial distribution functions for mixtures
such as those shown in g. 2.16 reveals that the maximum in each distribution
function gr occurs close to the diameter s describing the distance of closest
approach for the two molecules involved. Thus, it is better to describe the radial
distribution function in terms of the reduced distance r=s instead of the distance r.
This conclusion leads to the assumption that

THE STRUCTURE OF LIQUIDS

89

Fig. 2.16 Typical radial distribution functions of a two-component mixture plotted against
the reduced distance for the 22 distribution. (From reference 26, with permission.)


g11


 
 
r
r
r
g22
g12
s11
s22
s12

2:11:2

When the interaction energy is given by the LennardJones potential, one may
write
uij r 4eij

h
s n
s m i
ij
ij

r
r

2:11:3

where n is a coecient describing repulsive interactions and m, one describing


attractive interactions. As discussed earlier, n is often assumed to be 12, and m is 6
for dipoledipole interactions (see equation (2.3.35)). This expression includes the
case of a hard-sphere uid when n 1 and the term in m is neglected. As far as
liquids are concerned the more important contribution comes from the repulsive
component which predominates for molecules in close contact. The Lennard
Jones function is conformal because it has the same form independent of the
molecule, that is, of the values of eij and sij .
Changing the variable in equation (2.11.1) from r to y r=sij and substituting
the expression for uij r one obtains
3NkB T
N2 X
8p
U
xxe s 3
2
V ij i j ij ij
If one denes


1
1
g yy2 dy

yn ym ij

2:11:4

90

LIQUIDS, SOLUTIONS, AND INTERFACES

s3mix

xi xj sij 3

2:11:5

ij

and
emix

xi xj eij sij 3 =

ij

xi xj sij 3

2:11:6

ij

the energy equation simplies to


3NkB T
N2
8p
e s3
U
2
V mix mix


1
1
gyy2 dy

yn y m

2:11:7

where gy is any one of the distribution functions dened in equation (2.11.2).


This equation shows that the composition dependence of the internal energy U is
specied only through the quantities emix and smix For this reason, the properties
of the system at a given composition are those of a hypothetical pure uid with
properties dened by emix and smix . Thus, the model is called a one-uid model.
In the case of mixtures of simple molecules, the Gibbs energy for a one-uid
system may be written as
G emix kB T=emix  3NkB T ln smix

2:11:8

where the function kB T=emix is found by curve-tting the experimentally


observed data for G for the pure liquids as a function of temperature. The
other thermodynamic functions are determined by dierentiation.
The van der Waals one-uid theory is quite successful in predicting the properties of mixtures of simple molecules. Unfortunately, the systems usually considered by chemists are considerably more complex, and often involve hydrogen
bonding and other chemical interactions. Nevertheless, the material presented
here outlines how one could proceed to develop models for more complex systems
on the basis of the integral equation approach.

2.12 Concluding Remarks


The fundamental quantity used to describe liquid structure is the pair correlation
function gr. It has been estimated both experimentally and on the basis of
computer calculations for a great variety of liquid systems. Simple monoatomic
liquids such as the inert gases were of great interest to physicists because they
allowed them to test theories based on fairly simple models. Intermolecular forces
can be described using the LennardJones potential and the thermodynamic
properties of these liquids can be estimated reasonably well. On the other hand,
chemists are interested in much more complex polyatomic systems. When the
constituent molecule is polar, description of the intermolecular forces must at
least include dipoledipole interactions and often higher-order multipole interactions. In the case of protic liquids such as water, hydrogen bonding is a very
important factor in determining its structure as a liquid. This was seen directly
in the case of water from the correlation functions derived from neutron dirac-

THE STRUCTURE OF LIQUIDS

91

tion data and from the structural information obtained from Raman spectroscopy.
In discussing the statistical thermodynamics of liquids, emphasis has been
placed on the OrnsteinZernike equation and the integral equation approach to
obtaining thermodynamic properties from molecular ones. This is by no means
the only approach, an alternative one being based on the perturbation theory of
liquids. Perturbation theory has been developed in some detail and is quite successful in describing the properties of simple liquids [28, 29]. In addition, in
discussing the integral equation approach, simple approximations such as the
mean spherical approximation (MSA) have been emphasized, since they often
give analytical expressions for the thermodynamic functions. A good example
of such an outcome is the PercusYevick results for a hard-sphere uid discussed
in section 2.9. The nature of the approximations used in these methods can be
understood in detail using cluster diagrams. More about this method of describing
the integrals which arise in a detailed description of intermolecular interactions
can be found in monographs dealing with liquid structure [G1, G2].
In conclusion, the material in this chapter is meant to give only an introduction
to the subject of liquid structure. Much of what has been presented has dealt with
systems which can be represented as point dipoles embedded in hard spheres. Very
few liquid systems of chemical interest can be described in such simple terms.
However, the simple models can often be modied to make them more realistic.
For example, the eects of chemical interactions can be introduced by assuming
that the hard sphere experiences sticky interactions in a given direction with
respect to the central dipole. Other methods are available for dealing with the
eects of non-sphericity. Thus, the simple models can often be made relevant to
chemical systems after suitable modication.
In the following chapters, some of the theories introduced here are used to
discuss other systems, including polar solvents and electrolyte solutions. The
statistical mechanical tools introduced here are important because they help
one to develop an understanding of the way that molecular properties of a
given system inuence its macroscopic properties.

General References
G1. Egelsta, P. A. An Introduction to the Liquid State, 2nd ed.; Oxford University Press:
New York, 1992.
G2. Watts, R. O. and McGee, I. J. Liquid State Chemical Physics; John Wiley: New York,
1976.
G3. Eyring, H.; Henderson, D.; Stover, B. J.; Eyring, E. M. Statistical Mechanics and
Dynamics, 2nd ed.; John Wiley: New York, 1982.
G4. McQuarrie, D. A. Statistical Mechanics; Harper and Row: New York, 1976.

References
1. Barker, J. A.; Henderson, D. Rev. Mod. Phys. 1976, 48, 587.
2. London, F. Trans. Faraday Soc. 1937, 33, 8.
3. Verlet, L. Phys. Rev. 1968, 165, 201.
4. Yarnell, J. L.; Katz, M. J.; Wenzel, R. G.; Koenig, S. H. Phys. Rev. 1973, A7, 2130.

92

LIQUIDS, SOLUTIONS, AND INTERFACES

5. Kalman, E.; Palinkas, G. In The Chemical Physics of Solvation, Part B, Spectroscopy


of Solvation; Dogonadze, R. R., Kalman, E., Kornyshev A. A., Ulstrup, J., eds.;
Elsevier: Amsterdam, 1986, Chapter10.
6. Narten, A. H.; Levy, H. A. J. Chem. Phys. 1971, 55, 2263.
7. Hajdu, F.; Lengyel, S.; Palinkas, G. J. Appl. Crystallogr. 1976, 9, 194 .
8. Soper, A. K.; Phillips, M. G. Chem. Phys. 1986, 107, 47; Soper, A. K. Chem. Phys.
2000, 258, 121.
9. Narten, A. H.; Habenschuss, A. J. Chem. Phys. 1984, 80, 3387.
10. Yamaguchi, T.; Hidaka, K.; Soper, A. K. Mol. Phys. 1999, 97, 603.
11. Bertagnolli, H.; Zeidler, M. D. Mol. Phys. 1978 35, 177.
12. Radnai, T.; Itoh, S.; Ohtaki, H. Bull. Chem. Soc. Jpn. 1988, 61, 3845.
13. Kalman, E.; Serke, I.; Palinkas, G.; Zeidler, M. D.; Weisman, F. J.; Bertagnolli, H.;
Chieux, P. Z. Naturforsch. 1983, 38a, 231.
14. Bellisent Funel, M.C.; Nasr, S.; Bosio, L. J. Chem. Phys. 1997, 106, 7913.
15. Luzar, A.; Soper, A. K.; Chandler, D. J. Chem. Phys. 1992, 96, 8460.
16. Ornstein, L. S.; Zernike, F. Proc. Acad. Sci. Amsterdam 1914, 17, 793.
17. Percus, J. K.; Yevick, G. J. Phys. Rev. 1958, 110, 1.
18. van Leeuwen, J. M. J.; de Boer, J. Physica (Utrecht) 1959, 25, 792; Green, M. S.
J. Chem. Phys. 1960, 33, 1403.
19. Wertheim, M. S. J. Math. Phys. 1964, 5, 643.
20. Metropolis, N.; Rosenbluth, A. W.; Rosenbluth, M. N.; Teller, E.; Teller, A. H.
J. Chem. Phys. 1953, 21, 1087.
21. McDonald, I. R.; Singer, K. Quart. Rev. 1970, 24, 238.
22. Rahman, A. Phys. Rev. 1964, 136, A405.
23. Alder, B. J.; Wainwright, T. E. J. Chem. Phys. 1957, 27, 1208; 1959, 31, 459; 1960, 33,
1439.
24. Carnahan, N. F.; Starling, K. E. J. Chem. Phys. 1970, 53, 600.
25. Walrafen, G. E. J. Chem. Phys. 1964, 40, 3249.
26. Henderson, D.; Leonard, P. J. In Physical Chemistry, an Advanced Treatise; Eyring,
H., Henderson, D., Jost, W., eds.; Academic Press: New York, 1971; Vol. VIII B,
Chapter 7.
27. McDonald, I. R. In Statistical Mechanics, Specialist Periodical Reports; Chemical
Society: London, 1973; Vol. 1, p 134.
28. Henderson, D.; Barker, J. A. In Physical Chemistry, an Advanced Treatise Eyring, H.,
Henderson, D., Jost, W., eds.; Academic Press: New York, 1971; Vol. VIII B.
29. Smith, W. R. In Statistical Mechanics, Specialist Periodical Reports; Chemical Society:
London, 1973; Vol. 1, p 71.

Problems
1. The following molecules form liquids at room temperature. Calculate the
energy involved between two similar molecules at contact (r s) due to
dipoledipole, induced dipoledipole and London dispersion forces. The
molecules are assumed to be spherical with a diameter s. Express the results
in units of kB T at 258C.
Molecule

Diameter
s=pm

Dipole Moment
p/debye

Polarizability
1030 a=m3

Ionization Potential
I=MJ mol1

CCl4
CH2Cl2
CH3OH

538
450
371

0
1.60
2.87

10.49
6.48
3.26

1.107
1.090
1.047

THE STRUCTURE OF LIQUIDS

93

2. Calculate the LennardJones interaction potential for the following molecules and plot them on the same graph. The calculations should be carried
out for increments of r by 0.02s in the range 0.91.2s, and by 0.1s in the
range 1.22.4s.
Molecule

LJ k1
B =K

s=pm

Tb =K

423
333
298

592
491
431

342
462
374

Hexane
Dimethylsulfoxide
Nitromethane

Does the interaction potential give a good measure of cohesive forces in the
corresponding liquids? Discuss in terms of the boiling point.
3. The following table gives the distribution function gr for liquid argon at
85 K. The LennardJones parameters for argon are s 350 pm and
LJ k1
B 118 K. Estimate the LennardJones potential at each value of r,
and then use the PercusYevick equation to calculate the direct correlation
function cr (equation (2.6.5)). Plot gr and cr against r.
r=pm

gr

r=pm

gr

r=pm

gr

r=pm

gr

0
100
200
300
320
327
334
341
347
354
361
368
375
381
388
395
402
409
415
422
429
436
443
449
456

0
0
0
0
0.072
0.321
0.736
1.283
1.886
2.441
2.851
3.054
3.040
2.850
2.555
2.234
1.947
1.722
1.555
1.424
1.306
1.186
1.062
0.946
0.847

463
477
504
518
552
579
592
613
627
647
667
688
715
729
756
769
797
804
810
817
824
831
844
872
878

0.773
0.686
0.580
0.560
0.609
0.729
0.804
0.914
1.004
1.140
1.229
1.269
1.254
1.230
1.125
1.056
0.947
0.921
0.894
0.870
0.850
0.836
0.825
0.836
0.845

855
892
899
906
913
919
926
933
940
947
953
960
967
981
994
1008
1022
1042
1062
1075
1090
1103
1124
1144
1165

0.859
0.876
0.894
0.911
0.928
0.943
0.959
0.976
0.994
1.014
1.033
1.049
1.063
1.083
1.099
1.108
1.104
1.084
1.065
1.045
1.020
0.999
0.973
0.944
0.934

1219
1253
1273
1293
1345
1376
1410
1444
1485
1566
1655
1805
1900
1975
2057
2118
2227
2295
2377
2479
2547
2620
2683
1

0.954
0.984
1.014
1.034
1.046
1.026
1.007
0.989
0.971
0.993
1.020
0.988
1.000
1.009
1.000
0.994
1.000
1.004
1.000
0.998
1.000
1.002
1.000
1.000

94

LIQUIDS, SOLUTIONS, AND INTERFACES

4. Use the above data to calculate the internal energy per mole of argon at 85 K
given that its density is 21.25 atoms nm3 . The contribution to the internal
energy from internal degrees of freedom (equation (2.8.9)) should be
neglected. Develop a condition in your computer program so that numerical
integration is terminated when the integral becomes constant.
5. Estimate the direct correlation function for liquid argon at 85 K using the
hypernetted chain approximation with the data given in problem 3. Compare
the result with that found using the PercusYevick approximation.
6. Estimate the packing fraction for a hard-sphere liquid with a density of 21.25
atoms nm3 and a hard-sphere diameter of 350 pm. Use this result to calculate the PercusYevick product for the system at 85 K using the Carnahan
Starling equation of state (equation (2.9.11)).
7. Calculate the internal energy and entropy of the hard-sphere system
described in problem 6. Assume that the atomic weight of the hard sphere
is 39.95 g mol1 .
8. The following table gives the distribution function gOO r in liquid water at
258C. Use these data together with the density of water (0.997 g cm3 ) to
calculate the coordination number for a central oxygen atom assuming that
the pair correlation function should be integrated up to the rst minimum.
r=pm

gOO r

r=pm

gOO r

r=pm

gOO r

200
213
223
233
243
248
253
258
263
268
273

0
0.008
0.040
0.116
0.233
0.306
0.399
0.541
0.782
1.179
1.746

278
283
288
293
298
303
308
313
318
323
333

2.388
2.907
3.092
2.869
2.351
1.758
1.273
0.966
0.813
0.752
0.734

343
353
363
373
383
393
403
413
423
433
443

0.749
0.773
0.807
0.850
0.898
0.950
1.003
1.050
1.089
1.116
1.333

Electrolyte Solutions

Wilhelm Ostwald was born to a German family


in 1853 in Riga, Latvia, where he grew up and
attended school. In 1872 he entered Dorpat
University (now Tartu University in Estonia)
where he studied chemistry, obtaining the
diploma in 1875. At that time the Baltic States
were part of the Russian Empire with some
institutions of higher learning operating in
German for the German minority who lived in
that region of Europe. Ostwald stayed at
Friedrich Wilhelm Ostwald
Dorpat to study physics under Arthur von
Oettingen and chemistry under Carl Schmidt.
In 1877 he was appointed lecturer at Dorpat, and he obtained his doctoral
degree in 1878. He moved back to Riga in 1881 as professor of chemistry at
the Polytechnic Institute. In 1887 he accepted the Chair of Physical Chemistry
at Leipzig University and remained there until 1906. Ostwald is generally
considered to be the founder of modern physical chemistry. He began the rst
journal dealing with this subject, namely, Zeitschrift fur physikalische Chemie in
1887, and edited it until 1922. The main area of research interest for Ostwald
was electrolyte solutions, but he also contributed to other areas of physical
chemistry, especially reaction kinetics and catalysis. He had several famous
associates including S. A. Arrhenius, J. H. vant Ho, and W. Nernst, all of
whom won the Nobel Prize in Chemistry. Many young North American
chemists studied in his laboratory, and then went on to develop the new area
of physical chemistry at home. These included G. N. Lewis, A. A. Noyes, and
W. Lash Miller. Ostwald spent much of his time during his long retirement
studying the scientic basis for color. He won the Nobel Prize in Chemistry in
1909 for his work on catalysis, chemical equilibria, and reaction kinetics. He
died in 1932.

3.1 Electrolyte Solutions Are Always Non-Ideal


Electrolyte solutions are important in all branches of chemistry, but especially in
analytical chemistry, and biochemistry. These systems by their nature are always
non-ideal, and represented an early challenge to theoreticians interested in
describing their thermodynamic properties. The solute components are ions,
cations, and anions, which carry opposite charges and thus interact very dier95

96

LIQUIDS, SOLUTIONS, AND INTERFACES

ently with one another. The existence of electrolyte solutions depends on the polar
properties of the solvent through which the individual ions are stabilized. When
one recognizes the molecular nature of the solvent, one must also consider the
interactions between solvent dipoles and the ion. This results in changes in solvent
structure in the immediate vicinity of the ions. It follows that a complete description of an electrolyte solution at the molecular level requires the consideration of
iondipole, ionion, and dipoledipole interactions. In addition to these simple
electrostatic interactions, one must also consider the role of hydrogen bonding in
protic solvents like water.
In very dilute electrolyte solutions, the most important consideration is ion
dipole interactions. One expects these interactions to be dierent for cations and
anions. This follows from the fact that the solvent molecule is not a simple dipole
in the electrostatic sense but instead it has a chemical structure which is dierent
at each end of the molecular dipole. Each ion interacts locally with four to six
solvent molecules in its immediate surroundings. In the case of water, the concentration of water molecules in the pure liquid is 55.5 M; it follows that the
number of water molecules experiencing direct interaction with ions in dilute
solutions represents a small fraction of the total number.
As the electrolyte concentration increases, ionion interactions become more
important in determining the thermodynamic properties of the solution. The
electrostatic eld of an ion is long ranged, decreasing with the reciprocal of the
distance from the charge center of the ion. As a result a given ion has an ionic
atmosphere in which the concentration of oppositely charged ions in its vicinity is
slightly greater on the average than that of ions of the same charge. The properties
of the ionic atmosphere depend on temperature, that is, on the randomizing
eects of thermal motion. Thus, the composition of the ionic atmosphere uctuates with time, and the relative dierence between the local concentration of
cations and anions in the vicinity of a given ion varies with both temperature and
distance. As the electrolyte concentration increases, the average distance between
ions and the thickness of the ionic atmosphere both decrease.
Under some circumstances ionion interactions can be more important than
iondipole interactions. This is especially true when the valence of the ion is
greater than one, and the electrolyte concentration is high. Then, the formation
of ion pairs and higher aggregates is possible. Two types of ion pairs have been
recognized, namely, contact ion pairs in which the cation and anion are in physical contact, and solvent-separated ion pairs in which one or two solvent molecules are situated between the cation and anion. Ion pairing must be considered in
developing a complete picture of an electrolyte solution.
As was seen in chapter 2, both dipoledipole interactions and hydrogen bonding are important in determining the structure and thermodynamic properties of
pure water. In the immediate vicinity of an ion, the solvent structure is disrupted
so that local dipoledipole interactions and hydrogen bonding are dierent than
they are in pure water. These changes are also important because they aect the
local permittivity and the strength of ionion interactions.
In the present chapter, the properties of electrolyte solutions in water are
discussed in detail. Initially the solvation of ions in innitely dilute solutions is
considered on the basis of the Born theory. Then, the DebyeHuckel model for

ELECTROLYTE SOLUTIONS

97

ionion interactions in dilute solutions is described. Finally, the role of ion pairing
is outlined. Methods of improving the description of electrolyte solutions on the
basis of the MSA are also presented.

3.2 Ionic Size in Solutions


In order to apply the models which are introduced in this chapter, one needs an
estimate of the size of the ions which make up the electrolyte. This is most easily
done for monoatomic ions, since they are spherical, so that ionic size is known by
determining the ionic radius. Furthermore, accurate interparticle distances are
available from X-ray diraction studies of ionic crystals, and more importantly,
from X-ray and neutron diraction studies of aqueous electrolyte solutions [1].
One of the most widely known and used set of ionic radii are those estimated
by Pauling [2] on the basis of interionic distances in ionic crystals. He noted that
repulsive eects between ions of the same charge depend on the relative size of the
cation and anion in the crystal, and also took into consideration the coordination
number of the ion with oppositely charged neighbors in the crystal lattice. The
results obtained for the alkali metal and halide ions for the case that the coordination number is six (rock salt structure) are summarized in table 3.1.
As the collection of X-ray diraction data became more extensive, it was
possible to describe the electron density distribution in ionic crystals in more
detail. Using these data one can divide up the internuclear distance in the crystal
on the basis of the minimum in the electron density between the two oppositely
charged ions [3, 4]. For example, in the case of NaCl for which the internuclear
distance is 281 pm, the minimum in the electron density leads to radii of 117 pm
for Na and 164 pm for Cl. Radii derived on this basis are larger for cations and
smaller for anions than those of Pauling.

Table 3.1 Radii for the Alkali Metal and Halide Ions for a
Coordination Number of Six Estimated from Crystallographic
Data Together with IonOxygen Atom Distances from
Diffraction Studies of Aqueous Solutions
Ionic Radius / pm
Ion

Ion-Oxygen Distance in
Pauling [2] Shannon and Prewitt [5] Aqueous Solution [1] / pm

Li
Na
K
Rb
Cs

61
96
133
148
166

88
116
152
163
184

210
242
280

315

F
Cl
Br
I

134
181
195
217

119
167
182
206

262
310
334
363

98

LIQUIDS, SOLUTIONS, AND INTERFACES

Shannon and Prewitt [5] considered a very large collection of crystallographic


data for metal oxides and metal uorides. Included in these data were transition
metal compounds in which the bonding between cation and anion is both electrostatic and covalent in character. They noted that the eective radius for a given
ion depends on its coordination number in the crystal. In addition, for transition
metal ions the radius depends on whether the d electrons in the ion are in a high or
low spin state. By assigning a radius of 126 pm to the O2 ion and 119 pm to the
F ion when they are surrounded by six counter ions, they found that the eective
radii of the alkali metal ions and halide ions are very close to those obtained from
electron density maps for the corresponding crystals. Their results for these ions
are also summarized in table 3.1.
Another source of information directly relevant to ionic size in solution is
X-ray and neutron diraction studies of interatomic distances in aqueous electrolyte solutions [1]. Values of the ionoxygen distance found in these experiments
are given in table 3.1. In the case of the alkali metal ions, the dierence between
the ionoxygen distance and the ShannonPrewitt radius increases from 122 pm
in the case of Li to 131 pm in the case of Cs, the average dierence being
127 pm. The average value is very close to the eective radius of oxygen on the
ShannonPrewitt scale. In the case of Li, the average number of water molecules
around this cation is probably closer to four in concentrated solutions [6]. Thus, a
more appropriate value for the Li ion radius in water is 82 pm. As the atomic
number of the alkali metal cation increases, the average number of associated
water molecules increases and the eective radius in solution changes with respect
to the Shannon and Prewitt estimate accordingly.
In the case of the halide ions, the dierence between the ionoxygen distance
and the ShannonPrewitt radius increases from 143 pm for F, to 157 pm for I,
the average dierence being 149 pm. Assessment of this result is more dicult
because water molecules are oriented around anions via hydrogen bonding (see
g. 3.1). The fact that the average distance between an ion and the oxygen atom in
a water molecule is larger for an anion than a cation of the same size is easily
explained on the basis of the expected dierence in water orientation. Some
increase in the average number of water molecules associated with a given
anion is expected with increase in the anions atomic number.
Studies of pure water have resulted in the conclusion that water has a diameter
of 284 pm in a spherical representation [G3]. Thus, if the electrolyte solution is
represented as a collection of hard spheres, the distance between the center of a

Fig. 3.1 The orientation of a deuterated water molecule at a Li ion and Cl ion as
determined by neutron diraction. (From reference G3, with permission.)

ELECTROLYTE SOLUTIONS

99

K ion and that of an adjacent water molecule is 294 pm. The corresponding
distance for a Cl ion is 309 pm. Examination of these estimates with respect to
the experimental diraction data reveals that they are reasonable. However, if the
hard-sphere model relies on a point dipole description of the water molecule, the
chemical nature of the ionsolvent interactions is clearly neglected.
ShannonPrewitt radii for other monoatomic ions at various coordination
numbers are recorded in table 3.2. The choice of radius is important when estimating the solvation parameters of highly charged ions such as Al3. It is also
important to note that the estimated radii for transition metal ions such as Mn2
and Fe3 depend on the spin state of the d electrons in the ion. This also leads to
important dierences in solvation energies.
Radii have also been tabulated for polyatomic ions [7]. Since these species are
not truly spherical, such radii must be regarded as eective. However, it is useful
to have estimates of eective radii when comparing ionic solvation parameters. In
the following section, methods of determining the solvation parameters of single
ions in innitely dilute electrolyte solutions are considered. This is followed by a
discussion of simple models of ionic solvation in which ionic size is an important
factor.

Table 3.2 Shannon and Prewitt Radii for Monoatomic Ions


Determined from Crystallographic Data for Various
Coordination Numbers* [5]
Ion
Ag
Al3
Ba2
Ca2
Cd2
Co2
Co3
Cr2
Cr3
Cu2
FFe2
Fe3
Ga3

Coordination
Number
6
4
6
6
6
4
6
6
6
6
6
6
6
6
6
4
6
6
6
6
4
6

(ls)
(hs)
(ls)
(hs)
(ls)
(hs)

(ls)
(hs)
(ls)
(hs)

Radius
/pm
129
53
67
150
114
98
109
79
88
67
75
87
96
76
87
117
75
91
69
79
61
76

Ion
Hg2
In3
Li
Mg2
Mn2
Mn3
Na
Ni2
O2Pb2
S2
Se2
Sr2
Tl
Tl3
V2
V3
Zn2

Coordination
Number
6
6
4
4
6
6
6
6
6
4
6
6
6
6
6
6
6
6
6
6
4
6

(ls)
(hs)
(ls)
(hs)

Radius
/pm
116
93
73
63
86
81
96
72
79
113
84
126
132
170
184
130
164
102
93
78
74
89

*hs refers to the high-spin conguration of the d electrons in a transition


metal cation, and ls, to the low-spin conguration.

100

LIQUIDS, SOLUTIONS, AND INTERFACES

3.3 The Thermodynamics of IonSolvent Interactions


A very simple experiment that has been carried out for many electrolytes in water
is the measurement of the enthalpy associated with the dissolution of the electrolyte, which is often a solid, in water. This process can be either exothermic or
endothermic, and has an enthalpy change which depends on the relative amounts
of electrolyte and water. By studying the enthalpy of solution for one mole of
electrolyte as a function of the number of moles of water, which increase from one
experiment to the next, one can determine the enthalpy of solution associated with
the formation of an innitely dilute solution. In the case of NaCl, the relevant
process is
NaClcry 1H2 Ol ! NaClsl ; 1H2 O

3:3:1

with an enthalpy change equal to 3.9 kJ mol1, where the subscript cry represents the crystalline state, l, the liquid state, and sl, the solution. Under these
experimental conditions, and assuming complete dissociation of the electrolyte,
the value of the enthalpy change reects ionsolvent interactions in solution and
the lattice energy of the NaCl crystal. Since the solution is innitely dilute, ionion
interactions do not play a role in determining the magnitude of the enthalpy
change.
A much more suitable point of reference for assessing ionsolvent interactions
is the unsolvated ion in the gas phase. Thus, one would prefer to know the
enthalpy change associated with the reaction

Na
g Clg 1H2 Ol ! NaClsl ; 1H2 O

3:3:2


where Na
g and Clg are gas phase ions. In order to determine this quantity, the
enthalpy change associated with the reaction

NaClcry ! Na
g Clg

3:3:3

must be found. On the basis of tabulated thermodynamic data [G4], the enthalpy
change for reaction (3.3.3) is 787.4 kJ mol1. It follows that the enthalpy of reaction (3.3.2) is 783.4 kJ mol1. This quantity is called the enthalpy of solvation of
NaCl, sH. On the basis of other thermodynamic experiments, one can determine
the entropy change, sS, and the Gibbs energy change, sG, associated with the
same process.
Thermodynamic data for electrolyte solvation have been found experimentally
for many dierent electrolytes. Ultimately, one would like to be able to analyze
these results further to obtain separate contributions from the cation and anion.
However, that is not possible without making an extrathermodynamic assumption. As a result, a scale of single ion solvation parameters has been dened
relative to those for the H ion. For example, the enthalpy associated with the
process

H
g Clg / H2 O ! HCl; 1H2 O

3:3:4

is 1469.9 kJ mol1. If the enthalpy of solvation of H is dened to be zero, then


the enthalpy of solvation of Cl is 1469.9 kJ mol1. Using this result and the

ELECTROLYTE SOLUTIONS

101

value of sH for NaCl, the enthalpy of solvation of the Na ion is 686.5 kJ mol1.
The resulting scale of solvation enthalpies is called the conventional scale.
Another way of describing solvation parameters on the conventional scale is
by means of an exchange reaction between the ion in question and the proton.
Thus, the solvation parameters for the Na ion are dened by the reaction

Na
g H ; / H2 O ! Na ; 1H2 O Hg

3:3:5

From thermodynamic tables, the enthalpy of formation of H in an innitely


dilute aqueous solution is zero by denition; the same quantity for Na from
tabulated data is 240.1 kJ mol1. On the basis of these results, the enthalpy
associated with reaction (3.3.5) is 686.7 kJ mol1. This result agrees within experimental error with that obtained by comparing the heats of formation of innitely
dilute aqueous solutions of NaCl and HCl.
Estimation of the entropy of solvation requires calculation of the entropy of
the ion in the gas phase. For a monoatomic ion, the main contribution to the
entropy comes from its translational energy. Simple ions formed from the main
group elements have the electronic structure of an inert gas and therefore do not
have an electronic contribution to the entropy. On the other hand, ions formed
from transition metals may have an electronic contribution to the gas phase
entropy, which depends on the electronic conguration of the ions ground
state and of any other electronic states which are close in energy to the ground
state. The translational entropy is given by the SackurTetrode equation, which is
obtained from the solution of the SWE for a particle in a box (see section 2.2)
"
#
5R
2pmkB T 3=2 kB T
R ln
Strans
3:3:6
2
P
h3
Here m is the mass of the ion and the other symbols have their usual meaning. For
standard conditions of 25 C and 1 bar pressure, this equation becomes
Strans 108:856 12:472 ln M

3:3:7

where M is the atomic mass for the ion expressed in grams. The entropies of the
ions in solution have been estimated from a variety of thermodynamic data and
are given in standard tables [G4].
EXAMPLE

Estimate the enthalpy, entropy, and Gibbs energy of solvation of the S2 ion at
25 C and 1 bar using tabulated thermodynamic data together with the electron
anities of sulfur in the gas phase, which are
Sg e ! S 
g

H 200:4 kJ mol1

3:3:8

H 456 kJ mol1

3:3:9

and
2
S
g e ! Sg

The enthalpy of vaporization of solid sulfur is 278.8 kJ mol1. The enthalpy


of formation of H in the gas phase is 1536.2 kJ mol1. The enthalpy of formation of S2 in an innitely dilute aqueous solution is 33.1 kJ mol1. The
enthalpy of solvation of S2 is dened by the process

102

LIQUIDS, SOLUTIONS, AND INTERFACES


2
2H
g Sg ! H2 S; / H2 O

3:3:10

On the basis of the above data, sH for S2 is 3573.7 kJ mol1.
Using the SackurTetrode equation the entropies for H and S2 in the gas
phase are 108.95 and 152.10 J K1 mol1, respectively. The entropy of S2 in
an innitely dilute aqueous solution is 14.60 J K1 mol1 and that for H,
zero by denition. It follows that sS for S2 is 384.61 J K1 mol1.
The Gibbs energy of solvation is obtained using the relationship
s G s H  Ts S

3:3:11

On the basis of the above results, s G for S2 is 3459.0 kJ mol1


Values of sG and sS on the conventional scale are summarized in table 3.3.
Large variations are found in these quantities with ionic size and charge but they
are dicult to interpret without conversion to an absolute scale. Various methods
have been described to determine the absolute values of the solvation parameters
but they all require an extrathermodynamic assumption. On the other hand, the
Gibbs energy and enthalpy of formation of small water clusters containing a
single ion may be determined using mass spectrometry [8]. The number of
water molecules in a cluster is small, varying from one to six. By extrapolating
these results to obtain the values of G and H for an innite number of water
molecules in the cluster, one obtains the absolute solvation parameters, sG(abs)
and sH(abs). A method of carrying out this extrapolation has been developed [9]
which leads to the conclusion that sG(abs) is 1104.5 kJ mol1 and sH(abs),
1150 kJ mol1 for H ions at 25 C. The corresponding value of sS(abs) is
153 J K1 mol1. The value of sG(abs) obtained by the mass spectrometric
method is quite close to that estimated on the basis of measurements of the
work function for the H ion in an innitely dilute solution. The latter estimate,
which is 1096 kJ mol1 at 25 C is discussed in more detail in chapter 8.
On the basis of the values of sG(abs) and sS(abs) obtained in the mass
spectrometric experiments one may convert the results obtained on the conventional scale to the absolute scale. These results are also recorded in table 3.3. Of
course, it is an easy matter to obtain the value of sH on either scale using
relationship (3.3.11).
Having obtained absolute values of the thermodynamic properties describing
ion solvation it is interesting to examine various theories for ion solvation. The
best known of these is the Born model, which is described in the following section.

3.4 IonSolvent Interactions According to the


Born Model
The Born model [11] provides a means of estimating the Gibbs energy of solvation
for an ion in an innitely dilute solution. It is based on a continuum description of
the solvent as a uniform dielectric with a relative permittivity of es. The work of
transferring the ion from vacuum to the dielectric medium is estimated on the
basis of the following three-step process: (a) the ion is reversibly discharged in
vacuum; (b) the discharged ion, which is assumed to be a sphere of radius, ri, is

Table 3.3 Solvation Parameters for Monoatomic Ions in Water at


25 C and 1 bar [10]
Conventional Values
Ion

Absolute Values

sG / kJ mol1 sS / J K1 mol1 sG / kJ mol1 sS / J K1 mol1

Cations from the Main Group Elements


H
Li
Na
K
Rb
Cs
Be2
Mg2
Ca2
Sr2
Ba2
Al3
Ga3
In3
Tl
Tl3
Sn2
Pb2

0.0
575.1
680.8
752.6
775.2
798.4
289.3
277.6
600.7
729.9
857.3
1362.4
1370.2
820.7
746.1
822.0
619.1
681.6

0.0
10.7
20.0
56.9
66.1
72.2
48.1
68.8
9.9
20.7
57.3
144.8
165.9
7.9
59.3
40.3
32.5
53.0

1104
529
424
352
329
306
2498
1931
1608
1479
1352
4676
4684
4134
358
4135
1590
1527

153
164
133
96
87
81
354
375
296
285
249
604
625
451
94
499
273
253

84.5
9.5
174.4
29.4
64.0
125.5
74.6
89.0
11.1
57.2
14.4
55.2
23.1
10.7

3946
1933
4544
1868
1957
4429
2017
2095
583
2109
489
2057
1829
1859

543
315
633
335
370
584
380
395
164
363
139
361
329
295

429
304
278
243
1238

115
53
37
14
79

Transition Metal Cations


Sc3
Cr2
Cr3
Mn2
Fe2
Fe3
Co2
Ni2
Cu
Cu2
Ag
Zn2
Cd2
Hg2

632.7
276.0
1230.7
340.7
251.5
1115.8
192.2
113.5
521.1
100.2
615.8
152.2
379.8
349.8

Anions from the Main Group Elements


F
Cl
Br
I
S2

1533.6
1408.5
1382.2
1347.1
3446.6

268.3
205.8
190.1
166.9
384.6

104

LIQUIDS, SOLUTIONS, AND INTERFACES

transferred from vacuum to the dielectric liquid; and (c) the sphere is reversibly
charged up to become the original ion in the dielectric medium. In order to
estimate the associated work, one must be able to calculate the potential on the
surface of the ionic sphere due to its charge. According to Coulombs law, the
potential due to a charge zie0 at a distance ri is given by
zi e0

3:4:1
4pemed e0 ri
where zi is the ion charge number, e0, the electronic charge, emed, the relative
permittivity of the medium, and e0, the permittivity of free space. The work
done in charging up the sphere from zero charge to a nal charge of zie0 is then
z
i e0

w
0

q
dq
4pemed e0 ri

3:4:2

where q is any intermediate value of the charge. Carrying out the integration one
obtains
w

zi e0 2
8pemed e0 ri

3:4:3

The total work associated with the above three-step process for solvation can be
written
ws wa wb wc

3:4:4

Assuming that wb, the work associated with introducing the uncharged sphere
into the dielectric liquid, is zero, then
ws 

zi e0 2
z e 2
i 0
8pe0 ri 8pes e0 ri

3:4:5

where the rst term corresponds to the work associated with discharging the
sphere in vacuum (emed 1) and the second, to charging up the sphere in the
liquid (emed es). The work done per mole of ions is equated to the Gibbs
solvation energy of the ion, which may be expressed as


N z e 2
1
s Gi  L i 0
1
3:4:6
es
8pe0 ri
where NL is Avogadros constant. This is the basic result of the Born model.
Having obtained the Gibbs energy of solvation, one may now determine the
other thermodynamic parameters. The entropy is obtained from the temperature
derivative of s Gi :
s S i 

ds Gi NL zi e0 2 1 des

dT
8pe0 ri e2s dT

3:4:7

where des/dT is the temperature derivative of the relative solvent permittivity. It


should be noted that the radius of the ion has been assumed independent of
temperature, a reasonable assumption for monatomic ions. Since the solvent
permittivity decreases with increase in temperature, the Born model predicts

ELECTROLYTE SOLUTIONS

105

that the entropy of solvation is negative. This is an expected result, since the
solvation process is imagined to involve reorganization of local solvent molecules
around the ion to stabilize its presence in the medium.
The Gibbs energy and entropy may now be combined to obtain an expression
for the enthalpy of solvation:


N z e 2
1 T de
3:4:8
s Hi s Gi Ts Si  L i 0
1  2 s
8pe0 ri
es es dT
The enthalpy of solvation is clearly larger in magnitude (more negative) than the
Gibbs energy because the sign of the entropy and Gibbs energy contributions are
the same.
Estimates of sG and sS according to the Born model using the Shannon and
Prewitt radii are given in table 3.4. From the results, it is clear that the Born
estimates of sGi for the alkali metal cations are all too large in magnitude, the
dierence for the smallest ion, Li, being the largest. In the case of the halide
anions, the dierence between the Born estimate and experiment is not as great,
the Born estimate always being larger in magnitude. On the other hand, the Born
estimates of the entropy change accompanying solvation are usually too small.
The generally accepted explanation for the failure of the Born model is that the
structure of the solvent is signicantly altered near the ion by the eect its eld has
on the local water molecules. This eect is especially important for cations, which
are stabilized by the electron density on the oxygen atoms of water. One can
describe the local disruption of water structure as resulting in an eective decrease
in the dielectric constant of the solvent near the ion. As a result, the work associated with the charging the ionic system in solution is less negative, and the Born
estimates are too high in magnitude. In the case of anions, hydrogen bonds from
surrounding water molecules are important in stabilizing the ion. Disruption of
the local solvent structure also occurs but it is not as severe. As a result the Born
Table 3.4 Experimental Value and Estimates According to
the Born Model and Mean Spherical Approximation for
the Gibbs Energy and Entropy of Solvation of the Alkali
Metal Cations and Halide Anions at 25 C
Gibbs Energy s Gi / kJ mol1

Entropy s Si / J K1 mol1

Ion

Expt*

Born

MSA

Expt*

Born

MSA

Li
Na
K
Rb
Cs
F
Cl
Br
I

529
424
352
329
306
429
304
278
243

779
591
451
421
373
576
411
377
333

483
403
333
316
288
396
310
291
264

164
133
96
87
81
115
53
37
14

46
35
27
25
22
34
24
22
20

199
143
101
92
78
138
89
79
66

*Absolute value of the Gibbs energy of solvation from table 3.3.

106

LIQUIDS, SOLUTIONS, AND INTERFACES

estimates for anions are closer to the experimental quantities than for cations. It is
also apparent from table 3.4 that the Born model underestimates the magnitude of
the entropy change resulting from ion solvation especially for the smaller ions.
This is specically because it does not take into account the local restructuring of
water, which increases the orderliness of the system near the ion.
Many attempts have been made to improve the Born description of ion solvation. Most of these rely upon continuum descriptions of the solvent in which the
permittivity varies from a low value near the ion to the bulk value farther away.
This variation is described mathematically either as two or three regions with a
constant permittivity in each, or as a solvent with a continuously varying permittivity over a region of a few molecular diameters thick. Macroscopic concepts
such as the permittivity are not really valid at molecular dimensions. For this
reason these models are not considered further here. Instead, in the next section, a
model based on a discrete description of the electrolyte solution as a collection of
hard spheres is discussed.

3.5 Ion-Solvent Interactions According to the Mean


Spherical Approximation
In the Born model, the solvent was considered to be a continuum with uniform
dielectric properties, right up to an ion, which carries a discrete charge. As soon as
one recognizes the molecular nature of the solvent, one can imagine how the local
solvent structure near an ion is disrupted by the high electrical eld near the ion.
Another way of representing a polar solvent is as a collection of close-packed hard
spheres with centrally located point dipoles. Such a description ignores the chemical composition of the solvent molecule but takes into account its most important electrostatic feature, namely, that it has a dipole moment. No consideration is
given to the presence of higher-order moments, or to the possibility that the
solvent may also be involved in hydrogen bonding.
The simplest non-primitive model for representing a dilute electrolyte solution
is the mean spherical approximation (MSA). In its present application, the system
consists of hard spheres of two sizes, one size for the solvent molecules, and
another for the ions, both cations and anions. Since this model is only applied
here in the limit of innite dilution the restriction that cations and anions have
equal radii is of no consequence. On the basis of the discussion in chapter 2, the
MSA requires that the pair correlation function for any two spheres goes to zero
within the reference sphere because they are hard. Outside of any sphere, the
direct correlation function is set equal to the interaction energy between the
spheres divided by kBT. Solution of the statistical mechanical problem involves
applying the OrnsteinZernike (OZ) equation to obtain the pair correlation function outside of a given sphere. Since the system consists of a mixture of ions and
dipoles, the OZ equations appropriate for a mixture must be used with consideration of the ionion, iondipole, and dipoledipole interactions that are present.
Once the pair correlation functions have been found, the thermodynamic properties of the system may be calculated. In the following presentation, the equations
dening the problem are given as well as the solution, no attempt being made to

ELECTROLYTE SOLUTIONS

107

present all of the mathematics required to obtain the solution. The interested
reader is referred to the original literature [1214] for the mathematical details.
In the following, the radius of a solvent molecule represented as a sphere is
denoted by rs, and that of either a cation or anion by ri. The conditions which
dene the direct correlation function are the following.
For ionion interactions,
gij r 0;

r < 2ri

3:5:1

and
cij r buij r 

zi zj be20
;
4pe0 r

r > 2ri

3:5:2

where zi and zj are the charge numbers on ions i and j, and b 1=kB T.
For iondipole interactions,
gid r; o 0;

r < ri rs

3:5:3

and
cid r; o

zi e0 pbso
sr
;
4pe0 r2

r > ri rs

3:5:4

where p is the dipole moment of the solvent molecule, so , a unit vector in the
direction of the dipole, sr , one in the direction r, and o, an angular variable
dening the dipole orientation.
Finally, for dipoledipole interactions,
gdd o1 ; r; o2 0;

r < 2rs

3:5:5

and
cdd o1 ; r; o2

bp2
s1
sr s2
sr  s1 s2 ;
4pe0 r3

r > rs

3:5:6

where the dipole directions are dened by unit vectors s1 and s2 . Using the
OrnsteinZernike equation (2.6.1), one can now determine the total correlation
function for each of these interactions.
Only one result from this model is presented here, namely, the Gibbs energy of
iondipole interactions in the limit of innite dilution, Gid . Further, if one identies this with the Gibbs solvation energy, the result is



N L zi e0 2
1
1
3:5:7
s G i 
1
8pe0 ri
es
1 rs =ls ri
where ls is the polarization parameter for the solvent. This parameter is obtained
from the dielectric properties of the solvent, and on the basis of the work of
Wertheim [15] is given by
l2s 1 ls 4 16es

3:5:8

By using the bulk dielectric permittivity, the value of ls includes consideration not
only of the dipole moment of the solvent but also its polarizability and other
features which are necessary to describe iondipole and dipoledipole interac-

108

LIQUIDS, SOLUTIONS, AND INTERFACES

tions. In the case of water at 298 K, the value of ls estimated from es (78.46) is
2.65. It should be noted that the role of dipoledipole interactions in determining
s Gi is ignored in equation (3.5.7).
A more convenient way of writing the Gibbs solvation energy is



N z e 2
1
1
s G i  L i 0
3:5:9
1
8pe0
es
r i ds
where ds is equal to rs/ls and depends only on the nature of the solvent. If ds is
zero, the expression for s Gi becomes equal to that given by the Born model. It is
clear that ds is a correction to the ionic radius and results in estimates of s Gi
which are considerably smaller than the Born estimates. A reasonable value of rs
for water is 142 pm, so that the value of ds is 53.6 pm. This is not insignicant with
respect to the radii of simple monoatomic ions (see tables 3.1 and 3.2).
EXAMPLE

Acetonitrile is a polar solvent with a relative permittivity of 35.9. It may be


represented as a hard sphere with a diameter of 427 pm. Estimate the Gibbs
energy of solvation of Na in acetonitrile according to the Born and MSA
models. Compare the theoretical estimates with the experimental estimate
given that the Gibbs energy of transfer for Na from water to acetonitrile is
15.1 kJ mol1.
The Gibbs energy of solvation according to the Born model is given by
equation (3.4.6). The constant NLe02/8pe0 is equal to 6:945  105 J m mol1.
The radius of Na according to Shannon and Prewitt is 116 pm (table 3.1).
The factor (1  1/es) is equal to 0.972. The resulting value of s Gi is
581.9 kJ mol1.
In order to estimate s Gi according to the MSA, one must rst nd the
value of ls using equation (3.5.8). Solving this cubic equation, one obtains the
result that ls is equal to 2.26. Using a radius of 213.5 pm for acetonitrile, the
corresponding value of ds is 94.5 pm. Thus, the MSA estimate of s Gi for Na
is 320.7 kJ mol1 (equation (3.5.9)).
The absolute value of the Gibbs energy of solvation of Na in water according to experiment is 424 kJ mol1 (table 3.4). After transfer to acetonitrile,
s Gi is 409 kJ mol1.
The MSA estimate of s Gi is closer to the experimental value than the Born
estimate.
The entropy of solvation is obtained from the temperature derivative of s Gi
[16]. Recognizing that ls depends on temperature, the resulting expression is
"
#


ds Gi N L zi e0 2 1
1
des
1
1 dds
s S i 


1
3:5:10
es dT
dT
8pe0
e2s ri ds dT
ri ds 2
where the temperature coecient of ds is given by
dds
r dl
 s2 s
dT
ls dT

3:5:11

ELECTROLYTE SOLUTIONS

109

dls/dT can be determined by dierentiation of the Wertheim equation with


respect to temperature, which gives


dls
ls 1 ls 1 des

3:5:12
3ls 1 2es dT
dT
Since the dielectric permittivity decreases with temperature, the coecient dls/dT
is negative, and dds/dT is positive. As a result, both terms in the square brackets in
equation (3.5.10) give negative contributions to s S i . Given that des/dT for water
is 0.360 K1, the value of dls/dT is 2:48  103 K1 and dds/dT is 0.050 pm
K1.
Values of s Gi and s S i calculated according to the MSA for the alkali metal
cations and halide anions are recorded in table 3.4. The estimates of s Gi for the
cations are much better than those by the Born model and give acceptable results.
On the other hand, the results for the anions are signicantly lower than the
experimental values. The MSA estimates of s S i for most ions are too high in
magnitude. In general, the MSA provides a simple extension of the Born continuum model and gives better values for the fundamental thermodynamic quantities relating to ionic solvation. The major reason the simple MSA model fails is
that it has ignored dipoledipole interactions in the estimation of s Gi and s S i .
Dipoledipole interactions in the immediate vicinity of an ion are expected to be
repulsive in character and reduce the estimates of s Gi ands S i from those given
by equations (3.5.9) and (3.5.10).
An expression for the dipoledipole contribution to the solvation energy has
been derived on the basis of the MSA [12, 13] but it is generally felt to overestimate the repulsive eect. When one analyzes the functional form of the dipole
dipole term, it can be shown that it is similar to that for the iondipole contribution. As a result, a simple way of writing an improved expression for the Gibbs
solvation energy is



N L zi e0 2
1 
1
1  f dd
s Gi 
3:5:13
8pe0 ri ds
es
where fdd is a term depending on dipoledipole interactions which is much less
than one.
Another problem with the MSA is that it does not distinguish between the
solvation of cations and anions of the same size. Thus, although the K and F
ions have approximately the same radius, the F anion is more strongly solvated
than the K cation (table 3.4). This can be understood in terms of the eect that
each ion has on local water structure. The K ion disrupts this structure more so
that the stabilizing eect of the local iondipole interactions is oset by the work
done to break up the water structure, that is, to disrupt attractive dipoledipole
interactions and hydrogen bonding between local water molecules. This means
that the parameter ds should be dierent for cations and anions in the same
solvent (table 3.5).
It is interesting to examine the data for ions from the main group elements on
the basis of equation (3.5.13) using the absolute values of s Gi given in table 3.3.
In order to do this, the equation is rearranged as follows:

110

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 3.5 MSA Parameters Relating to the


Solvation of Monoatomic Ions of the Main Group
Elements in Water on the Basis of Equation (3.5.14)
Polarization
Parameter, ds / pm

DipoleDipole Interaction
Parameter, fdd

49
0

0
0.26

Cations
Anions

z2i
ks ri ds
s Gi

3:5:14

where
ks

N L e20 1

8pe0 es
 f dd es  1

3:5:15

It follows that a plot of z2i s Gi 1 should be linear against the ionic radius ri,
and that fdd and ds can be calculated from the slope and radius, respectively.
The quality of the t of equation (3.5.14) to the experimental data is illustrated
in g. 3.2. It is clear from this plot that the behavior of cations and anions is
signicantly dierent. On the other hand, the linear plots obtained for each species are very good. The radius correction parameter ds for cations is slightly
smaller than the value predicted by the Wertheim equation but that for anions
is considerably smaller. This is clearly a result of the fact that cations disrupt the
structure of water much more than anions. On the other hand, dipoledipole

Fig. 3.2 Plots of z2i s Gi 1 against ionic radius ri for the alkali metal cations (*),
alkaline earth metal cations (&), halide anions (~) and the sulde anion (!). The parameters ds and f dd are determined from the intercept and slope of these plots, respectively,
according to equation (3.5.14). The plot for cations has been shifted vertically by 1 mol
MJ1 for the sake of clarity.

ELECTROLYTE SOLUTIONS

111

interactions are negligible for water molecules arranged around a cation, whereas
they are signicant in the solvation of anions. The latter result reects the role of
hydrogen bonding in anion solvation. In assessing the results one must keep in
mind the fact that it has been assumed that the appropriate radii for all ions are
those estimated for a coordination number of six. This is probably not correct for
smaller ions such as Li and Mg2. For these ions, the radii estimated for a
coordination number of four may be more appropriate. If smaller radii are chosen
for the smaller ions, the characteristics of the plots in g. 3.2 change. This would
aect both the polarization parameter ds and the dipoledipole interaction parameter fdd.
The above empirical model can be extended to estimation of the entropy of
solvation. When equation (3.5.13) is dierentiated with respect to temperature,
one must consider the temperature variation of ds and fdd as well as the temperature dependence of es. However, the number of data points is too few to determine
all the temperature coecients which arise.
In summary, the empirical approach to ionic solvation based on the MSA is
quite successful for monoatomic ions of the main group elements. It helps one to
understand the important dierences between the way cations and anions are
solvated in water. It can also be applied to other ions, including polyatomic
ions, provided the solvation is essentially electrostatic in character. Thus, one
may estimate eective radii for anions such as nitrate and perchlorate from the
Gibbs solvation energy using the value of ds calculated for the halide ions.
Considering the simplicity of the model, it provides an useful means of understanding the thermodynamics of solvation.

3.6 The Thermodynamics of Electrolyte Solutions


Electrolyte solutions are non-ideal by their nature. This follows from the fact that
the interactions among the three species in solution, namely, cations, anions, and
solvent molecules, are all dierent. Ions with the same charge strongly repel one
another, whereas oppositely charged ions attract one another. Interactions of ions
with the solvent molecules depend on ionic charge. From a fundamental point of
view one would like to understand each interaction in detail at the molecular level.
However, thermodynamically one may study the properties of the electrolyte as a
whole, or of the solvent. In this section, the thermodynamic conventions for
dealing with the properties of electrolytes are presented. As will be seen, these
conventions depend largely on the fact that cations and anions are always present
at concentrations such that the net charge in the solution is zero.
In general one distinguishes two types of electrolyte solutions. The rst is
formed from strong electrolytes, also called ionophores. Strong electrolytes exist
as ions in the solid state, a well-known example being NaCl. When they dissolve
in a polar solvent such as water, the individual ions are stabilized by iondipole
interactions with solvent molecules. Otherwise the properties of the system reect
long-range electrostatic ionion interactions. On the other hand, a weak electrolyte or ionogene is a compound which is molecular in nature as a pure substance.
It forms ions by interaction with water molecules. A familiar weak electrolyte is

112

LIQUIDS, SOLUTIONS, AND INTERFACES

acetic acid, which interacts with water to form solvated protons and acetate ions.
Usually, dissociation of the molecule into ions is not complete, so that a dissociation constant is required to determine the ionic concentrations in solution.
It is important to note that ionophores are not always completely dissociated.
For example, when NaCl is dissolved in a solvent of lower relative permittivity,
such as methanol, it is ion paired to some extent. The thermodynamics of systems
with ion pairing is considered separately in section 3.10. Under these circumstances the ionophore behaves in the same way as a weak electrolyte. On the
other hand, all ionogenes are not weak electrolytes. For example, HCl, which is
a molecule in the gas phase, is completely dissociated in water and therefore is a
strong electrolyte. Acetic acid is completely dissociated in liquid ammonia, which
is a much stronger base than water. Thus, the solvent plays an important role in
determining the extent of electrolyte dissociation in solution. In the following
discussion the traditional terms, strong and weak electrolytes, are used.
A. Strong Electrolytes
Consider a simple 11 electrolyte MX which is completely dissociated in dilute
solutions. The chemical potential of MX can be written as
mMX mMX RT ln aMX

3:6:1

where aMX is the activity of the electrolyte. Activity is related to the concentration
of the electrolyte on the appropriate scale. Although one cannot directly measure
separately the cationic activity aM and anionic activity aX, one can consider these
quantities conceptually. They are dened by the relationship
aM aX aMX

3:6:2

and are not necessarily equal, in spite of the fact that the concentrations of M and
X must be equal. The electrolyte concentration is commonly expressed either in
terms of molality or molarity. Using the former, the activity of ion i is given by
ai gi m e

3:6:3

where gi is the activity coecient on the molal scale and me, the electrolyte
molality. The mean ionic activity coecient is dened by the equation
g2 gM gX

3:6:4

Since individual ionic activity coecients cannot be measured experimentally,


only the mean quantity is tabulated. It follows that the activity of a 11 electrolyte
is given by
3:6:5
aMX g2 m2e
and its chemical potential by

2RT ln g me
mMX mMX

3:6:6

The concentration dependence of g is an important feature involved in the


experimental and theoretical evaluation of electrolyte behavior. The chemical

potential of the standard state, mMX
, is that for a hypothetical one-molal solution
in which all real interactions are imagined to be absent (g 1.00). Thus, the

ELECTROLYTE SOLUTIONS

113

standard state for the electrolyte solution is chosen on the basis of the Henry law
convention (see section 1.11).
One may also write expressions for the chemical potential of the electrolyte on
the molarity and mole fraction scales. In the former case, the expression is
mMX mMX 2RT ln y ce

3:6:7

mMX

is the standard chemical potential and y , the corresponding activity


where
coecient. On the mole fraction scale, one writes
mMX mMX 2RT ln f xe
D

3:6:8

where mMX is the standard chemical potential, f , the corresponding activity


coecient, and xe, the mole fraction of the electrolyte. As with the molal scale,
the standard states are dened with respect to hypothetical ideal solutions of unit
concentration. The mole fraction scale is not often used for electrolytes for the
obvious reason that the electrolyte concentration cannot be varied over the whole
range of mole fractions because of its limited solubility. On the other hand, the
molar scale is popular. In order to convert values of activity coecients which are
usually tabulated on the molal scale [G1] to the molar scale, one needs to know
the concentrations on the two scales, ce and me, and the density of the pure
solvent, rs . The relationship between the activity coecients is
c
g e  y
3:6:9
me rs
The above equations for a 11 electrolyte are easily extended to a more complex electrolyte MaXb. Dissociation of this electrolyte give cations Mb and
anions Xa-:
Ma Xb ! n Mb n Xa

3:6:10

The stoichiometric numbers n and n give the number of moles of cations and
anions, respectively, resulting from the dissolution of one formula of electrolyte.
Their sum is designated as n:
n n n 

3:6:11

On the basis of equation (3.6.2) the electrolyte activity is


ae a n a n

3:6:12

Each of these activities is the product of an activity coecient and a concentration. On the molality scale, one may write
ae g m n g m n

3:6:13

m n m e

3:6:14

m  n m e

3:6:15

Now,

and

The mean molality m is dened on the basis of a geometric average so that

114

LIQUIDS, SOLUTIONS, AND INTERFACES


n

m n m n m n n nn mne

3:6:16

Now one denes a mean activity coecient using the equation


g n g n g n

3:6:17

It follows that the electrolyte activity is


ae n n n n g n mne

3:6:18

One may also dene a mean electrolyte activity, a , which is given by


n

a n nn 1=n g me

3:6:19

It is easily seen that this expression yields the correct result for a 11 electrolyte
when n and n are set equal to unity.
EXAMPLE

A 0.1 m solution of MgCl2 in water has a density of 1.0047 g mL1 at 258C. The
mean ionic activity coecient on the molal scale is 0.528. Calculate the mean
activity and electrolyte activity on this scale. Repeat the calculations for the
molarity scale.
For this electrolyte, the concentration of Mg2 ions is 0.1 m n 1 and
that of Cl ions 0.2 m n 2. Thus the mean ionic molality on the basis of
equation (3.6.16) is
m 1  22 1=3 me 41=3 0:1 0:1587

3:6:20

The mean activity is


a g m 0:528  0:1587 0:0838

3:6:21

The electrolyte activity on the molality scale is


ae a3 0:08383 5:89  104

3:6:22

The molecular mass of MgCl2 is 95.22 g. Thus, 9.522 g of MgCl2 are dissolved in 1000 g of water to form a 0.1 m solution. Given that the density of the
solution is 1.0047, its volume is
V

9:522 1000
1004:8 mL
1:0047

3:6:23

0:1
0:0995 M
1:0048

3:6:24

Its molar concentration is


ce

The mean ionic concentration is


c 41=3 0:0995 0:1579 M

3:6:25
1

Given that the density of pure water at 258C is 0.997 g mL , the activity
coecient on the molar scale (equation (3.6.9)) is
y

me rso g 0:1  0:997  0:528


0:529

0:0995
ce

Thus, the mean electrolyte activity is

3:6:26

ELECTROLYTE SOLUTIONS

a y c 0:529  0:1579 0:0835

115

3:6:27

The electrolyte activity on the molarity scale is


ae a3 5:83  104

3:6:28

It is important to remember that the mean ionic concentration and activity


are based on the geometrical mean of the concentrations of the two ions in
non-symmetrical electrolytes, not on their arithmetic mean.
B. Weak Electrolytes
In order to develop the thermodynamics of a weak electrolyte, one extra parameter is required, namely the dissociation constant Kdiss . Using the same terminology as above, the dissociation process for a weak 11 electrolyte is
MX (
+ M X
The equilibrium constant for this process is
a a
Kdiss M X
aMX

3:6:29

3:6:30

where aM and aX are the activities of the ions, and aMX , that of the undissociated
molecule. On the molality scale, this may be written as
Kdiss

g2 m2
gMX mMX

3:6:31

where g is the mean ionic activity coecient on the molality scale, m , the mean
ionic molality, gMX , the activity coecient of the molecular species, and mMX , its
molality. This relationship is often written in terms of the fraction of weak electrolyte which is dissociated, namely, ai . If me is the stoichiometric molality of the
weak electrolyte, that is, the molality of the undissociated molecule plus that of
the dissociated form, then equation (3.6.31) bcomes
Kdiss

g2 a2i me
gMX 1  ai

3:6:32

An expression can now be written for the chemical potential of the weak
electrolyte system. On the basis of the composition of the solution

mMX ai m
M ai mX 1  ai mMX

m
M

3:6:33

m
X

and
are the chemical potentials of the free ions and mMX , that of the
where
undissociated molecular. Writing each chemical potential in terms of its standard
value and the corresponding activity, one obtains
mMX mMX ai RT ln aM aX 1  ai RT ln aMX

3:6:34

mMX ai mM ai mX 1  ai mMX

3:6:35

where
In these equations, mi is the standard potential of species i and ai , its activity.
Finally, from equilibrium (3.6.29), one may write that

116

LIQUIDS, SOLUTIONS, AND INTERFACES



mMX m
M mX

3:6:36

RT ln Kdiss mMX  mM  mX

3:6:37

so that
By substituting equations (3.6.30) and (3.6.37) into equation (3.6.34), a much
simpler expression for mMX is obtained:
mMX mM mX RT ln aM aX

3:6:38

This result shows that the chemical potential of the weak electrolyte system may
be expressed in terms of the activities of the ions only, without explicitly including
the activity of the undissociated molecule. Equation (3.6.38) is no dierent in
form from those for a strong electrolyte (equations (3.6.1) and (3.6.2)). Of course,
the activities of the ions are much less for the weak electrolyte than those for the
strong electrolyte for a given molality. Thus, on the basis of the present analysis
for a weak electrolyte
aM aX a2i g2 m2e

3:6:39

When these equations are written in terms of the concentration (molarity) the
results are
mMX mM X RT ln aM aX

3:6:40

aM aX a2i y2 c2e

3:6:41

where
mM

mX

and
are the standard potentials of the two ions on the molarity scale, y ,
the mean ionic activity coecient, and ce , the molarity of the weak electrolyte
system.

3.7 The Experimental Determination of Activity


Coefcients for Electrolytes
In general, one may distinguish two methods of determining the activity of an
electrolyte in solution. One type is based on the direct measurement of electrolyte
activity. The most popular technique in this category involves electromotive force
measurements with electrochemical cells. This subject is not discussed here, but
later in the chapter dealing with electrochemical equilibria (chapter 9). The second
type of measurement involves determination of the activity of the solvent, for
instance, by measuring its vapor pressure. These activity data are used to calculate
the activity of the electrolyte on the basis of the GibbsDuhem relationship.
Methods related to determination of the solvents vapor pressure include the
determination of the lowering of the melting point, and the elevation of the
boiling point. The latter two techniques have the inconvenience that the activity
coecients are determined at the freezing point or boiling point of water, and not
at room temperature or the usual experimental temperature of 258C. Thus, the
most often used technique is the direct determination of the vapor pressure of the
solvent as a function of electrolyte concentration at 258C. The experimental techniques have been described in detail by Robinson and Stokes [G1].

ELECTROLYTE SOLUTIONS

117

Having obtained the solvent vapor pressure, one may immediately relate it to
the activity of the electrolyte using the GibbsDuhem relationship. Thus,
 
P
3:7:1
ne d ln ae ns d ln as ns d ln s
Ps
where the subscript e denotes electrolyte, and the subscript s, solvent.
Furthermore, if one works with molalities, such that ne is equal to me and ns to
1000 M 1
s where Ms is the molecular mass of the solvent, then
1000
nme d ln g me 
d ln as
3:7:2
Ms
At this point, it is convenient to introduce a quantity called the osmotic coecient, j. It is dened according to the equation
1000
ln as
3:7:3
nme j 
Ms
One often nds values of j tabulated for electrolyte solutions as well as the mean
activity coecient g [G1, G5]. Taking the total derivative of equation (3.7.3), one
obtains
1000
d ln as
3:7:4
nme dj nj dme 
Ms
Combining this with equation (3.7.2), one may write
d ln g dj j  1 d ln me

3:7:5

Remembering that both g and j go to unity as me goes to zero, one obtains


m
e
3:7:6
ln g j  1 j  1 d ln me
0

This relationship is used to calculate mean ionic activity coecients using values
of the osmotic coecient, j. Alternatively, one may calculate the osmotic coecient given the mean ionic activity coecient. From equations (3.7.2) and (3.7.3)
dnme j 

1000
d ln as nme d ln g me
Ms

3:7:7

Integrating from zero molality, one obtains


m
e

nme j

nme d ln g me

3:7:8

or
1
j1
me
EXAMPLE

m
e

me d ln g

3:7:9

The activity of water (Pw/Pw ) in a 6:4  103 m NaCl solution is 0.9997754.


Estimate the osmotic coecient and mean ionic activity coecients for the

118

LIQUIDS, SOLUTIONS, AND INTERFACES

electrolyte. In more dilute solutions, it may be assumed [G1] that the relationship between the osmotic coecient and molality is
j 1  0:330 m1=2
e

3:7:10

From equation (3.7.3), the osmotic coecient is


j

1000
1

 ln 0:9997754 0:9738
18:02 2  6:4  103

3:7:11

Note that the value of the osmotic coecient agrees with that estimated from
equation (3.7.10).
Combining equations (3.7.6) and (3.7.10), one obtains
m
e

ln g 0:0262 

0:330 m1=2
e d ln me
0
m
e

0:0262 

0:330 me1=2 dme

3:7:12

0:0262  2  0:330 me1=2 0:0790


The value of g is 0.924.
Values of the water activity and osmotic coecient for NaCl solutions in water
for concentrations up to 6 m are shown in g. 3.3. First, it is apparent that the
vapor pressure of water decreases continuously with increase in salt concentration
as one would expect. The value of aw at the most dilute concentration considered
(0.1 m) is 0.99665. Measurements of vapor pressure lowering for lower concentrations are extremely dicult. The concentration dependence of the osmotic coecient j reported in the same gure is quite dierent from that of the water activity.
This quantity at rst decreases, and then rises to values which are signicantly

Fig. 3.3 Plots of the water activity, aw, and corresponding osmotic coecient, j, for
aqueous solutions of sodium chloride at 25 C.

ELECTROLYTE SOLUTIONS

119

greater than unity. Tables of the osmotic coecients for a large number of electrolytes in water at 25 C are available in the monograph by Robinson and Stokes
[G1], and in the more recent compilation by Lobo [G5].
In order to calculate the mean ionic activity coecient, g , from the osmotic
coecient, j, one must perform a numerical integration to evaluate the integral in
equation (3.7.6). The value of the integrand, chosen to be 1  j=me , is shown as
a function of electrolyte molality using the NaCl data in g. 3.4. This function is
clearly nite in the limit that me goes to zero, and is equal to one. As a result, there
is no problem in evaluating the integral by numerical techniques, and thereby
estimating ln g .
In many cases, it is more convenient to use activity coecients on the molarity
scale. Not only is molarity more commonly used as a concentration unit in
chemistry but values of y are more directly related to the results of statistical
mechanical theories of electrolyte solutions discussed later in this chapter. For a
given molality, me, one must calculate the corresponding molarity, ce, using the
relationship
ce

1000me rs
me Me 1000

3:7:13

where rs is the density of the solution and M e, the molecular mass of the electrolyte. The solution density is not related in a simple way to either the molality or
molarity. It has been tabulated [G5] for many electrolyte solutions but often not
at the specic concentrations of interest. In this regard, there is a useful empirical
relationship which can be used to describe the variation in solution density with
molality [G6]:
ln rs ln rs

Ae me Me
me Me 1000

3:7:14

Fig. 3.4 Plots of the function (1j)/me, where j is the osmotic coecient against solute
molality, me, for solutions of sodium chloride in water at 25 C.

120

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 3.6 Values of the Constant


Ae in Equation (3.7.14) which
Relates the Solution Density to Its
Molality for Aqueous Solutions of
the Alkali Metal Halides
Anion
F

Cl

Br

I

1.0260
0.8471
0.9710
1.2595

0.5667
0.6938
0.6323
0.7748
0.8308

0.8248
0.8388
0.7624
0.9077
0.8536

0.8697
0.9146
0.8310
0.848
0.6420

Cation
Li
Na
K
Rb
Cs

Values of the constant Ae determined via least-squares ts of density data for


aqueous solutions of the alkali metal halides are given in table 3.6. Similar ts
may be made for other electrolyte solutions so that the conversion of molality to
molarity is easily carried out. Once the concentration units are known, values of
y are easily calculated from g using equation (3.6.9). These quantities are given
in table 3.7 for the NaCl system for concentrations up to 2.4 m.
The above results illustrate the importance of non-ideality for electrolyte solutions and also of the use of the GibbsDuhem relationship in obtaining electrolyte

Table 3.7 Mean Activity Coefcients


for the Aqueous NaCl System on the
Molality and Molarity Scales
Molality/me

Molarity/ce

0.010
0.020
0.050
0.100
0.200
0.300
0.500
0.600
0.700
0.800
0.900
1.000
1.200
1.400
1.600
1.800
2.000
2.200
2.400

0.903
0.872
0.822
0.779
0.735
0.710
0.681
0.673
0.667
0.662
0.659
0.657
0.654
0.654
0.657
0.661
0.668
0.675
0.683

0.010
0.020
0.050
0.100
0.199
0.298
0.494
0.592
0.689
0.786
0.883
0.979
1.170
1.360
1.548
1.734
1.919
2.101
2.282

0.900
0.869
0.820
0.780
0.738
0.714
0.687
0.680
0.675
0.672
0.670
0.669
0.669
0.671
0.677
0.684
0.694
0.705
0.716

ELECTROLYTE SOLUTIONS

121

activity coecients from vapor pressure measurements for the solvent. Although
activity coecients can be measured directly for some electrolytes, they can
always be obtained indirectly from the solvent activity.
In the next section a model developed to account for non-ideality is considered
and its ability to predict experimental results assessed.

3.8 IonIon Interactions According to the


ckel Theory
DebyeHu
The rst successful theory of electrolyte solutions was proposed by Debye and
Huckel. It is based on a model in which the ions are represented as point charges
embedded in a dielectric continuum. The model uses fundamental electrostatics to
calculate the average local potential at any given ion due to its ionic atmosphere
[17]. The main problem is to determine a distribution function for the ions in the
atmosphere. This is achieved by assuming that the probability of nding an ion at
a distance, r, from the central ion is given by the Boltzmann distribution law
which accounts for the randomizing eects of thermal motion in the presence
of the electrical eld. The potential at the reference ion may then be used to
calculate the excess Gibbs energy due to the ionion interactions present in the
electrolyte solution. In the DebyeHuckel model, solution non-ideality is attributed to the ionion interactions and related to the excess Gibbs energy through
the activity coecient, yi for ion i.
It is important to recognize that the average potential in a uniform phase, such
as an electrolyte solution, is constant in the absence of an external eld, such as an
electrical eld. However, the problem solved by Debye and Huckel is the estimation of the average local potential which is dierent from the average potential.
The local potential is sometimes called the micropotential, whereas the average
potential is called the macropotential. It will be seen that the micropotential
uctuates in the solution, being more positive at a cation and more negative at
an anion. The theory presented below gives an estimate of how the ionic atmosphere aects these uctuations.
Two equations are required to solve the problem in question. The rst is the
Poisson equation, which describes how the micropotential, , varies in space. As
a partial dierential equation it is written as
r2  div grad 

rz
es e0

3:8:1

where rz is the average charge density at a distance, r, from the central ion. It is
derived by combining two fundamental laws of electrostatics, namely, Coulombs
law and Gauss law. In vector notation, these are
E grad 

3:8:2

div D rz

3:8:3

and

122

LIQUIDS, SOLUTIONS, AND INTERFACES

where E is the electrical eld and D, the electric displacement (D ee0 E) (see
Appendix B). The Laplacian of , r2 , describes the spatial variation of the
potential and in Cartesian coordinates is given by
r2 

@2  @2  @2 
2 2
@x2
@y
@z

3:8:4

However, the present problem is more conveniently solved in spherical coordinates because an estimate of the average charge density at a distance r is sought.
In this case,  depends only on r and not on the Eulerian angles, which dene an
exact location in spherical coordinates. As a result, equation (3.8.1) can be written
as


1 d 2 d
r
2
3:8:5
r  2
r
 z
dr
dr
e
r
s e0
The second equation is obtained by applying Boltzmann statistics to estimate
the charge density, rz. The local concentration of ion i at a distance r from the
central reference ion, cri , diers from its average concentration, c i , because the
potential, , is dierent from the average potential. Using Boltzmann statistics
these quantities are connected by the relationship
cri c i expzi f 

3:8:6

where c i the concentration in moles per cubic meter and f e0/(kBT) F/(RT). If
the central ion is a cation, and  is positive, then the local concentration of other
cations is lower and that of anions higher. The extent to which the local concentration diers from the average concentration depends on the relative values of
the electrostatic energy, zie0, and the thermal kinetic energy, kBT. For a simple
electrolyte solution containing one cation with charge number z and one anion
with charge number z, the charge density at distance r is
rz z Fc expz f  z Fc  expz f 

3:8:7

where F is the Faraday constant (F NLe0). In a more general situation where the
solution contains more than two types of ions, one may write
rz

n
X

zi Fc i expzi f 

3:8:8

i1

Combination of equations (3.8.5) and (3.8.8) gives the PoissonBoltzmann


equation for the system:


n
X
1 d 2 d
zi Fc i
r


expzi f 
3:8:9
dr
ee
r2 dr
i1 s 0
There are two important problems with this equation. First, it is a non-linear
dierential equation because of the exponential terms in  and therefore cannot
be solved in a simple way. The second problem is that the solution of the statistical problem is not consistent with the fundamental laws of electrostatics. These
problems were overcome by Debye and Huckel [17] in a fairly simple way. In the
case that the electrostatic energy is small in comparison to the thermal kinetic

ELECTROLYTE SOLUTIONS

123

energy, the exponential term in equation (3.8.9) can be expressed by the rst two
terms in its Taylor series expansion. Thus, the expression for the charge density
becomes
rz

n
X

zi Fc i 

i1

n
X

z2i Ffc i 

3:8:10

i1

The rst term on the right-hand side of equation (3.8.10) gives the sum of the ionic
charges in the solution, which must add to zero. From the second term, one
denes an important quantity used in assessing the properties of electrolyte solutions, namely, the ionic strength, I. The denition is
I

n
1X
z2 c
2 i1 i i

3:8:11

For a 11 electrolyte, the concentrations of cations and anions are equal to the
overall bulk concentration c e and the charge numbers zi are 1 and 1. Then, the
ionic strength is also equal to the bulk concentration c e . For a 21 electrolyte,
such as ZnCl2, the cationic concentration is equal to c e , whereas the anionic
concentration is 2c e . In this case, the ionic strength is 3c e and recognizes the
higher charge on the cations. For a 22 electrolyte, such as ZnSO4, the ionic
strength is four times the bulk concentration. Of course, the ionic strength may
be expressed in other concentration units, including the molality me. It is an
important property of an electrolyte solution, especially in evaluating the extent
of departure of its properties from ideality.
When the DebyeHuckel approximation for the charge density rz is used, the
PoissonBoltzmann equation can be written as


1 d 2 d
2FfI
r

 k2 
3:8:12
2 dr
dr
es e0
r
where the constant k is given by
k



2FfI 1=2
es e0

3:8:13

Dimensional analysis shows that k has units of reciprocal length, and it is called
the DebyeHuckel reciprocal distance. It depends on the ionic strength of the
solution, the dielectric properties of the solvent, and temperature. For an aqueous
solution containing a 11 electrolyte at a concentration of 1 M (1000 mol m3) at
25 C, k is equal to 3.288 nm1. As will be seen below, 1/k corresponds to the
eective thickness of the ionic atmosphere, which would be 304 pm for a 1 M
solution.
The solution to the PoissonBoltzmann equation is now rather easily obtained.
First of all, one makes the substitution
y r
Then,

3:8:14

124

LIQUIDS, SOLUTIONS, AND INTERFACES

dy
d
r

dr
dr

3:8:15

d2 y
d
d2 
r 2
2
2
dr
dr
dr

3:8:16

and

The left-hand side of equation (3.8.12) gives




1 d 2 d
2 d d2 
r
2

dr
r dr
r2 dr
dr

3:8:17

so that the PoissonBoltzmann equation becomes


d2 y
k2 y
dr2

3:8:18

This is a well-known dierential equation in mathematical physics, whose general


solution is
y r k1 ekr k2 ekr

3:8:19

The constants k1 and k2 are determined by the boundary conditions for the
system. One of these states that the potential, , must go to zero as the distance,
r, goes to innity. This leads to the conclusion that term in ekr cannot contribute
to the potential ; as a result the constant k2 is zero. The solution to the Poisson
Boltzmann equation with one undetermined constant k1 is then


k1 kr
e
r

3:8:20

In order to determine the constant k1, one makes use of the relationship
between the charge density rz and local potential . From equations (3.8.10)
and (3.8.11),
n
X
rz 
z2i Ffc i  2FfI es e0 k2 
3:8:21
i1

The total charge in the solution outside a given reference ion must be equal and
opposite to the charge on the ion in order to maintain electroneutrality. Each ion
has an excluded volume around it into which the center of another ion may not
enter. For spherical ions this volume may be considered also to be spherical and
to have a radius a related to the sum of the radii of the cation and anion in a
simple electrolyte but not necessarily equal to that sum (see g. 3.5).
The cuto distance a denes the lower limit for integrating the charge density
outside of a reference ion in a calculation which allows one to determine the
constant k1. If the charge on the reference ion is zie0, one may write
1

4pr2 rz dr zi e0

3:8:22

where the integration involves adding the charge density in spherical shells of
volume 4pr2dr. Combining this with equations (3.8.20) and (3.8.21), one obtains

ELECTROLYTE SOLUTIONS

125

Fig. 3.5 Models for the excluded


volume around (a) a contact ion pair
and (b) a solvent-separated ion pair
with consideration of interaction of
their solvation atmospheres. The
radius of the excluded volume is
designated as a.
1

4prk1 es e0 k2 ekr dr zi e0

3:8:23

Integrating by parts, the result is


4pk1 es e0 kaeka eka zi e0

3:8:24

so that
k1

zi e0 eka
1
4pe0 es 1 ka

The solution of the PoissonBoltzmann equation is thus


 ka 
zi e0 ekr
e

4pe0 es r 1 ka

3:8:25

3:8:26

To proceed further, one must separate the contribution to  due to the ionic
atmosphere from the contribution that the ion makes itself in the absence of other
ions, that is, the so-called self-atmosphere potential. The latter quantity is given
by
ze
self i 0
3:8:27
4pe0 es r
It follows that atm estimated at r a, the distance to which other ions are absent,
is




zi e0
1
zi e0
zi e0
k

atm

3:8:28
4pe0 es a 1 ka
4pe0 es a
4pe0 es 1 ka
The remaining part of the problem involves relating the work done in forming
the ionic atmosphere to the activity coecient yi. If all departure from ideality is
attributed to the eects of ionion interactions, and the work done is estimated in
an imaginary charging process in which the reference ion acquires its charge in the
presence of all of the other ions, then
z
i e0



z2i e20
k
atm dzi e0 
8pe0 es 1 ka

3:8:29

For a mole of these ions, the relationship between the contribution to the Gibbs
energy due to the non-ideality and the work done is

126

LIQUIDS, SOLUTIONS, AND INTERFACES

RT ln yi 



NL z2i e20
k
8pe0 es 1 ka

3:8:30

Note that the activity coecient estimated is designated yi because the concentration of the ions is expressed in molarity units. Since k 3.288 I1/2 nm1 at 25 C in
water, the expression for ln yi for these conditions is
ln yi 

1:174 z2i I 1=2


1 3:288 a I 1=2

3:8:31

ADH z2i I 1=2


1 BDH aI 1=2

3:8:32

In general one may write


ln yi 

where ADH and BDH are the well-known DebyeHuckel constants. If the ionic
strength is expressed in moles per liter, then these constants are given by the
expressions

1=2
NL e20 F
2000
3:8:33
ADH
8p
e0 es RT3
and


2000 1=2
3:8:34
BDH F
e0 es RT
where the factor of 1000 is introduced to convert moles per liter to moles per cubic
meter. Values of ADH and BDH for water in the temperature range 0 to 50 C are
given in table 3.8.
The DebyeHuckel theory is also used to estimate activity coecients for dilute
solutions on the molality scale. In this case, equation (3.8.32) becomes
ln gi

0
ADH
z2i I 1=2
0
1 BDH aI 1=2

3:8:35

where I 1/2, A 0 , and B 0 are now the ionic strength and the DebyeHuckel constants
on the molality scale. Thus,
Table 3.8 Values of the DebyeHuckel Constants on the
Molarity Scale Together with the Density and Relative
Permittivity of Water in the Temperature Range 050 C
T/ C

rs/kg L1

es

ADH / L1/2 mol1/2

BDH/nm1 L1/2 mol1/2

0
10
20
25
30
40
50

0.99984
0.99970
0.99820
0.99705
0.99565
0.99222
0.98804

87.81
83.99
80.27
78.46
76.67
73.22
69.90

1.1309
1.1455
1.1638
1.1741
1.1856
1.2100
1.2374

3.2473
3.2611
3.2784
3.2881
3.2987
3.3212
3.3462

ELECTROLYTE SOLUTIONS

127

1X 2
z i mi
3:8:36
2
0
0
where mi is the molality of ion i. The constants ADH
, and BDH
for dilute solutions
(see equation (3.7.13)) are given by
 1=2
0
ADH
ADH rs
3:8:37
I

and
0
BDH
BDH rs 1=2


0
ADH

1=2

0
BDH

3:8:38

1:1724 kg mol
and
3:2832 nm kg mol1=2
Thus, at 25 C,
on the molality scale.
The DebyeHuckel equation as presented above is often called the extended
DebyeHuckel law (EDHL) because a simpler expression is used for very dilute
solutions. When the ionic strength is less than 0.001 M, the term in the denominator of equation (3.8.32) goes to one, and one may write
1=2

ln yi ADH z2i I 1=2

1

1=2

3:8:39

This result is known as the limiting DebyeHuckel law (LDHL) and gives a
remarkably simple way of estimating the eects of non-ideality in very dilute
electrolyte solutions. Although the model does not recognize the nite size of
the ions in solution or the structure of the solvent in a molecular sense, it points
out the importance of the ionic strength in determining the degree of departure
from ideality.
In order to examine the predictions of the model with respect to experimental
data, one must estimate the mean molar activity coecient. On the basis of
equation (3.6.17), this can be obtained from the relationship
n ln y n ln y n ln y
n z2 ADH I 1=2  n z2 ADH I 1=2

3:8:40

Electroneutrality requires that


jn z j jn z j

3:8:41

jn z2 j jn z z j

3:8:42

jn z2 j jn z z j

3:8:43

so that

and

Using equation (3.6.11), the expression for the LDHL becomes


ln y ADH jz z jI 1=2

3:8:44

In the same way, the corresponding expression for the EDHL is


ln y

ADH jz z jI 1=2
1 BDH aI 1=2

3:8:45

128

LIQUIDS, SOLUTIONS, AND INTERFACES

EXAMPLE

Estimate the mean ionic activity coecient for 0.04 M CaCl2 using the LDHL
and the EDHL at 258C assuming that the ion size parameter a is 0.47 nm.
Compare with the experimental value, which is 0.597.
The ionic strength of the solution is
I 1=20:04  4 0:08  1 0:12 M

3:8:46

According to the LDHL,


ln y Ajz z jI 1=2 1:174  2  0:121=2 0:8134
or
y 0:443

3:8:47

According to the EDHL,


ln y 

0:8134
0:5298
1 3:288  0:47  0:121=2

or
y 0:589

3:8:48

The result from the EDHL is much closer to the experimental value, as one
would expect.
Experimental values of ln y for NaCl are plotted against the square root of the
ionic strength in g. 3.6. Also shown are the values of ln y predicted by the
LDHL. It is clear that the limiting law agrees with the experimental data only
for the most dilute solutions (I < 0:001). At higher concentrations, the experimental results fall above the limiting law predictions, mainly because one must

Fig. 3.6 Plot of y on a logarithmic scale against the square root of the ionic strength, I 1=2
for aqueous NaCl at 258C. The straight line shows the prediction of the limiting Debye
Huckel law (equation (3.8.39)).

ELECTROLYTE SOLUTIONS

129

consider the eect of ionic size as expressed through the extended DebyeHuckel
equation. For electrolytes containing ions of higher charge the t between theory
and experiment is limited to even more dilute solutions.
In order to examine the eect of ionic size on the value of ln y , the experimental data are plotted in another way. Equation (3.8.45) may be rearranged to
give


Ajz z jI 1=2
1 BaI 1=2
ln y

3:8:49

Accordingly, a plot of the function on the left-hand side should give a straight line
when plotted against I 1=2 with a slope equal to Ba and an intercept of unity on the
y-axis. Such a plot with data for NaCl is shown in g. 3.7. It is apparent that these
conditions are met for ionic strengths less than 0.1 M I 1=2 < 0:3. At higher
concentrations there are positive deviations from the value of the ordinate predicted by the EDHL. The slope of the initial linear portion is 1.39, from which the
estimate of the ion size parameter is 420 pm.
Several reasons can be cited for the failure of the DebyeHuckel theory at
higher concentrations. One important reason is the fact that this model only
considers the fact that the central ion has size, and ignores the nite size of the
other ions in the atmosphere. As a result the thickness of the ionic atmosphere is
underestimated in concentrated solutions. In addition, the extra work involved in
introducing additional electrolyte ions into a concentrated solution while maintaining constant volume is neglected. This fact is mainly responsible for the
experimentally observed increase in ln y with increase in ionic strength (see g.
3.6). Finally, the structure of the solvent, water, is strongly aected by ionsolvent
interactions. As the concentration of the electrolyte increases, the fraction of

Fig. 3.7 Plot of the activity coecient data for aqueous NaCl at 258C according to equation (3.8.49). The value of the ion size parameter a from the slope in the limit of low
concentrations is 420 pm.

130

LIQUIDS, SOLUTIONS, AND INTERFACES

water molecules associated with ions increases, and the dielectric permittivity of
the solution decreases. This results in an increase in the strength of ionion
interactions and eventually can lead to ion pairing. In the following section a
method for estimating the activity coecients of electrolytes in more concentrated
solutions is considered, using a version of the MSA which ignores the molecular
nature of the solvent.

3.9 Ion-Ion Interactions According to the MSA


Although the DebyeHuckel theory of electrolyte solutions gives a good description of their physical properties when they are very dilute, it fails in a serious way
at higher concentrations, especially for electrolytes involving ions of higher
charge. In these systems the neglect of the nite size of all constituent ions is an
important defect and leads to overestimation of the eects of the ionion interactions. One way of overcoming this defect is to represent the electrolyte solution
as a collection of hard spheres of varying sizes, corresponding to the constituent
cations, anions, and solvent molecules. This approach was described earlier in the
discussion of ionsolvent interactions (section 3.5), and has also been applied to
the assessment of ionion interactions, especially in very dilute solutions [12].
Such an approach is called non-primitive because it considers the discrete nature
of the solvent molecules and ions which make up the electrolyte solution. A
method of treating these systems which falls between the DebyeHuckel model
and a non-primitive model represents the ions as hard spheres and the solvent as a
dielectric continuum. Such an approach is denitely primitive because it neglects
the molecular nature of the solvent, but it allows one to consider the eects of
ionic size more carefully than in the DebyeHuckel model, in which only the size
of the central ion was taken into account. In the MSA, all of the ions have a nite
size. As a result the distribution of ions around the central one is determined not
only by the local electrostatic potential but also by how well they can be packed in
space. It follows that the ionic distribution functions are not always smooth but
can have an oscillatory character, especially near the point of reference at the
central ion. When the cation and anion are assumed to have equal sizes the
present MSA treatment is called a restricted primitive model. Although presentations of the unrestricted version of the MSA are available [1820] the discussion
here is limited to the restricted version.
In the following model, the electrolyte is assumed to consist of ions having
radius ri and charge number zi . Since the solution is electrically neutral, the sum
of the concentration of each ion, c i times its valence zi must equal zero, that is
X
zi ci 0
3:9:1
i

The ions are embedded in a dielectric continuum of relative permittivity es . The


MSA boundary conditions for this system are
gij r 0;
and

r < 2ri

3:9:2

ELECTROLYTE SOLUTIONS

cij r buij r

zi zi be20
;
4pe0 es r

r > 2ri

131

3:9:3

On the basis of these conditions and the OrnsteinZernike equation, one obtains
the distribution functions gij r and cij r for all values of r.
An important parameter obtained in the solution of this problem is , which is
related to the thickness of the ionic atmosphere:
!1=2
NL e20 b X
z2i c i
3:9:4

4e0 es i 1 2ri 2
The concentration c i is expressed in moles per cubic meter. For the case that the
ions all have the same radius ri , 2ri is equal to the distance of closest approach, a,
dened in g. 3.5. Then, the summation in equation (3.9.4) can be related to the
ionic strength and the expression for  can be written as
k
3:9:5

21 a
where k is the DebyeHuckel reciprocal distance dened earlier (equation
(3.8.13)). It is obvious that in the limit that the ion size parameter a goes to
zero, 2 is equal to the reciprocal distance k. Solving equation (3.9.5) for ,
one obtains


1 2ak1=2  1
2a

3:9:6

In dilute solutions, the pair distribution function is


gij r

bzi zj e20 2r


e
4pe0 es r

3:9:7

This is exactly the form expected for gij r on the basis of the DebyeHuckel
model if 2 replaces k as the screening parameter.
The thermodynamic properties of the electrolyte solution are derived by rst
calculating the excess internal energy due to electrostatic interactions, Ues . This
quantity is given by
N e2 X z2i c i
3:9:8
Ues  L 0 
4pe0 es
1 2ri
i
where Ues has units of J m3 molec1 . For the case that all ions have the same
size, this reduces to
Ues 

NL e20
I
2pe0 es 1 a

3:9:9

The corresponding excess Helmholtz energy is estimated using the thermodynamic relationship
@bAes
Ues
@b

3:9:10

132

LIQUIDS, SOLUTIONS, AND INTERFACES

After some algebra, one obtains the result


Aes Ues

3
3pb

3:9:11

Since b 1=kB T, the term kB 3 =3p can be identied as the excess entropy
per unit volume associated with electrostatic interactions. One may now extract
the electrostatic contribution to the single ion activity coecient, which is


@bAes
be20 z2i 
bz2 Ues
ln yi es
i
3:9:12


NL @ci
4pe0 es 1 a
2NL I

After application of equation (3.8.42), the expression obtained for the mean ionic
activity coecient is
ln y es

bjz z jUes
2NL I

3:9:13

In order to complete the MSA estimate of ln yi one must add the hard-sphere
contribution, which accounts for the fact that work must be done to introduce the
ions as hard spheres into the solution. It is obtained from the PercusYevick
model for non-interacting hard spheres. For the case that all ions (spheres)
have the same radius, the result is (see equation (3.9.22))
ln yi hs

6z 3z2 2z

 2  3

3:9:14

where
1z

3:9:15

and
NL pa3
z

c i

3:9:16

Since ln yi is equal to ln yi hs when all the ions have the same size, the resulting
expression for the mean ionic activity coecient is
ln y ln y es ln y hs

3:9:17

Estimation of this quantity requires that only one adjustable parameter be specied, namely the mean ionic diameter a.
EXAMPLE

Estimate the mean activity coecient for 0.25 M NaCl according to the MSA
assuming an ion size parameter equal to 360 pm and a temperature of 258C.
For an ionic strength of 0.25 M, the DebyeHuckel parameter k is equal to
1.644 nm1 . The MSA  is now estimated using equation (3.9.6):


1 2  0:36  1:6441=2  1
0:6635 nm1
2  0:36

3:9:18

ELECTROLYTE SOLUTIONS

133

Now, Ues is calculated using equation (3.9.9). The constant NL e20 =2pe0 es is
equal to 3:541  106 J m mol1 so that
Ues

3:541  106  6:635  108  0:25  1000


1 0:6635  0:36

3:9:19

4:741  105 J m3 mol1


From equation (3.9.13)
ln y es

4:741  105
0:382
2  8:3144  298:2  250

3:9:20

In order to estimate the hard-sphere contribution the packing fraction z is


calculated rst:
z

6:022  1023  p  3:6  1010 3  250  2


7:36  103
6

3:9:21

Using equation (3.9.14),


ln y hs

6  7:36  103 3  7:36  103 2 2  7:36  103

0:060
0:9926
0:99262
0:99263
3:9:22

Thus,
ln y 0:382 0:060 0:322

3:9:23

The resulting estimate of y (0.725) agrees very well with the experimental
value (0.726).
The MSA model was tted to the activity coecient data for aqueous NaCl
solutions on the molarity scale following the procedure used in the above example. The results are shown in g. 3.8 for the case that the mean ionic diameter is
assumed to be 360 pm. An excellent t was found for concentrations up to 0.3 M.
At higher concentrations, the estimated value of ln y is higher than that found
experimentally. This is clearly a result of the hard-sphere contribution, which is
positive. Results obtained using the extended DebyeHuckel model are shown in
the same gure. This model requires that a higher average ionic diameter be
assumed and produces results which agree with experiment up to 0.1 M. The
DebyeHuckel model overestimates the eects of non-ideality at higher concentrations because it ignores the eects due to the size of all the ions in the system,
considering only the eect of the size of the central ion.
The t of the MSA to activity coecient data for aqueous electrolyte solutions
can be considerably improved if one takes into consideration the decrease in
solvent permittivity which accompanies the increase in electrolyte concentration.
This phenomenon is clearly related to the eect that ions have on solvent structure
and was studied originally in aqueous solutions by Hasted et al. [21, 22]. More
recently, data have been collected for a large number of electrolytes by Barthel
and coworkers [23]. In the case of NaCl solutions, the change in dielectric permittivity with electrolyte concentrations up to 2 M is given by

134

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 3.8 Plot of the mean ionic activity coecient for NaCl at 258C on a logarithmic scale
against the square root of the molar ionic strength. The points give the experimental data;
the curves give the theoretical ts for the MSA and extended DebyeHuckel models with
ion size parameters as indicated.

es 78:46  19ce 5c3=2


e

3:9:24

At a concentration of 0.1 M, the value of es is 76.7 but when the concentration is


1 M, es falls to 64.5. The extent to which the permittivity changes with concentration also depends on the nature of the electrolyte. This aspect of solvent properties
is discussed in more detail in section 4.6.
When the variation in es with electrolyte concentration is considered the
expression for ln yi es becomes
ln yi es

bz2i Ues
be20 I
@es

2NL I
2e0 e2s 1 a @c i

bz2 Ues bUes @es



i
2NL I
NL es @c i

3:9:25

Making use of equation (3.9.13), the mean ionic activity coecient is


ln y es

jz z jbUes bUes @es



2NL I
nNL es @c e

3:9:26

where
@es
@e
@e
n s n s
@c e
@c
@c

3:9:27

@es =@c e can be measured experimentally and in the present example is calculated
from the concentration derivative of equation (3.9.24).
The t of the MSA model with varying solvent permittivity is shown in g. 3.9.
These results demonstrate the importance of considering the true solvent permit-

ELECTROLYTE SOLUTIONS

135

Fig. 3.9 As in g. 3.8, but with a varying dielectric permittivity for the solvent in the MSA
model (see equation (3.9.26)).

tivity in estimating ionion interactions. The value of the size parameter a which
yields the best t (436 pm) is somewhat larger than that found for the simpler
MSA t with a constant permittivity equal to that of the pure solvent. At concentrations higher than 1 M, the MSA curve lies above the experimental results.
This undoubtedly reects a small extent of ion pairing in concentrated solutions
of 11 electrolytes so that the true ionic strength is somewhat less than that
estimated on the basis of the stoichiometric concentration.
It should be noted that redening the DebyeHuckel constants so that they
change with electrolyte concentration to reect the corresponding change in es
does not extend the concentration range over which this model ts experimental
data. This result emphasizes that it is important to include the nite size of all ions
in a model which is applied in a concentration range greater than 0.1 M.
Inclusion of the change in solvent permittivity in the MSA description is an
eective way of dealing with the change of solvent properties which accompany
the addition of an electrolyte to a polar solvent. Since permittivity data are now
available for a large number of electrolyte solutions in water [23], the MSA model
can be applied to a wide variety of systems. However, there is one feature of
electrolyte solutions which has been neglected in the treatments presented up to
this point, namely, the existence of ion aggregates. This feature of electrolyte
solutions is discussed in the following sections of this chapter.

3.10 The Thermodynamics of Ion Association


Two important factors which determine whether ionic association is present in an
electrolyte solution are the charge on the ions and the dielectric permittivity of the
solvent. Their roles are clearly seen on the basis of Coulombs law, which shows

136

LIQUIDS, SOLUTIONS, AND INTERFACES

that the force between two ions increases with increase in the product of their
charges and with decrease in the solvents permittivity, that is
Fc

zi zj e20
4pe0 es r2ij

3:10:1

where zi and zj are the valences of the two ions, and rij , the distance between them.
Another factor to be considered is chemical bonding between two ions to form a
molecule. This phenomenon falls under the general classication of weak electrolytes, which were discussed in section 3.6.
Derivation of the thermodynamic equations for an electrolyte system with ion
pairing follows the same procedure given for a weak electrolyte. However, in the
following the ion pairing equilibrium is dened in terms of an association process.
For a 11 electrolyte, ion pairing is described as
M X  (
+ MXip

3:10:2

where MXip represents the neutral ion pair. The association equilibrium constant
Kas is given by
aip
3:10:3
Kas
aM aX
where aM and aX are the activities of the cation and anion, respectively, and aip ,
that of the ion pair. The association constant may be written in terms of the
standard potentials of each of these species as follows:
RT ln Kas mM mX  mip

3:10:4

Here mM and mX are the standard chemical potentials for the two ions on the
molarity scale, and mip , that for the ion pair.
As a result of ion pairing, a fraction ai of the dissolved electrolyte remains in
solution as ions and a fraction 1  ai exists as ion pairs. Thus, the chemical
potential of the electrolyte can be expressed as
mMX ai mM ai mX 1  ai mip

3:10:5

where mM and mX are the chemical potentials of the ions and mip , that of the ion
pair. Substituting equations (3.10.3) and (3.10.4) into equation (3.10.5), one
obtains
mMX mM mX RT ln aM aX

3:10:6

This result shows that the chemical potential of the electrolyte can be expressed in
terms of the activities of the two ions without considering that of the ion pair. It
was obtained earlier for weak electrolytes as equations (3.6.38) and (3.6.40).
Because of ion pairing the ionic activities aM and aX are less than they would be
on the basis of the stoichiometric concentration of the electrolyte, ce . Expanding
the activities in equation (3.10.3) in terms of activity coecients and concentrations, one can write
Kas

yip cip
1  ai yip

yM c M yX c X
y2 a2i ce

3:10:7

ELECTROLYTE SOLUTIONS

137

where yip is the activity coecient of the ion pair, cip , its concentration, yM and
yX , the activity coecients for the individual ions, y , the mean ionic activity
coecient, and cM and cX , the concentration of the two free ions, which are equal
to each other. One may also write the activity product aM aX as
aM aX a2i y2 c2e

3:10:8

It is clear that the value of Kas must be known in order to assess the thermodynamic properties of an electrolyte system in which ion pairing takes place. The
above equations may also be written on the molality scale (see section 3.6).
It should be noted that experimental activity coecient data for systems
known to undergo ion pairing are tabulated ignoring ion pairing. In this case
the tabulated ionic activity coecient on the molality scale must be regarded as
giving ai g , not  . For example, moderate ion pairing occurs in NaF solutions.
Given that the tabulated mean ionic activity coecient for 0.1 m NaF is 0.765 and
assuming Kas 1 and gip 1, the value of ai in this solution is 0.941 on the basis
of equation (3.10.7). It follows that the true mean ionic activity coecient is
0.765/0.941, that is, 0.813. This calculation requires a value of Kas which must
be obtained on the basis of additional experimental information. Small changes in
the assumed value of Kas have a large eect on the result of the calculation,
especially at high electrolyte concentrations.
EXAMPLE

A reasonable estimate of the thermodynamic association constant for MgSO4


is 164. The experimental value of g in 0.4 m MgSO4 is 0.0756. Estimate the
true value of g assuming that the activity coecient of the ion pair is unity.
On the basis of equation (3.10.7), one may write on the molal scale with
gip 1,
1a
Kas 164
g2 a2 me

3:10:9

Substituting for ai g , 0.0756, and for me , 0.4, one obtains


1  ai 0:375

3:10:10

Thus, the fraction dissociated ai is 0.625 and the true activity coecient g is
0.121.
The above example shows that the same analysis can be applied to a symmetrical electrolyte containing ions of higher charge, for example MgSO4. In the case
of non-symmetrical electrolytes such as MgCl2, the ion association process can be
more complex. For the 21 electrolyte MX2, two association steps are possible:
M2 X (
+ MX

Kas1

3:10:11

+ MX2
MX X (

Kas2

3:10:12

and
+

Formation of the ion pair MX is expected to take place under most circumstances. However, formation of the ion triplet MX2 may not be signicant, especially in aqueous solutions. Important factors determining the magnitude of the

138

LIQUIDS, SOLUTIONS, AND INTERFACES

association constants are the charges on the ions and the solvent permittivity, as
can be seen from equation (3.10.1). An analysis of the properties of a system
containing more than one association step to obtain the concentrations and activities of the component ions is obviously a complicated problem. However, if the
association constants are known, methods exist for estimating the activity coecients of the system over a wide concentration range [24].
Considerable eort has been made to develop a model for the parameter Kas on
the basis of statistical theories using simple electrostatic concepts. The rst of
these was proposed by Bjerrum [25]. It contains important ideas which are
worth reviewing. He assumed that all oppositely charge ions within a certain
distance of a central ion are paired. The major concept in this model is that
there is a critical distance from the central ion over which ion association occurs.
Obviously, it must be suciently small that the attractive Coulombic forces are
stronger than thermal randomizing eects. Bjerrum assumed that at such short
distances there is no ionic atmosphere between the central ion and a counter ion
so that the electrostatic potential due to the central ion may be calculated directly
from Coulombs law. The value of this potential at a distance r is


zi e0
4pe0 es r

3:10:13

where zi e0 is the charge on the central ion. The concentration of counter ions with
charge zj e0 at the same distance is estimated using Boltzmann statistics so that
crj c j expzj f 

3:10:14

where c j is the bulk concentration in ions per cubic meter and f e0 b. Combining
these equations one obtains an expression for the probability Pr of nding two
oppositely charged ions at a distance r from each other:
!
zi zj e20 b
2
Pr 4pr cj exp
3:10:15
4pe0 es r
This function has two opposing trends: rstly, as r increases the exponential term
decreases due to the decrease in Coulombic attraction; secondly, the volume
associated with the sphere containing possible counter ions increases as 4pr2 .
Thus, the probability has a minimum whose location can be found by dierentiating Pr with respect to r. The condition for a minimum is

q

q
dPr
q
B
B
8prc j exp
4pr2 c j B2 exp
0
3:10:16
dr
r
r
r
where
zi zj e20 b
3:10:17
4pe0 es
Dening rB as the distance corresponding to the minimum, it follows that
qB

rB

zi zj e20 b
qB

8pe0 es
2

3:10:18

ELECTROLYTE SOLUTIONS

139

The value of the Bjerrum distance rB depends on the ionic charges, the nature of
the solvent and the temperature but not on electrolyte concentration. For aqueous
solutions of 11 electrolytes at 258C, it is equal to 357 pm. Bjerrum proposed that
all ions contained in a sphere with this radius are paired. This is a reasonable
proposal for aqueous systems, since ions of typical size would be close to contact
at such small separations. However, if the solvent has a lower dielectric permittivity, the distance over which ions are considered to be paired increases and the
assumption that they are in contact is more dicult to accept. For example, when
the solvents relative permittivity is 10, the Bjerrum distance rB increases to
2800 pm.
A plot of the Bjerrum probability function against distance r is shown for an
aqueous solution in g. 3.10. The probability of nding an oppositely charged ion
rises rapidly from the minimum at 357 pm as the distance between ions gets
smaller. An increase in probability is also seen as distance increases from the
minimum. The function Pr is limited for small values of r by the fact that
oppositely charged ions can approach the central ion up to the distance of closest
approach a. However, there is no limit in Pr for large values of r. Bjerrum
obtained an estimate of the number of paired ions by integrating Pr from the
distance of closest approach a to the minimum on the probability curve rc . In this
way, he was able to obtain an estimate of the association constant Kas . Further
details may be found in the monograph by Robinson and Stokes [G1].
As suggested by the above discussion, there are serious problems with the
Bjerrum model. One of these relates to the fact that unreasonably large critical
distances are involved in dening an ion pair in solutions of low permittivity. The
second relates to the fact that the probability distribution is not normalized and
continues to increase with increase in distance r. The latter problem is eectively
avoided by considering only those values of Pr up to the minimum in the curve.

Fig. 3.10 Bjerrum probability function Pr for oppositely charged ions plotted against r,
the distance from a central ion for a 11 electrolyte at 1 M in water at 258C with es 78:46:

140

LIQUIDS, SOLUTIONS, AND INTERFACES

Fuoss [26] revised the distribution function taking into account the fact that the
probability should go to zero for large values of r. However, the modied function
describing Pr is essentially the same as that given by Bjerrum for small values of
r. Therefore, the simpler theory is that usually used.
Fuoss developed a new theory of ion association in 1958 [27] which overcame
some of the diculties associated with the Bjerrum approach. The cations in the
solution were assumed to be conducting spheres of radius a and the anions to be
point charges. The ions are assumed to be immersed in a dielectric continuum of
permittivity es . Only oppositely charged ions separated by the distance a are
assumed to form ion pairs. The resulting expression for the association constant
is


4000pa3 NL
jqB j
Kas
exp
3
a

3:10:19

The most important quantity determining the magnitude of Kas is the ion size
parameter a, which appears to the third power in the numerator and also in the
exponential term. The role of the solvent and the charges on the two ions is
expressed through the parameter qB (equation (3.10.17)). This quantity increases
with the charge product jzi zj j and with decrease in the solvent permittivity. In the
case of MgSO4, assuming a is equal to 450 pm, the value of jqB j=a is 6.35. The
estimate of Kas according to equation (3.10.19) is 132. This result is the correct
order of magnitude on the basis of other experimental evidence.
The Fuoss estimate of Kas is based on a more reasonable model than that of
Bjerrum and therefore is preferred. However, there are also problems with the
Fuoss treatment in so far as it considers the solvent to be a dielectric continuum.
Dielectric saturation eects are expected to be important, especially near the ions
involved in ion pair formation. The second problem relates to the choice of the
eective size for the ions. In the calculation made here the value of a for MgSO4
was chosen to be much bigger than the crystallographic radius of Mg2 . This
presumably is because the cation is strongly hydrated in aqueous solution. One is
then faced with the question whether the ion pair involves contact of the two ions
or whether it is better considered to be a species in which the two ions are
separated by at least one water molecule. These questions can only be properly
resolved using other experimental methods.
In summary, both models are useful from a qualitative point of view in assessing the strength of ion pairing in a given system. They demonstrate the importance of the ionic charge and the dielectric permittivity of the medium in
determining Kas . In order to obtain a good quantitative estimate of Kas , as, the
size of the ions involved must be carefully determined.

3.11 Ion Association According to the MSA


In the treatment of ionic activity coecients according to the MSA it was emphasized that the nite size of the ions is an important factor in estimating their Gibbs
energy. Accordingly, the work done to introduce an additional ion to the solution

ELECTROLYTE SOLUTIONS

141

increases at constant solution volume with increase in electrolyte concentration.


This is the hard-sphere contribution to the activity coecient which depends on
the size of the ions and on their concentration.
When ion pairing is present there are three solute species, the additional one
being the ion pair. This species is expected to be larger than either the cation or
the anion, and to be a factor in determining the hard-sphere contribution to the
Gibbs energy. In more traditional treatments of ion pairing, the activity coecient
of the ion pair was assumed to be unity. On the basis of the MSA it is greater than
one, and depends on electrolyte concentration.
For the case of symmetrical electrolytes with ion pairing, the electrolyte activity
is given by
aM aX a2i y2 c2e
3:11:1
where ai is the fraction of the ions remaining free, y , the mean activity coecient
on the molarity scale, and ce , the electrolyte molarity. On the basis of the ion
pairing equilibrium
Kas

1  ai yip
y2 a2i ce

3:11:2

where Kas is the ion pairing equilibrium constant and yip , the activity coecient of
the ion pair. Estimation of the activity coecients and the fraction ai requires
knowledge of two parameters, namely Kas , and a, the mean diameter of the three
solute species. As outlined earlier (section 3.9), y consists of an electrostatic
contribution and a hard-sphere contribution. The rst is
ln y es

jz z jbUes bUes @es



2NL I
nNL es @c e

3:11:3

where Ues is dened by equation (3.9.9) and c e is the concentration in moles per
cubic meter. The hard sphere contribution is given by equations (3.9.14)(3.9.16)
in the restricted approximation. It is then equal for all solute species so that
ln yip ln y hs ln yi hs

3:11:4

Finally, the experimentally available activity coecient is (y exp where


y exp ai y ai y es y hs

3:11:5

Given values of a and Kas , the activity coecient y is calculated in the following way. Initially assuming ai 1, the value of (y es is estimated using equations
(3.11.3) and (3.11.4) with the values of c e and a. Now equation (3.11.2) may be
solved for ai given Kas . The process is repeated using the new estimate of ai until
successive estimates of y agree to the required precision.
Results of such an analysis for the MgSO4 system are shown in g. 3.11. The
best values of a and Kas for this system are 610 pm and 185 L mol1 , respectively.
On the basis of dielectric relaxation experiments, the permittivity of MgSO4
solutions as a function of electrolyte concentration is given by
es 78:5  31:8ce 12:8c3=2
e

3:11:6

An excellent t between the MSA model and experimental data is possible for
concentrations up to 1.5 M (see g. 3.11). At higher concentrations, the theory

142

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 3.11 Plot of the eective mean ionic activity coecient for MgSO4 at 258C on a
logarithmic scale against the square root of the molar ionic strength. The curve gives the
t with the modied MSA assuming a 610 pm and Kas 185 L mol1 ; the straight line
shows the prediction of the limiting DebyeHuckel law.

predicts values of y which are higher than those found experimentally. This is
probably because the eective size of the ions, especially the strongly hydrated
Mg2 ion, decreases at high concentrations, where there are fewer water molecules
available per ion.
It is very interesting to examine how the mean activity coecient for the ions,
y , the ion pair, yip , and the fraction of electrolyte dissociated, ai , vary with
electrolyte concentration. These quantities are plotted against ce for the range
over which the theory is successful in g. 3.12. The mean ionic activity coecient

Fig. 3.12 Plots of yip , y , and ai on a logarithmic scale for the MgSO4 system according to
the modied MSA model at 258C against electrolyte concentration ce in water.

ELECTROLYTE SOLUTIONS

143

y falls to very low values as one would expect for a 22 electrolyte at high ionic
strength. In this regard it should be remembered that a concentration of 1.5 M
corresponds to an ionic strength of 6 M, so that the theory has been very successful in describing the electrostatic interactions. At the same time the activity coecient of the ion pair increases reaching values greater than 2. This has an
important inuence on the estimate of ai and the nal estimate of the overall
mean electrolyte activity coecient ai y . The fraction of electrolyte dissociated is
initially close to 0.6 and then slowly increases. This reects changes in the apparent association constant with ionic strength and is an important factor in determining the ionic strength. On the basis of equation (3.11.2) the apparent
association constant may be dened as
Kap

Kas y2
yip

3:11:7

It decreases with increasing ionic strength due to the corresponding decrease in


y and increase in yip . As a result, there is a slow increase in ai , the fraction
dissociated, at higher concentrations.
In conclusion, the MSA provides an excellent description of the properties of
electrolyte solutions up to quite high concentrations. In dilute solutions, the most
important feature of these systems is the inuence of ionion interactions, which
account for almost all of the departure from ideality. In this concentration region,
the MSA theory does not dier signicantly from the DebyeHuckel model. As
the ionic strength increases beyond 0.1 M, the nite size of all of the ions must be
considered. This is done in the MSA on the basis of the hard-sphere contribution.
Further improvement in the model comes from considering the presence of ion
pairing and by using the actual dielectric permittivity of the solution rather than
that of the pure solvent.

3.12. Concluding Remarks


The theory of electrolyte solutions developed in this chapter relies heavily on the
classical laws of electrostatics within the context of modern statistical mechanical
methods. On the basis of DebyeHuckel theory one understands how ionion
interactions lead to the non-ideality of electrolyte solutions. Moreover, one is able
to account quantitatively for the non-ideality when the solution is suciently
dilute. This is precisely because ionion interactions are long range, and the
ions can be treated as classical point charges when they are far apart. As the
concentration of ions increases, their nite size becomes important and they are
then described as point charges within hard spheres. It is only when ions come
into contact that the problems with this picture become apparent. At this point
one needs to add quantum-mechanical details to the description of the solution so
that phenomena such as ion pairing can be understood in detail.
The above comments also apply to the description of ionsolvent interactions. The traditional treatment of a solvent molecule is to represent it as a hard
sphere with a central point dipole. Such a model ignores the details of the

144

LIQUIDS, SOLUTIONS, AND INTERFACES

chemical nature of the interactions between the ion and the surrounding solvent
molecules.
In summary, the models discussed in this chapter focus on the physical
aspects of electrolyte solutions but they ignore the chemical aspects. This is
especially apparent in the treatment of ion solvation where an empirical correction to the MSA model was applied to treat the dierences in behavior seen for
cations and anions in water. The same problem arises in using classical electrostatics to describe ion pairing. In spite of the fact that the Bjerrum and Fuoss
models give a good qualitative description of an ion association, this phenomenon can only be understood in detail by using quantum-mechanical methods.
Needless to say, such calculations in condensed media are much more dicult to
carry out.
The problems outlined here can be greatly elucidated using spectroscopic methods. With the appropriate technique one can probe the strength of ionsolvent
interactions, and measure the extent of contact ion pairing. Spectroscopic studies
of electrolyte solutions have certainly greatly improved the understanding of these
important systems. Major spectroscopic methods and results of their application
to these systems are considered in detail in chapter 5.

General References
G1. Robinson R. A.; Stokes, R. H. Electrolyte Solutions, 2nd ed.; Butterworths: London,
1968.
G2. Petrucci, S. Ionic Interactions; Academic Press: New York, 1971; Vols. I and II.
G3. Marcus, Y. Ion Solvation; Wiley-Interscience: New York, 1985.
G4. Wagman, D. D.; Evans, W. H.; Parker, V. B.; Schumm, R. H.; Halow, I.; Bailey, S.
M.; Churney, K.L.; Natall, R. L. J. Phys. Chem. Ref. Data 1982, 11, Supp. 2.
G5. Lobo, V. M. M. Handbook of Electrolyte Solutions; Elsevier: New York, 1989.
G6. Horvath, A. L. Handbook of Aqueous Electrolyte Solutions; Ellis Horwood:
Chichester, 1985.

References
1. Ohtaki, H.; Radnai, T. Chem. Rev. 1993, 93, 1157.
2. Pauling, L. The Nature of the Chemical Bond, 3rd ed.; Cornell University Press: Ithaca,
NY, 1960; Chap. 13.
3. Gourary, B. S.; Adrian, F. J., Solid State Phys. 1960, 10, 125.
4. Morris, D. F. C. Struct. Bonding 1968, 4, 63.
5. Shannon, R. D.; Prewitt, C. T. Acta Crystallogr. 1969, B25, 925.
6. Szasz, G. I.; Heinzinger, K.; Palinkas, G. Chem. Phys. Lett. 1981, 78, 194.
7. Jenkins, H. D. B.; Thakur, K. P. J. Chem. Educ. 1979, 56, 576.
8. Bowen, K. H.; Castleman, A. W. J. Phys. Chem. 1996, 100, 12911.
9. Tissandier, M. D.; Cowen, K. A.; Feng, W. Y.; Gundlach, E.; Cohen, M. H.; Earhart,
A. D.; Coe, J. V.; Tuttle, Jr., T. R. J. Phys. Chem. A 1988, 102, 7787.
10. Fawcett, W. R. J. Phys. Chem. B 1999, 103, 11181.
11. Born, M. Z. Phys. 1920, 1, 45.
12. Chan, D. Y. C.; Mitchell, D. J.; Ninham, B. W. J. Chem. Phys. 1979, 70, 2946.
13. Garisto, F.; Kusalik, P. G.; Patey, G. N. J. Chem. Phys. 1983, 79, 6294.
14. Blum, L.; Fawcett, W. R. J. Phys. Chem. 1992, 96, 408.
15. Wertheim, M. S. J. Chem. Phys. 1971, 55, 4291.
16. Fawcett, W. R.; Blum, L. J. Chem. Soc. Faraday Trans. 1992, 88, 3339.

ELECTROLYTE SOLUTIONS

17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.

145

Debye, P.; Huckel, E. Phys. Z. 1923, 24, 185.


Blum, L. Mol. Phys. 1975, 30, 1529.
Blum, L.; Hoye, J. S. J. Phys. Chem. 1977, 81, 1311.
Humray, A. A. J. Phys. Chem. 1983, 87, 5521.
Hasted, J. B.; Ritson, D. M.; Collie, C. H. J. Chem. Phys. 1948, 16, 1.
Haggis, G. H.; Hasted, J. B.; Buchanan, T. J. J. Chem. Phys. 1952, 20, 1452.
Barthel, J.; Buchner, R.; Munsterer, M. Electrolyte Data Collection, Part 2: Dielectric
Properties of Water and Aqueous Electrolyte Solutions; Dechema: Frankfurt/Main,
1995.
Pitzer, K. S. Activity Coecients in Electrolyte Solutions, 2nd ed.; CRC Press: Boca
Raton, FL, 1991.
Bjerrum, N. Kg. Danske Videnskab. Selskab. 1926, 7, 9.
Fuoss, R. M. Trans. Faraday Soc. 1934, 30, 967.
Fuoss, R. M. J. Am. Chem. Soc. 1958, 80, 5059.

Problems
1. Nitromethane (NM) is a polar solvent with a relative permittivity of 35.8
at 258C. It has a diameter of 431 pm when represented as a sphere.
Estimate the Gibbs energy of solvation of K+, whose diameter is
276 pm, in NM according to the Born model and MSA at 258C.
Compare these estimates with the experimental estimate, which is
300 kJ mol1 .
2. Estimate the entropy of solvation of K+ in NM given that the temperature coecient of the permittivity is 0:161 K1 . Use both the Born model
and the MSA. Compare these with the experimental estimate of
181 J K1 mol1 at 258C. What are the contributions to long-range interactions which depend on des =dT, and local interactions which depend on
dds=dT, in this estimate?
3. Estimates of the Gibbs energy of solvation of the alkali metal ions in
acetonitrile are 464 (Li+), 374 (Na+), 307 (K+), 288 (Rb+), and
257 kJ mol1 (Cs+) at 258C. Estimate the MSA parameter ds for acetonitrile using a plot of s Gm 1 against cation radius. Compare this
result with the value estimated from the permittivitry which is equal to
35.9.
4. The activity coecient on the molality scale for NaI at 258C is 0.938 at
0.1 m and 0.991 at 1 m. Estimate the corresponding concentrations in mol
L1 using the density data summarized in table 3.6, and hence, the activity
coecients on the molarity scale.
5. Use the extended DebyeHuckel theory to estimate the mean ionic activity
coecient for Na2SO4 at concentrations of 0.01 and 0.1 M and 258C
assuming an ion size parameter of 400 pm. Also calculate the mean electrolyte activity and the electrolyte activity.

146

LIQUIDS, SOLUTIONS, AND INTERFACES

6. Given the following activity coecient data determine the average ionic
radius for each electrolyte according to the extended DebyeHuckel equation. All data were obtained in water at 258C.
y
Conc/M

NaCl

CaCl2

0.001
0.002
0.005
0.01
0.02
0.05
0.1
0.2
0.5

0.965
0.953
0.927
0.900
0.869
0.820
0.780
0.738
0.687

0.888
0.851
0.787
0.729
0.664
0.577
0.517
0.469
0.444

Rearrange the extended DebyeHuckel equation so that the experimental


data may be plotted as a straight line depending on the square root of the
ionic strength whose slope is proportional to the average ionic radius.
7. On the basis of the equation
ln y

ADH zA zB I 1=2
CI
1 BDH aI 1=2

derive an expression for the ionic strength at which ln y is a minimum.


Given that the minimum value of y for CaCl2 is 0.444, and using the
results obtained in question 6, determine the appropriate value of C to t
the equation to these data. Calculate y for ce 1 and 3 M. Then plot ln
y versus I 1=2 showing the prediction of the LDHL on the graph.
8. The true solubility product (I 0) for calcium hydroxide is 6:5  106 at
258C. Estimate its solubility in (a) water, and (b) 0.1 M NaNO3 using the
EDHL BDH a 1 to estimate activity coecients. Calculate the pH of
the solutions in each case.
9. Estimate the activity coecient for KBr in water at 258C using the MSA
with an ion size parameter of 470 pm at concentrations of 0.1 M and
0.5 M. Estimate the solution permittivity using equation (3.9.18).
Compare with the experimental values, which are 0.818 (0.1 M) and
0.666 (0.5 M).
10(a). Use the Fuoss equation (3.10.19) to estimate an association constant for
ZnSO4 assuming an ion size parameter of 650 pm.
(b). Estimate the fraction a of free ions using the formula

ELECTROLYTE SOLUTIONS

Kas

147

1a
g2 a2 ce

which assumes that the activity coecient of the ion pair is unity. It is
necessary to use an iterative technique to solve this problem.
11(a). Estimate the DebyeHuckel constants ADH and BDH in dimethylsulfoxide
at 258C given that the density of DMSO is 1.096 g cm3 and its permittivity 46.7.
(b). Use the following activity coecient data for LiCl in DMSO to estimate
an ion size parameter for the electrolyte on the basis of the EDHL.
m

0.005
0.01
0.02
0.03
0.05
0.08
0.10
0.12

0.859
0.803
0.736
0.698
0.644
0.600
0.578
0.559

Polar Solvents

Peter Debye was born in 1884 at Maastricht,


the Netherlands, where he also grew up. After
secondary school he studied electrical
technology at the Institute of Technology in
Aachen and graduated in 1905. After two years
as an assistant in the same institute, Debye
moved to Munich University to study physics
and obtained a Ph.D. in physics in 1908. In
1911, he was appointed Professor of
Theoretical Physics at Zurich University. He
Peter Joseph Wilhelm Debye held chairs at Utrecht, and Gottingen, before
moving to ETH Zurich in 1920 as Professor of
Physics and Principal. In 1927, he held the same post at Leipzig University and
in 1934 he was appointed Director of the Max Planck Institute at the Kaiser
Wilhelm Institute of Physics in Berlin. With the outbreak of war in Europe,
Debye moved to Cornell University in the United States as Professor of
Chemistry and Chair of the Chemistry Department. He held that position until
his retirement in 1952. Debyes work is remembered in several, quite dierent,
areas of physical chemistry. One of his rst important contributions was made
in 1912 to the theory of specic heat of solids, in which he extended the earlier
work of Einstein. In 1923, while at Zurich, he published the famous theory of
strong electrolytes, together with Erich Huckel. He worked extensively on the
dielectric properties of matter and published his famous monograph Polar
Molecules [1] in 1929. Another area in which he contributed signicantly was
X-ray crystallography. Debye was awarded the Nobel Prize for Chemistry in
1936 for his contribution to explaining the structure of molecules, his research
into dipole moments, and his work on the electronic diraction of gases. His
devotion to science gained him many distinctions and international awards. He
died in Ithaca, New York, in 1966.

4.1 What Constitutes a Polar Liquid?


Polar solvents are those liquids whose relative permittivity is suciently high that
electrolytes can be dissolved in them. The best-known example of such a liquid is
water. The oxygen end of this simple molecule is electron-rich and can stabilize
cations. The hydrogen atoms are electron-poor and thus are involved in the
solvation of anions. The structure of pure water is very much inuenced by the
148

POLAR SOLVENTS

149

hydrogen bonding between the negative end of the molecular dipole at oxygen
and a hydrogen atom on an adjacent molecule. The special properties of water as
a solvent for electrolytes are the central reason for its importance in living systems.
There are many other solvents which can be classied as polar. Some of them,
such as the alcohols, have the same polar group as the water molecule, namely,
the hydroxyl group OH. These solvents are also involved in hydrogen bonding,
and are generally classied as protic. Other examples of protic solvents are simple
amides such as formamide and acetamide. In these systems, the protic group is
NH2, the hydrogen atom being involved in hydrogen bonding with the oxygen
atom in the carbonyl group on an adjacent molecule.
There are other polar solvents which are not protic. These involve liquids with
large dipole moments. Some examples are acetonitrile, propylene carbonate, and
dimethylsulfoxide. In each case, the solvent molecule possesses an electronegative
group which is rich in electrons. The opposite end of the molecule is electron
decient but does not have acidic hydrogen atoms which can participate in hydrogen bonding. This class of solvents is called aprotic.
In this chapter, the properties of polar solvents are discussed, especially as they
relate to the formation of electrolyte solutions. Polar solvents are arbitrarily
dened here as those liquids with a relative permittivity greater than 15.
Solvents with zero dipole moment and a relative permittivity close to unity are
non-polar. These include benzene, carbon tetrachloride, and cyclohexane.
Solvents with relative permittivities between 3 and 5 are weakly polar, and
those with values between 5 and 15 are moderately polar. The latter systems
are not considered in the discussion in this chapter.
Initially, some relevant thermodynamic and molecular properties of polar solvents are considered. Then, their dielectric properties are considered in detail. Ion
solvation in these solvents is also discussed with emphasis on some non-thermodynamic methods of dividing experimentally measured data for electrolytes into
contributions for the cation and anion. Finally, the important characteristics of
the solvent in its direct interaction with the solute, namely, its acidity and basicity,
are also described.

4.2 Some Important Properties of Polar Solvents


A number of properties, including dielectric properties, should be considered in
assessing a given polar solvent. Important bulk properties are density, vapor
pressure, thermodynamic properties related to vaporization, heat capacity, viscosity, compressibility, and surface tension. Some of these are summarized in table
4.1 and are discussed briey in this section.
Water is unique among polar solvents in that it is a small molecule with a low
molar volume. As a result, the concentration of water in pure water is 55.5 M.
This means that the mole fraction of water in dilute aqueous solutions is close to
one, and the partial molar quantities in these solutions are close to the corresponding quantities for the pure solvent. Other solvents have considerably higher
molar volumes, and therefore, lower concentrations in the pure solvent. The

Table 4.1 Thermodynamic Properties of Selected Polar Solvents at 25 Ca

Solvent

Molecular
Mass
/g mol1

Molar
Volume
/cm3 mol1

Enthalpy of
Vaporization
/kJ mol1

Entropy of
Vaporizationb
/K1 mol1

Molar Heat
Capacity
/J K1 mol1

18.02
32.04
46.07
60.10
74.12
45.04
59.07

18.07
40.73
58.69
75.14
92.0
39.89
59.14

44.0
37.4
42.3
47.5
52.4
65.0
59.6

108.9
104.8
110.1
111.3
110.4
98.1
99.8

75.3
81.5
112.3
143.8
177.1
107.6
123.8

58.08
41.05
103.12
69.11
87.12
73.09
78.13
179.20
99.13
123.11
61.04
55.08
102.08
120.17
116.16

74.04
52.86
103.06
87.87
93.05
77.4
71.3
175.7
96.4
102.7
54.0
70.9
85.2
95.3
120.3

31.3
32.9
55.5
39.3
49.2
47.5
52.9
61.1
54.0
55.0
38.3
36.1
65.3
79.5
45.5

88.4
84.0
98.9
88.1
98.7
90.0
93.3
112.2
94.0
84.2
91.9
83.6
93.1
107.3
101.4

124.9
91.5
190.3
155.8
176
148.4
153.2
321.3
166.4
177.1
105.8
119.7
160.2
180.0
229.6

Protic
1.
2.
3.
4.
5.
6.
7.

Water (W)
Methanol (MeOH)
Ethanol (EtOH)
1-Propanol (PrOH)
1-Butanol (BuOH)
Formamide (F)
N-methylformamide (NMF)

Aprotic
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
a

Acetone (AC)
Acetonitrile (AcN)
Benzonitrile (BzN)
Butyronitrile (BuN)
Dimethylacetamide (DMA)
Dimethylformamide (DMF)
Dimethylsulfoxide (DMSO)
Hexamethylphosphoramide (HMPA)
N-methylpyrrolidinone (NMP)
Nitrobenzene (NB)
Nitromethane (NM)
Propionitrile (PrN)
Propylene carbonate (PC)
Tetramethylenesulphone (TMS)
Tetramethylurea (TMU)

Obtained from compilations by Marcus [2] and Riddick et al. [G4].


Estimated at the normal boiling point.

POLAR SOLVENTS

151

concentration of methanol in pure methanol is 24.6 M; the corresponding concentration of 1-butanol is 10.9 M. The largest solvent molecule considered here is
hexamethylphosphoramide, which has a concentration of only 5.7 M in the pure
liquid. The molar volume of the solvent is obviously an important parameter in
assessing the degree of departure from ideality of its solutions.
The enthalpy of vaporization is an important parameter which can be used
to assess intermolecular forces in a given liquid. As discussed earlier, the ratio
vap Hm =Vm gives the internal pressure of the liquid (section 1.7). The entropy of
vaporization is also useful. When it is measured at the normal boiling point,
this quantity is close to 89 kJ mol1 in an unstructured solvent according to
Troutons rule. The data in table 4.1 show that vap S is signicantly greater
than 89 J K1 mol1 for the protic solvents, which are hydrogen-bonded liquids.
However, this quantity is also larger in some aprotic solvents for which dipole
dipole interactions are strong.
The dielectric properties of the solvents considered here are summarized in
table 4.2. These properties are important in evaluating the solvation of ions in
polar solvents under both static and dynamic conditions. The relative permittivity
of a solvent at high frequencies, eop, can be calculated from the refractive index,
nop, the relationship being
eop n2op

4:2:1

Relaxation parameters obtained by studying the frequency dependence of the


relative permittivity are also summarized in this table. In the case of the aprotic
solvents the summarized parameters were usually obtained by analyzing the
experimental data on the basis of the Debye model, which is discussed in detail
later in this chapter. Protic solvents follow a more complex behavior because of
hydrogen bonding and are generally considered to exhibit multiple relaxations.
For these systems the relaxation time listed in table 4.2 is that for the slowest
solvent relaxation, whereas the value of the high-frequency permittivity, e1, is
that for the fastest relaxation process. More details about the behavior of these
systems are given later. It should be noted that e1, which is usually measured in
the far infrared region, is slightly higher then eop, which is measured at visible
optical frequencies. The distinction between these quantities results from the fact
that the Debye treatment is based on a continuum model which does not recognize the molecular nature of the solvent and the features of its vibrational spectrum in the infrared region.
Some molecular properties of polar solvents are summarized in table 4.3. The
dipole moment and molecular polarizability are the molecular parameters which
lead to the solvent permittivity. The other parameters listed are the molecular
diameter and the LennardJones interaction energy, eLJ. These are of interest in
assessing the role of van der Waals forces in determining the properties of a polar
liquid.
In assembling the properties of polar solvents, attention has been focused on
their dipolar properties, that is, their ability to stabilize electrolytes in solution. As
will be seen in the following chapter, it is not sucient to consider only the
electrical properties of these molecules as dened in classical electrostatics. The

Table 4.2 Dielectric Properties of Selected Polar Solvents at 25 Ca

Solvent

Relative
Static
Permittivity
es

Temperature
Coecient
des =dT

Refractive
Index
nop

Temperature
Coecient
dnop =dT  104

Debye
Relaxation Timec
tD =ps

Temperature
Coecientb
HD =kJ mol1

High-Frequency
Permittivity
e1

78.46
32.70
24.55
20.33
17.51
111.0
182.4

0.360
0.197
0.147
0.142
0.132
0.72
1.6

1.3325
1.3265
1.3594
1.3837
1.3973
1.4468
1.4300

1.05
3.83
4.0
3.72
3.9
1.44
3.8

8.32
51.5
163
329
517
37.3
128

18.2
15.8
18.0
20.0
23.8
15.2
19.3

4.49
2.79
2.69
2.44
2.22
4.48
3.20

20.7
35.9
25.2
24.5
37.78
36.71
46.68
30.0
32.0
34.82
35.8
28.2
66.1
43.7
23.1

0.0977
0.160
0.091
0.108
0.213
0.178
0.106
0.175
0.140
0.180
0.161
0.119
0.240
0.115

1.3560
1.3416
1.5259
1.3820
1.4356
1.4282
1.4773
1.45
1.4680
1.5500
1.3796
1.3636
1.4209
1.4820
1.4493

5.0
4.5
4.8
4.3
5.4
4.6
3.58
3.6
5.0
4.6
4.5
4.5
3.75
3.4

3.2
3.2
37.9
6.6
16.0
10.4
18.9
80.0
21.0
45.0
4.0
5.0
43.1

31

6.5
8.3
(10.6)
8.8
11.6
10.0
11.7
(14.6)
(12.1)
13.1
6.6
8.65
15.8

1.89
2.26
3.80
(2.5)
3.04
2.94
5.3
3.3
4.06
4.10
2.0
(2.4)
4.14

4.5

Proticc
1.
2.
3.
4.
5.
6.
7.

W [5, 6]
MeOH [5, 6]
EtOH [5, 6]
PrOH [5, 7]
BuOH [7, 8]
F [6, 9]
NMF [6, 9]

Aprotic
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
a

AC [10]
AcN [9, 11]
BzN [12]
BuN [11]
DMA [9, 13]
DMF [6, 9]
DMSO [14]
HMPA [15]
NMP [16]
NB [12]
NM [6]
PrN [11]
PC [6, 9]
TMS
TMU [17]

The majority of the data were obtained from compilations by Marcus [2], Riddick et al. [G4], and Karapetyan and Eychis [3]. Specic references to relaxation data are given with
each solvent. Numbers in parentheses are estimates.
b
Temperature coefcient of  D dened as R @ln  D/@(1/T).
c
In the case of the protic solvents which have several relaxation processes, the value of  D is for the rst relaxation.

POLAR SOLVENTS

153

Table 4.3 Molecular Properties of Selected Polar Solvents

Solvent

Dipole Momenta
p/debye

Polarizabilityb
103 ap /nm3

Diameterc
s/nm

LennardJones
Energyd
eLJ k1
B =K

1.85
1.70
1.69
1.58
1.66
3.73
3.83

1.47
3.26
5.13
6.96
8.79
4.23
6.05

0.274
0.371
0.436
0.498
0.540
0.382
0.452

79
234
324

320

2.88
3.92
4.18
4.07
3.80
3.82
3.96
5.54
4.09
4.22
3.46
4.05
4.98
4.81
3.47

6.41
4.42
12.54
8.11
9.63
7.90
7.99
18.97
10.62
12.97
4.95
6.26
8.56
10.77
12.80

0.476
0.427
0.574
0.532
0.548
0.517
0.491
0.698
0.569
0.574
0.431
0.477
0.536
0.581
0.544

362
275
520

450
380
333
670

609
298

400

Protic
1.
2.
3.
4.
5.
6.
7.

W
MeOH
EtOH
PrOH
BuOH
F
NMF

Aprotic
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.

AC
AcN
BzN
BuN
DMA
DMF
DMSO
HMPA
NMP
NB
NM
PrN
PC
TMS
TMU

From gas phase data when possible [4] or from the compilations of Marcus [2] (1 debye is equal to 3:3356 
1030 C m).
b
Estimated using the LorentzLorenz equation (4.3.21).
c
Estimated from gas phase solubilities [18]; when these data were not available, the solvents diameter was
estimated on the basis of a linear correlation between existing experimental data and the cube root of the molar
volume.
d
From the compilations of Marcus [2].
a

specic chemical interactions between an ion and polar solvent molecule are also
important. Methods of including consideration of both electrical and chemical
interactions are outlined later in this chapter.

4.3 The Static Solvent Permittivity on the Basis


of Continuum Models
The task of statistical thermodynamics in describing the dielectric properties of a
liquid is to develop a model for the liquid permittivity in terms of the dipole
moment and polarizability of the component molecules. The usual approach has
been to assume that the liquid molecule can be represented as a polarizable hard

154

LIQUIDS, SOLUTIONS, AND INTERFACES

sphere with a point dipole which is embedded in a dielectric continuum. In the


presence of an applied external eld E, the molecule experiences a local eld Ee . An
important feature of the model is the method used to estimate the local eld.
A. The Debye Model
The rst solution to this problem as given by Debye [1] for the case of dipolar
molecules in the gas phase. The potential energy of a molecule with dipole
moment p in a eld E is equal to
u pE cos y

4:3:1

where y is the angle between the eld vector E and the dipole. The degree of
orientation of the molecules in the eld varies with the temperature upon which
randomizing thermal motion depends. The average value of the angle y is now
determined on the basis of the Boltzmann distribution law. The number of molecules lying within a solid angle, d, in the direction y, is given by
dNV AN ebu d

4:3:2

where AN is a constant related to the total number of molecules per unit volume,
NV and b 1/(kB T). It follows that
2p

NV

AN expbp E cos yd

4:3:3

where the integration is carried out over all possible values of the solid angle, .
The increment d can be estimated by considering cones of semi-angle y and y
dy dened with respect to the eld vector, E. On this basis it follows that
d 2p sin y dy

4:3:4

The component of the dipole moment in the direction of the eld is p cos y. To
obtain the average value hpi, one adds up values of p cos y over all possible angles.
Thus, the average is
p
hpi

p cos y expbp E cos y sin y dy


p

4:3:5
expbp E cos y sin y dy

After integration by parts one obtains


hpi p cothbpE 

1
bE

4:3:6

The function coth x  1=x is called the Langevin function so that the average
dipole moment is equal to its magnitude times the Langevin of bpE. The value of
bpE is usually much smaller than unity. For instance, the value of bp for a
molecule with a dipole moment of 3 debyes is 2.4  109 m V1 at 25 C. The
applied eld would have to be 4.1  108 V m1 in order to make bpE unity. The

POLAR SOLVENTS

155

applied eld is normally much smaller, so that the average value of the dipole
moment can be estimated using the value of coth(bpE) in the limit that bpE is
small. Expanding the exponential terms in coth(bpE) retaining the rst four terms
in the expansion, one obtains
b2 p2 E2
1
bpE
2!

cothbpE

3
b3 p3 E3 bpE
2bpE 2
3!
22

4:3:7

Thus, the approximate expression for hpi is


hpi

bp2 E
3

4:3:8

The total polarization of the medium per unit volume considering also the molecular polarizability becomes
!
bp2
P NE p
4:3:9
3
The units of the polarization P are coulombs per square meter; this quantity gives
the eective dipole of the medium per unit volume containing NV molecules.
EXAMPLE

A parallel-plate capacitor is set up at 25 C with a voltage of 105 V between the


plates, which are separated by 1 mm. Dimethylsulfoxide (DMSO) vapor at low
pressure is introduced into the gap between the plates. Estimate the average
dipole moment of each DMSO molecule in the direction of the eld.
The eld in the capacitor gap is 108 V m1 . Since a dilute gas is present in the
gap the local eld can be assumed to be equal to the applied eld.
The dipole moment of DMSO is 3.96 debyes (table 4.3):
p 3:96  3:336  1030 1:32  1029 C m

4:3:10

The average dipole moment in the direction of the eld is


hpi

1:32  1029 2  108


1:41  1030 C m
3  1:38  1023  298:2

4:3:11

This is equivalent to 0.423 debyes.


Even though the eld is quite high, the eects of thermal motion result in the
average dipole moment of the molecule in the direction of the eld being much
less than the permanent dipole moment.
In applying this relationship to dipolar molecules in dense gases and liquids the
eld E is understood to be the local or eective eld Ee. In order to estimate Ee
one must solve the statistical mechanical problem which relates the local quantity
to the macroscopic applied eld E. The problem is solved by estimating the local
eld in a spherical cavity within the dielectric (g. 4.1). The cavity is assumed to
have molecular dimensions with diameter a. The material within the sphere is
considered in terms of individual molecules, whereas that outside the sphere is

156

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 4.1 Schematic diagram of a


spherical cavity within a
homogenous dielectric between
the plates of a parallel-plate
capacitor.

assumed to have homogeneous properties with an isotropic relative permittivity


es. One also imagines the dielectric to be between the plates of a parallel-plate
capacitor so that the eld and polarization vectors have a dened direction.
In order to estimate Ee one must consider three contributions, namely, the eld
E1 imposed on the medium via the charge on the plates of the capacitor, the eld
E2 due to the polarization charge on the surface of the spherical cavity, and
nally, the eld E3 due to the molecules within the sphere. E1 is obviously identied with the experimentally controlled eld E. The eld E2 is calculated by integrating the polarization in the direction of the eld over the surface of the
spherical cavity. This gives
p
E2
0

P cos y2pr2 sin y dy


4pe0 r2

4:3:12

where 2pr2 sin y dy is the area of an element on the sphere dened by the angles y
and y dy. The result is
E2

P
3e0

4:3:13

In order to estimate E3, one must know how the individual molecules are
arranged within the cavity. For example, if they are located on a cubic lattice
or when the molecules form an ideal gas, E3 is zero. In the solution to the problem
given here, E3 is assumed to be zero. Thus,
Ee E

P
3e0

4:3:14

This relationship was originally derived by Lorentz [19].


In order to proceed further one must make use of the fundamental electrostatic
relationship between the electric displacement D, the electric eld E, and the
polarization P, which is
D e0 E P e0 es E

4:3:15

P e0 Ees  1

4:3:16

It follows that

POLAR SOLVENTS

157

It is clear from these relationships that the electric displacement D has the same
units as the polarization P, namely, C m2 . Now, from equation (4.3.14)
Ee

es 2
E
3

4:3:17

Identifying the eld in equation (4.3.9) as the local eld Ee when this expression is
applied to liquids, and substituting in equation (4.3.16) for P, one obtains the
result
!
es  1
N
bp2


4:3:18
es 2 3e0 p
3
for N molecules. For one mole of molecules, one may write
Nv

NL
N
Lr
Vm
M

4:3:19

where NL is the Avogadro constant, Vm , the molar volume of the liquid, r, its
mass density, and M, its molecular mass. Equation (4.3.18) is then rewritten in the
form
!


es  1 M N L
bp2

Pm

4:3:20
es 2 r
3e0 p
3
where the quantity on the left-hand side is called the molar polarization. It is
familiar from the analysis of dielectric permittivity data for liquids and solids, and
is usually expressed in units of cubic centimeters per mole. Equation (4.3.20) is the
well-known Debye equation.
For pure liquids, the Debye equation suggests that the molar polarization
should be a linear function of the reciprocal temperature. Furthermore, one
should be able to analyze relative permittivity data for a polar liquid like water
as a function of temperature to obtain the dipole moment and polarizability from
the slope and intercept, respectively. In fact, if one constructs such a plot using
data for a polar solvent, one obtains results which are unreasonable on the basis
of known values of p and ap from gas phase measurements. The reason for the
failure of the Debye model in liquids is the fact that it neglects the eld E3 due to
dipoles in the immediate vicinity of a given molecule. However, it provides a
reasonable description of the dielectric properties of dilute polar gases. In liquids,
relatively strong forces, both electrostatic and chemical, determine the relative
orientation of the molecules in the system, and lead to an error in the estimation
of the orientational component of the molar polarization.
There are two circumstances under which equation (4.3.20) proves useful. The
rst of these is at frequencies suciently high that the orientational component of
Pm is eectively zero. Then, one can write


eop  1 M N L ap
Rm

4:3:21
eop 2 r
3e0
This is called the LorentzLorenz equation, and is used to estimate the molecular
refraction Rm from the refractive index or eop. Since the polarizability ap is often

158

LIQUIDS, SOLUTIONS, AND INTERFACES

not known from gas phase data, it has been customary to estimate it for many
molecules using equation (4.3.21).
EXAMPLE

Given that the refractive index of water at 25 C is 1.3325 and its molar volume
18.07 cm3, estimate the molecular polarizability of the water molecule. Then
estimate the same quantity at 50 C where the value of n is 1.3291, and the
molar volume 18.234 cm3.
At 25 C
eop n2 1:7756

4:3:22

eop  1
0:7756
 18:07 3:712 cm3 mol1
Vm
3:7756
eop 2

4:3:23

Thus,

The corresponding value of ap is


ap

3:712  106  3e0


1:637  1040 C m2 V1
NL

4:3:24

This result may be expressed in the more customary units of cubic meters or
cubic nanometers by dividing by 4pe0 . Thus, ap is equal to 1:472  103 nm3 at
258C. When the calculation is repeated at 508C the result is ap 1:471  103
nm3 . One expects the polarizability to be independent of temperature in a
range where the electrons in the molecule remain in the same molecular orbitals. The small change in the polarizability reects the weakness of the
LorentzLorenz model, which is based on continuum concepts. However,
the estimated change is small, so that one may assume that the model is reasonably good.
The second situation where equation (4.3.20) is often applied is to the analysis
of data for the dielectric permittivity of dilute solutions of a polar compound in a
non-polar solvent such as benzene or carbon tetrachloride. Under these circumstances local structure due to dipoledipole interactions can be neglected, and the
dipole moment of the polar solute can be calculated from the change in molar
polarization with concentration of the polar solute. Then, the molar polarization
can be written


es  1 M1 x1 M2 x2
4:3:25
Pm x1 Pm1 x2 Pm2
es 2
r
where Pm1 is the molar polarization of the non-polar solvent, Pm2 , that due to the
polar solute, and r, the density of the solution. Pm1 is assumed to be constant,
independent of solution composition, and Pm2 is determined as a function of the
mole fraction x2 . From the experimental data, one extrapolates to x2 0 to
obtain the limiting value, P0m2 . The dipole moment is then calculated using the
Debye equation with the polarization component being estimated from the corresponding data for the refractive index. Although this method has been often

POLAR SOLVENTS

159

applied, it can be criticized on fundamental grounds [G1]. Therefore, molecular


data obtained using this approach should be regarded as approximate.
EXAMPLE

Using the data given below for dilute solutions of nitromethane in benzene,
calculate the molar polarization and refraction of the solute in the limit of
innite dilution. Then, estimate the dipole moment of nitromethane on the
basis of the Debye model.
The following data were reported by Balakier [20] at 293.2 K.
Mole Fraction
of Nitromethane
x2

Solution
Density
r/g cm3

Relative
Permittivity
es

Refractive
Index
nop

0.0000
0.0197
0.0392
0.0593
0.0798

0.8789
0.8830
0.8860
0.8893
0.8926

2.284
2.587
2.863
3.188
3.457

1.5011
1.4992
1.4976
1.4958
1.4943

Given that the molecular weight of nitromethane is 61.04 and that of benzene, 78.12, one rst calculates the molar volume of the solution. For example,
when x2 0:0197,
Vm

61:04  0:0197 78:12  0:9803


88:09 cm3 mol1
0:8830

4:3:26

The molar polarization is estimated using the dielectric constant following


equation (4.3.20):
Pm 88:09 

1:587
30:48 cm3 mol1
4:587

4:3:27

The molar refraction is calculated in the same way using the optical dielectric
constant, that is, the square of the refractive index:
Rm 88:09 

1:50112  1
25:87 cm3 mol1
1:50112 2

4:3:28

The results obtained as a function of mole fraction are tabulated below.


Mole Fraction
of Nitromethane
x2

Molar
Volume
Vm =cm3 mol1

Molar
Polarization
Pm =cm3 mol1

Molar
Refraction
Rm /cm3 mol1

0.0000
0.0197
0.0392
0.0593
0.0798

88.88
88.09
87.42
86.71
85.99

26.64
30.48
33.49
36.57
38.72

26.19
25.87
25.61
25.32
25.05

160

LIQUIDS, SOLUTIONS, AND INTERFACES

Now one calculates the molar polarization due to the solute. For example,
when x2 0:0197,
Pm2

30:48  26:64  0:9803


221:4 cm3 mol1
0:0197

4:3:29

Similarly, for the molar refraction due to the solute:


Rm2

25:87  26:19  0:9803


10:1 cm3 mol1
0:0197

4:3:30

Values of Pm2 and Rm2 are plotted against the mole fraction x2 in g. 4.2.
Extrapolation to x2 0 gives the values of these parameters in the limit of
innite dilution. They are Pm20 232:7 cm3 mol1 and Rm20 9:8 cm3 mol1 .
From equation (4.3.20), one may write
Pm20  Rm20

NL bp2
9e0

4:3:31

Thus,
9  8:854  1012  1:381  1023  293:2  232:7  9:8  106
p
6:022  1023
1:09  1029 C m 3:27 debyes

!1=2

4:3:32

B. Other Models for the Static Permittivity


Another approach to a continuum model for the electric permittivity which considers the eld E3 was given by Onsager [21]. This model also makes use of a

Fig. 4.2 Plot of the molar polarization Pm2 and molar refraction Rm2 for nitromethane
against its mole fraction in benzene.

POLAR SOLVENTS

161

spherical cavity but limits it to one molecule. As a result it is applicable only to


liquids without strong directional forces. The equation obtained by Onsager is
es  eop 2es eop 2
es eop 22

Vm

NL bp2
9e0

4:3:33

where Vm is the molar volume of the liquid. It is clear that the distortional
contribution to the polarization is not explicitly available in this expression but
is included in a complex way in the quantity on the left-hand side. The model
corrects some of the problems of the Debye model but in the end it still fails to
account for the correlation of a given dipole to its neighbors.
Further developments in the theory of the structure of polar liquids included
estimates of the correlation of a given dipole to its neighbors. Important contributions were made in this direction by Kirkwood [22] and Frohlich [23]. In
Kirkwoods model, the eld E3 is calculated by considering all possible orientations of surrounding dipoles in a spherical cavity for a xed orientation of
the central dipole. By averaging over these orientations, Kirkwood obtained
an improved estimate of the polarization of the medium. For the case of nonpolarizable dipoles the result is
es  12es 1
N g bp2
Vm L k
3e0
3es

4:3:34

where gK is a correlation parameter describing the degree of local order. This


parameter is unity when the average dipole moment of the molecules immediately
surrounding a central molecule which is held xed is the same as the dipole
moment of an isolated molecule. In other words, xing the position of one molecule does not aect the positions of the surrounding dipoles except through longrange electrostatic forces. On the other hand, if the neighboring dipoles tend to
line up in a parallel fashion as a result of the xing of a central dipole, the
parameter gK rises to values greater than unity. Similarly, if xing one dipole
tends to line up the surrounding dipoles in an antiparallel direction, the parameter
gK will be less than one. Equation (4.3.34) diers from the Onsager equation
(equation (4.3.33)) in two ways. If the distortional contribution in equation
(4.3.33) is neglected by setting eop equal to one, and the correlation between
dipoles is neglected by setting gK equal to one in equation (4.3.34), these expressions are the same. The distortional contribution is not an important factor for
polar molecules so that the version of the Kirkwood equation given here may be
applied to the systems considered in this chapter. Inclusion of the correlation
parameter gK in this equation gives an important improvement in the description
of the interactions between molecules in these systems. This is especially important when the interactions are chemical in nature, for example, when hydrogen
bonding is present. In principle, it is possible to calculate gK if the structure of the
liquid is known, but in general, it is considered to be an adjustable parameter.
Dielectric permittivity data for water and acetonitrile in the temperature range
from 0 to 508C are plotted according to the Kirkwood equation in g. 4.3. The
straight lines shown are based on one-parameter least-squares ts, the slopes
giving the value of NL gK p2 =3kB e0 . On the basis of this analysis for water, assum-

162

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 4.3 Plot of the molar polarization according to the Kirkwood model against 1000/T,
where T is the absolute temperature for water (*) and acetonitrile (^) in the temperature
range 0508C.

ing that its dipole moment is 1.85 D, the value of the correlation parameter gK is
4.5. This result is higher than one would estimate on the basis of the structure of
liquid water determined by neutron diraction and Raman spectroscopic studies
(see section 2.10). The high value reects the eects of hydrogen bonding in this
very structured liquid. In the case of acetonitrile, assuming p 3:92 D, the value
of gK is 1.3. In this solvent the degree of correlation between adjacent molecules is
much weaker. Since hydrogen bonding is absent in acetonitrile, the only source of
correlation would be the formation of dimers resulting from the antiparallel
association of the dipole vectors due to the CN groups in this molecule.
The above examples illustrate that continuum models such as the Kirkwood
model are reasonably successful in describing the static permittivity, provided one
has an independent means of estimating the correlation parameter gK .
Unfortunately, these estimates are available for only a few polar solvents, so
that gK must be considered an independent parameter. The version of
Kirkwoods theory presented here only considers orientational polarization.
When distortional polarization, that is, the eect of molecular polarizability, is
included, interpretation of experimental results is less clear. Since the approach
taken here involves continuum concepts, it is necessarily limited. In the following
section, a simple model based on a molecular description of a polar liquid is
presented.

4.4 The Static Solvent Permittivity According to the MSA


The approach taken in non-primitive models for the dielectric properties of polar
solvents is quite dierent from that described above. The rst step in a molecular
model is to calculate the pair correlation function for molecules in the liquid.

POLAR SOLVENTS

163

Then, when one knows the dipole moment and polarizability, one should be able
to estimate the dielectric constant of the medium using the position and average
orientation of each molecule in the system. Since dipoledipole interactions are
long range, the problem is not simple and approximations are made in order to
nd a solution. The usual approximation is to represent each molecule as a hard
sphere with a central point dipole p and polarizability ap . Such a representation of
the system should give a good representation of aprotic solvents but does not have
any feature which is able to describe hydrogen bonding.
A treatment for polar solvents on the basis of the mean spherical approximation was rst given by Wertheim [24, 25]. The closure conditions are based simply
on the dipoledipole interaction energy between the polar molecules in the system.
Neglecting molecular polarizability, these conditions are
go1 ; r; o2 0

for

r > ss

4:4:1

and
co1 ; r; o2

bp2
s1  sr s2  sr  s1  s2 
4pe0 r3

for

r > ss

4:4:2

where ss is the diameter of a hard sphere, sr , a unit vector in the direction r, and s1
and s2 , unit vectors in the directions of the two dipoles which give rise to the
interaction energy. By solving the OZ equation (see section 2.6), using this simple
expression for the direct correlation function, cr, one can nd the form of the
pair correlation function gr as a function of distance from any given hard
sphere, averaging out the angular dependence. One may then estimate the thermodynamic properties of the system using the methods described earlier (see
section 2.8).
On the basis of Wertheims solution of the MSA for dipolar hard spheres it is
convenient to dene a polarization parameter ls which is obtained directly from
the relative static permittivity, that is, by solving the equation
l2s 1 ls 4 16es

4:4:3

The value of ls for a typical polar solvent is approximately two. This equation
was introduced earlier in the development of the MSA for ionsolvent interactions (section 3.5). It was seen that the MSA gives an improved description of ion
solvation parameters with respect to the Born model. However, it fails to distinguish between the solvation of cations and anions of the same size. In other
words, it fails to distinguish between the short-range chemical interactions
which stabilize ions of diering charge.
It is obvious that a model for the dielectric properties of a polar solvent must
consider the eects of hydrogen bonding and other chemical interactions which
are not included in a point dipole model for solvent molecules. A simple way of
doing this is to introduce a directional sticky parameter [26]. Thus, each solvent
molecule is represented by a hard sphere with a central point dipole which is
polarizable. The surface of the hard sphere is modied so that it can interact
attractively or repulsively with the surface of an adjacent sphere. Stickiness is
an eective method of introducing short-range chemical forces. It amounts to
assuming that interactions along the line of the dipole vector may be stronger

164

LIQUIDS, SOLUTIONS, AND INTERFACES

or weaker than one estimates on the basis of the simple point dipole model.
Equation (4.4.3) then becomes


t0 2
2
4
16es
4:4:4
ls 1 ls 1 
ls
where t0 is the longitudinal stickiness parameter.
Further development of the theory leads to an expression for the excess
internal energy in terms of molecular solvent parameters and ls . The result is
ex

Um

dp2 b2 bVm
2ps3s

4:4:5

where
b2

6ls  1
ls 2

4:4:6

Vm is the molar volume of the solvent, and dp , a parameter related to the strength
of dipoledipole interactions. With consideration of dipole polarizability, dp is
given by
"
#
NL a2 bp2 a ap
2
dp

4:47
Vm 3e0
e0
where
a

3s2s
3s3s  b2 ap pe0 

4:4:8

and NL is the Avogadro constant. The parameter dp may also be estimated on the
basis of the polarization parameter ls and the stickiness parameter t0 dened by
equation (4.4.4). This relationship is
"
#

l2s ls 22
t0 2
16
2
1
dp
 2
4:4:9
9
ls
ls 1 ls 4
Equations (4.4.4)(4.4.9) give a relationship between the molecular parameters p
and ap and the macroscopic relative permittivity es via the two MSA parameters
ls and t0 . Equations (4.4.4) and (4.4.9) are non-linear equations from which one
obtains ls and t0 once the parameter dp has been estimated.
The above equations can be solved using iterative techniques to obtain values
of ls , t0 , and dp which are self-consistent. First of all, equation (4.4.4) is solved for
ls , assuming that t0 is zero. This value of ls is used to obtain an initial estimate for
dp using equations (4.4.6), (4.4.7), and (4.4.8). Equation (4.4.9) is now solved for
t0 . The entire calculation is repeated using this estimate of t0 to obtain a second
estimate of ls from equation (4.4.4). By going through an iterative scheme several
times, the solution converges to give constant values of ls and t0 . In the case of
water, the revised estimate of ls is 2.50 and the stickiness parameter is 0:40. The
negative value of t0 indicates that dipoledipole interactions are enhanced by the
sticky chemical interactions. In the case of water, dp2 is 30% larger with these
interactions than when estimated without them.

POLAR SOLVENTS

165

EXAMPLE

Estimate the MSA parameters for DMSO using the dielectric properties given
in table 4.2 and the molecular properties in table 4.3.
The rst step is to estimate ls on the basis of the Wertheim equation (4.4.3)
and the value of es (46.68). The equation is
ls 1 ls 2 16  46:681=2 27:33

4:4:10

The solution of this cubic equation gives ls 2:385.


The molecular properties of DMSO are
ss 4:91  1010 m
p 3:96  3:336  1030 1:32  1029 C m
ap 4pe0  7:99  1030 C m2 V1
The second step is to estimate dp from equation (4.4.9). The estimate of b2
(equation (4.4.6)) is
b2

6  1:385
1:895
4:385

4:4:11

The estimate of a (equation (4.4.8)) is


a

3  4:91  1010 3
1:206
3  4:91  1010 3  4  7:99  1030  1:895

4:4:12

The number density for the solvent molecules is


NL 6:022  1023

8:45  1027 molec m3


Vm
7:13  105

4:4:13

It follows that
1:2062  8:45  1027  1:32  1029 2
4p  1:206  8:45
3  8:854  1012  4:115  1021
 1027  7:99  1030
19:60 1:02 20:62
4:4:14

dp2

From equation (4.4.9)




9dp2
t0 2
16
1
2
2
2
ls
ls ls 2
ls 1 ls 4
9  20:61
16

1:718
2
2
2:385 4:385
2:3852 3:3854
and t0 0:74:
Now a new value of s is estimated using equation (4.4.4):


16  46:68 1=2
ls 1 ls 2
20:85
1:718

4:4:16

166

LIQUIDS, SOLUTIONS, AND INTERFACES

The result is ls 2:129. dp2 is now estimated again, the result being 19.56. The
iteration process is repeated until successive values are the same to a reasonable
level of precision. The results for DMSO are ls 1:85 and t0 1:53.
Values of ls and t0 have been estimated for the polar solvents considered in this
chapter and are summarized in table 4.4. Also included in this table are values of
the Kirkwood correlation parameter gK . It is dened in the MSA model as
gK

es  12es 1
3es dp2

4:4:17

As can be seen from the results the values of ls are usually close to two. In
general, they are higher for the protic solvents than the aprotic ones. The stickiness parameter is negative for aprotic solvents and positive for most protic solvents. A negative value of t0 indicates that the degree of order in the solvent is
higher than one predicts on the basis of the simple point dipoledipole model. It
also reects the fact that the dipole moment is not centrally located in the solvent
molecules considered.
Table 4.4 MSA Parameters for Selected Polar Solvents

Solvent

Polarization
Parameter
ls

Stickiness
Parameter
t0

Molecular
Polarizability
103 ap /nm3

Kirkwood
Correlation
Parameter
gK

2.50
2.58
2.62
2.68
2.69
2.08
3.28

0.40
0.80
1.11
1.36
1.47
2.36
0.33

1.48
3.29
5.21
7.10
8.99
4.26
6.20

2.79
2.99
3.08
3.23
3.26
2.04
4.52

1.70
1.47
1.52
1.39
1.99
1.80
1.85
1.71
1.74
1.77
1.55
1.45
1.98
1.74
1.81

0.79
2.53
1.65
1.93
0.77
1.30
1.53
1.28
1.29
1.32
2.14
2.17
1.70
1.77
0.62

6.51
4.48
13.05
8.29
9.91
8.12
8.24
19.61
10.99
13.54
5.04
6.37
8.80
11.19
13.16

1.49
1.18
1.23
1.09
1.89
1.60
1.67
1.44
1.52
1.56
1.38
1.15
1.86
1.53
1.64

Protic
1.
2.
3.
4.
5.
6.
7.

W
MeOH
EtOH
PrOH
BuOH
F
NMF

Aprotic
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.

AC
AcN
BzN
BuN
DMA
DMF
DMSO
HMPA
NMP
NB
NM
PrN
PC
TMS
TMU

POLAR SOLVENTS

167

A trend in the value of t0 can be seen for a series of solvents with the same polar
groups and alkyl groups of increasing size. For example, for water and the alcohols, t0 increases from 0:40 for water to 1.47 for butanol. A similar trend is seen
for the nitriles where t0 increases from 2:54 for acetonitrile to 1:67 for benzonitrile. These values of t0 are plotted in g. 4.4 against b2p =d 3 e0 , the quantity which
characterizes the strength of dipoledipole interactions in the medium. There is a
clear linear relationship between these parameters. As the size of the alkyl groups
increases, the dipolar group moves further away from the center of the molecule.
This results in a decrease in dipole moment, an increase in molecular size, and a
corresponding decrease in the strength of dipoledipole interactions. These
changes require that the stickiness parameter change as well to account for the
fact that the dipoledipole interactions cannot be treated by the simple point
dipole model. Examination of the data for aprotic solvents in table 4.4 also reveals
a general trend according to which t0 becomes more negative as the strength of
dipoledipole interactions increases [26].
The estimates of the correlation parameter gK give an idea of the degree of
local structure in the polar solvent. In the case of water and the alcohols, this
parameter is relatively high and increases with the length of the hydrocarbon
chain. The result for water, namely, 2.79, is remarkably close to the value estimated by Kirkwood [22] on the basis of the well-known tetrahedral structure for
the surrounding hydrogen-bonded water dipoles (2.65) (see also g. 2.14) [G2].
The increase in gK in the alcohols suggests a tendency to form hydrogen-bonded
chains in these systems. The value of gK is also large for N-methyl formamide, a
strongly structured solvent [27]. In the case of the aprotic nitriles, the average
value of gK is 1.2. This result indicates that local ordering is minimal in these
systems. Dimethylsulfoxide, which has approximately the same dipole moment as
acetonitrile, is known to be strongly dimerized in the liquid state [28]. As a result it

Fig. 4.4 Plot of the stickiness parameter t0 against the values of bp2 =e0 d3 ), which characterizes the strength of dipoledipole interactions for two selected solvent groups.

168

LIQUIDS, SOLUTIONS, AND INTERFACES

has a higher value of gK . An even higher value is found for propylene carbonate
(1.86), which is also associated in the liquid state. In summary, the values of gK
give a useful indication of local order in polar solvents and may be related to more
detailed structural information when this is available.
One may also use the MSA model to describe the permittivity of the system at
optical frequencies. Under these circumstances the system responds to the electrical eld only through electronic polarization, the orientational component
being frozen. The directional stickiness of the dipoles is then unimportant so
that t0 is eectively zero at very high frequencies. Under these circumstances, the
polarization parameter is given by
l2op 1 lop 4 16eop

4:4:18

where lop is the value of the polarization parameter at optical frequencies. The
expression for dp , the parameter which characterizes the excess energy of the
system, becomes
dp2

NL aap
e0 V m

4:4:19

where a is given by equation (4.4.8) and


b2

6lop  1
lop 2

Alternatively, dp may be estimated from the following equation:




l2op lop 22
1
1
dp2
eop
9

4:4:20

4:4:21

Since values of the molecular polarizability are not available from gas phase
measurements for most of the polar solvents considered here, they may be estimated using the MSA in the following way. First, a value of lop is calculated by
solving equation (4.4.18) using the experimental value of eop . Then, the parameter
dp is estimated using equation (4.4.21). Finally, the polarizability is found from
equation (4.4.19). The results obtained are summarized in table 4.4. They are very
close to estimates obtained on the basis of the LorentzLorenz equation (see
equation (4.3.21) and table 4.3), usually being a few percent higher.
In summary, the MSA provides a remarkably simple and eective way of
describing the dielectric properties of polar solvents. By including stickiness in
the model one has a very easy method of dealing with the eects of non-sphericity,
the non-central location of the polar group, and hydrogen bonding. These eects
collectively make up the chemical part of the problem of estimating the permittivity of a polar liquid from its dipole moment and polarizability. One should note
that the polarization parameter used here is quite dierent from that introduced
in section 3.4 in the discussion of ionsolvent interactions. Although it arises in
the model in the same way, it is dierent because the chemical interaction between
a solvent dipole and an ion depends on the chemical nature of the polar group in
the solvent and whether it is able to participate in hydrogen bonding. This leads to
the necessity of introducing dierent values of this parameter for cations and

POLAR SOLVENTS

169

anions. On the other hand, the polarization parameter used here describes the
interaction of one dipole with neighboring dipoles. These examples show that
simple modication of the MSA leads to an excellent description of the properties
of real systems without recourse to complex mathematical treatments.

4.5 Dielectric Relaxation Phenomena


When a polar solvent is placed in a changing electrical eld, the molecules must
realign so that their dipole vectors maintain the orientation corresponding to
minimum energy. Because of intermolecular forces, this process does not occur
innitely fast but on a time scale which depends on the properties of the medium
and which is usually on the order of 1100 ps. Dielectric relaxation experiments
provide very useful information about molecular motion in polar liquids and the
ability of the solvent molecules to respond to changing electrical conditions.
The theory of dielectric relaxation is based on a macroscopic model which
considers how the polarization of the medium changes with time. As seen earlier,
the polarization is made up of an orientational and a distortional component so
that one may write
P Po Pd

4:5:1

When an electrical eld is applied to the system, the distortional component


relaxes very quickly on a time scale corresponding to electronic motion. On the
other hand, the orientational component relaxes on a time scale consistent with
molecular motion. In deriving an expression for the kinetics of the relaxation
process, it is assumed that the rate of relaxation is proportional to the departure
of the orientational polarization from its equilibrium value, that is,
dPo Poe  Po

dt
t

4:5:2

where Poe is the equilibrium value of the orientational polarization and t is the
relaxation time. The reciprocal of t is the equivalent of the rst-order rate constant for the relaxation process.
From the fundamental laws of electrostatics, the relation between the polarization and the electrical eld is
P e0 Ee  1

4:5:3

where e represents the value of the permittivity at time t. If E is changing, then the
polarization depends on the time dependence of both E and e. At equilibrium the
total polarization is given by
Pe e0 E es  1

4:5:4

This equation shows that the static permittivity is the appropriate value when the
system is equilibrated. At very high frequencies only the distortional component
of the polarization remains so that
Pd e0 E e1  1

4:5:5

170

LIQUIDS, SOLUTIONS, AND INTERFACES

The permittivity e1 is the value reached at the highest frequency used in the
relaxation experiment. Normally this corresponds to microwave frequencies of
the order of 1 THz but it can extend into the far infrared.
Now, one may estimate the orientational polarization as
Po P  Pd e0 E e  e1

4:5:6

At equilibrium, this contribution is


Poe Pe  Pd e0 E es  e1

4:5:7

It is also important to be able to relate the orientational polarization to the


electric displacement D. On the basis of equation (4.3.15), one may write
D e0 E Po Pd

4:5:8

P o D  e0 e1 E

4:5:9

so that

Under the usual circumstances, dielectric relaxation is studied at an electrical


eld which is controlled, for example, by controlling the voltage drop across a
parallel-plate condenser. On the basis of equation (4.5.2), substituting for Po and
Poe using equations (4.5.7) and (4.5.9), one obtains the following dierential
equation in D:
t

dD  e0 e1 E
D  e0 e1 E e0 Ees  e1
dt

4:5:10

Suppose that the dielectric system relaxes due to the application of a constant eld
E at time t 0. Then equation (4.5.10) simplies to
t

dD
D e0 es E D e
dt

4:5:11

where D0 is the equilibrium value of the electric displacement. The dierential


equation may also be written as
dD  De
dt

D  De
t

4:5:12

D De D0  De et=t

4:5:13

for which the solution is

where Do is the initial value of D. This equation describes an exponential decay in


D which is characterized by a relaxation time t, from the initial value D0 to the
equilibrium value De .
Most experimental studies involve measurements of the electrical permittivity
as a function of frequency using an alternating voltage or eld E. Then, the eld
varies with time according to the equation
E Em cos ot

4:5:14

where Em is the amplitude of the a.c. eld and o is its angular frequency. These
experiments are commonly discussed in terms of the frequency f , where

POLAR SOLVENTS

o
2p

171

4:5:15

The electrical displacement also varies in a sinusoidal fashion but is not necessarily in phase with the electrical eld. The relationship between these quantities is
obtained by solving equation (4.5.10). When the alternating eld is initially
applied to the system, there are some transients which describe the initial relaxation. The solution to the dierential equation presented here ignores the initial
eects, and considers only the properties of the system at a steady state. Under
such circumstances any uctuation in the system occurs at the same frequency as
that of the perturbing eld E.
In order to make the mathematics easier, the dierential equation is solved
using a complex number representation of the sinusoidally varying quantities (see
appendix A). Thus, the eld E is written as
E Em ejot

4:5:16

where
ejot cos ot j sin ot
4:5:17
p
and j is equal to 1. By comparing the magnitudes to the quantities associated
with cos ot and sin ot, one is able to estimate the phase angle of the alternating
quantity. The steady-state solution to the dierential equation for D is given by
D AD ejot

4:5:18

Substituting this expression for D into equation (4.5.10) one obtains


jotAD ejot  e0 e1 Em ejot AD ejot  e0 e1 Em ejot e0 Em ejot es  e1

4:5:19

Simplifying and solving for AD , the result is


AD

e0 Em es j!te1  es o2 t2 e1 
1 o2 t2

4:5:20

Under non-equilibrium conditions


D e e0 E

4:5:21

A D e e0 E m

4:5:22

It follows that

Now one can write the following equation for the varying permittivity:
e e
e e
4:5:23
e e1 s 212  jot s 212
1o t
1o t
This result obtained by Debye [1] describes the frequency dependence of the
permittivity e. In the following discussion the relaxation time measured with
the electrical eld E as the controlled variable is called the Debye relaxation
time and is given the symbol tD .
From equation (4.5.23) the in-phase component of the permittivity is
e e
ein e1 s 212
4:5:24
1 o tD

172

LIQUIDS, SOLUTIONS, AND INTERFACES

At very low or static frequencies (o 0, the in-phase component is equal to es as


one would expect. In the limit of very high frequencies, the in-phase component is
equal to e1 . For angular frequencies which are close to 1=tD , ein drops rapidly
from es to e1 , reaching the value (es e1 =2 when ot is equal to one.
The out-of-phase component is
eout

otD es  e1
1 o2 t2D

4:5:25

It is zero in the limits of very low and very high frequencies, and reaches a
maximum value equal to (es  e1 when ot is one. The fact that this term is
multiplied by j in the overall expression shows that the out-of-phase component
lags the in-phase component by 908.
Plots of the in- and out-of-phase components of the permittivity of a hypothetical solvent with typical parameters (es 50, e1 2, and tD 20 ps) are shown
as a function of the logarithm of the frequency in g. 4.5. The frequency range
over which most of the change in these quantities occurs is from 100 MHz to 1
THz. The upper limit is beyond the range of most microwave experiments, which
is about 300 GHz. The out-of-phase component reaches a maximum value when
otD 1, which occurs at a frequency of 8 GHz in this example. This is also the
frequency at which the rate of change in ein with frequency is a maximum.
Obviously, the frequency range shown in this plot could not be covered in a
normal microwave experiment. Thus, extrapolation techniques are often used to
estimate e1 and tD from real experimental data.
An alternative experiment is one in which permittivity changes are studied at
constant electrical displacement D, for example, for constant charge on the plates
of a capacitor. The resulting relaxation phenomena are then characterized by a

Fig. 4.5 Plots of the in-phase, ein , and out-of-phase, eout , components of the dielectric
permittivity of a hypothetical Debye solvent against the logarithm of frequency. The parameters assumed are ein =50, eout =2, and tD 20 ps.

POLAR SOLVENTS

173

dierent relaxation time and it is useful to examine this situation further. On the
basis of equation (4.5.10) when D is constant,
tD e0 e1

dE
D e0 es E
dt

4:5:26

Rearranging, one may write


tD e1 dE D  e0 es E

e
es
es 0 dt

4:5:27

de0 es E  D
D  e0 es E
dt

4:5:28

or
tL
where
tL

e1 tD
es

4:5:29

tL is known as the longitudinal relaxation time. Integration of equation (4.5.28)


leads to the result that
D  e0 es E D  e0 es E0 et=tL

4:5:30

where E0 is the initial value of E. Since the electric displacement is constant and
equal to the equilibrium value De , equation (4.5.30) can be rewritten as
E  Ee E0  Ee et=tL

4:5:31

where De is related to Ee through equation (4.5.21). Equation (4.5.31) shows that


the decay of E back to its equilibrium value Ee is described by a rate constant
1=L . It is analogous to equation (4.5.13), which was obtained for the case of
constant electrical eld E.
The relaxation properties of a polar solvent may be studied by carrying out
experiments in which the electrical eld E or displacement D are changed suddenly in a step fashion. In the case that the eld is the independently controlled
quantity, one follows the change in D with time. An analysis of the transient
observed experimentally allows one to determine the Debye relaxation time tD
on the basis of equation (4.5.13). Similarly, if one studies the relaxation transient
under conditions that D is suddenly changed, for instance, by suddenly changing
the charge on the plates of a capacitor, one observes a transient involving the
electrical eld E. Analysis of these data allows one to determine the longitudinal
relaxation time tL . If both experiments are conducted, comparison of tD and tL
allows one to estimate the high-frequency permittivity e1 assuming that the static
permittivity is already known.
However, dielectric relaxation experiments are usually conducted in the presence of sinusoidally varying electrical elds as a function of frequency. Many
such experiments have been carried out in various pure liquids and solutions [G5,
416, 29], and values of the in-phase and out-of-phase permittivity reported as a
function of frequency over a wide range. Analysis of these data to obtain es , e1 ,
and tD can be carried out in a variety of ways. On the basis of equations (4.5.24)

174

LIQUIDS, SOLUTIONS, AND INTERFACES

and (4.5.25), eliminating the common factor es  e1 =1 o2 t2D , one obtains the
equation
ein e1

eout
otD

4:5:32

This shows that a plot of ein against eout =o should be linear, with e1 being
obtained from the intercept and 1=tD from the slope. This method of data analysis
normally involves extrapolation because the experimental frequency range does
not include values of ein close to e1 . An alternative way of analyzing the data
results in estimates of es and tD from a linear plot. Multiplying equation (4.5.25)
by otD and adding (es  e1 =1 o2 t2D to both sides, one obtains
otD eout

es  e1
es  e1
1 o2 t2D

4:5:33

Combining this with equation (4.5.24), the result is


ein es  otD eout

4:5:34

Accordingly, a plot of ein against oeout should be linear with a slope of tD . Such
a plot is shown in g. 4.6 using data obtained for water at 258C [G5]. A linear
relationship is obtained with the data for frequencies less than 40 GHz. On the
basis of a straight line tted in this region, the value of es from the intercept is
78.20 and the value of tD from the slope, 8.38 ps r 0:9998.
A plot of the same data according to equation (4.5.32) is shown in g. 4.7. A
straight line can be drawn through the points obtained at frequencies below 40
GHz. The slope of this line gives 1=tD from which the value of tD is 8.37 ps. This
is in excellent agreement with the result from the previous plot. The intercept gives
the value of e1 , which is 6.02 for this system.

Fig. 4.6 Plot of ein against oeout using dielectric relaxation data for water at 258C [G5]. The
straight line is drawn considering only the data obtained at frequencies below 40 GHz.

POLAR SOLVENTS

175

Fig. 4.7 Plot of ein against eout =o using dielectric relaxation data for water at 258C [G5].
The straight line was tted using the data points shown as lled circles.

An important question is why the data obtained at frequencies above 40 GHz


do not follow the simple Debye model. A plot of eout against ein for data in the
high-frequency region is shown in g. 4.8. It is clear that the experimental results
lie above the values predicted by the Debye model using the best values of the
parameters found from data at lower frequencies. This suggests that another
relaxation process involving much higher frequencies is present in water. In the
alcohols [47], two high-frequency relaxation processes are found. The complex
nature of dielectric relaxation in this group of solvents is attributed to hydrogen
bonding.

Fig. 4.8 Plot of eout against ein using dielectric relaxation data for water in the frequency
range 60410 GHz [G5]. The solid line shows the contribution from the low-frequency
relaxation process.

176

LIQUIDS, SOLUTIONS, AND INTERFACES

It is often possible to describe the dielectric data for complex liquids in terms of
multiple relaxation processes, each of which follows a Debye relaxation based on
equation (4.5.2). The resulting equations for ein and eout are
ein en1

n
X
ei0  ei1
i1

1 o2 t2i

4:5:35

and
eout

n
X
ei0  ei1 oti
i1

1 o2 t2i

4:5:36

ei0 and ei1 are the low- and high-frequency values of the permittivity for the
relaxation process with relaxation time ti . The static permittivity es is equal to
the low- frequency permittivity for the rst relaxation process e10 . In addition, the
high-frequency permittivity for the ith relaxation ei1 is equal to the low-frequency
permittivity for the (i 1)th relaxation ei10 . Thus, for a liquid having n relaxation processes, there are n values of ei0 which must be specied together with n
dierent relaxation times, ti , and nally the high-frequency permittivity for the
last relaxation process, en1 .
In the case of water, it has been shown that the dielectric data can be described
in terms of two relaxation processes. Further analysis of the data shown in g. 4.8
leads to the following parameters: e20 6:02, e21 4:57, and t2 0:97 ps [G5].
The second relaxation process is much faster than the rst and is characterized by
frequencies in the terahertz range. The slow relaxation process which is characterized by a large amplitude (e10  e11 72 is attributed to a cooperative process
involving clusters of water molecules connected through hydrogen bonding. The
fast process is attributed to hydrogen bond formation and breakup. More will be
said about the nature of these processes in section 4.7.
Other relationships which have been used to describe dielectric relaxation data
include the ColeCole and ColeDavidson equations [29]. These are preferred
when a distribution of relaxation times rather than a single relaxation time is
more appropriate to describe the data in a given frequency range. Nevertheless,
the Debye model in its simple version or multiple relaxation versions works quite
well for most of the solvents considered here.
The principal problem with existing data in the literature is that they often are
not available over a suciently wide frequency range so that a reasonable analysis
at the high-frequency end cannot be made. Only recently have experiments been
carried out above 100 GHz. For solvents with rapid relaxation processes experiments above 1 THz in the far infrared region are required.

4.6 The Permittivity of Electrolyte Solutions


When an electrolyte is added to a polar solvent, the resulting solution has very
dierent electrical properties than those of the pure solvent. The most obvious
change is the fact that the solution has an easily measured conductivity due to the
presence of the ions. The solvent is a dielectric which behaves as a capacitor but its

POLAR SOLVENTS

177

dielectric properties change in the presence of the electrolyte. This is partially due
to the fact that the structure of the solvent is disrupted in the immediate vicinity of
the ions. Thus, in terms of an equivalent circuit, an electrolyte solution consists of
a resistor and capacitor in parallel.
By studying the frequency dependence of the impedance of an electrolyte solution one can learn something about both ionsolvent and ionion interactions and
how these aect solution structure. Dielectric relaxation data have been collected
for a number of electrolyte solutions, both aqueous and non-aqueous [G5, 29].
These data are obtained by measuring the impedance of the solution and then
correcting for solution conductivity. When simple electrolytes which do not ion
pair are involved, the permittivity data often can be treated by the Debye model.
A typical example is KCl in water. Values of ein plotted as a function of oeout for
this system at two dierent concentrations are shown in g. 4.9. On the basis of
equation (4.5.34), these plots give the value of es from the intercept and tD from
the slope. In this case, es is 76.58 at a concentration of 0.1 M, and 67.05 at 1 M.
The static permittivity decreases noticeably with increase in electrolyte concentration. This result is attributed to two factors. When the electrolyte ions do not
possess a dipole moment, as is the case for monoatomic ions, they do not respond
to the electrical eld applied to the system in the relaxation experiment. However,
they occupy volume in the system, so that the overall permittivity of the solution
decreases with increase in the mole fraction of the electrolyte. The second eect
related to the addition of electrolyte is connected to the breakup of solvent structure due to solvation of the ions. This is especially important in water solutions,
where hydrogen bonding plays an important role in determining solvent structure.
The value of the relaxation time also decreases with increase in electrolyte concentration. In the present case, tD varies from 8.26 ps for 0.1 M KCl to 8.05 ps for
1 M KCl.

Fig. 4.9 Plot of ein against oeout using dielectric relaxation data for aqueous KCl solutions:
(*) 0.1 and (^) 1 M.

178

LIQUIDS, SOLUTIONS, AND INTERFACES

The extent to which the dielectric permittivity of the solution departs from that
of the pure solvent depends not only on the electrolyte concentration but also on
the nature of the electrolyte. Considering the alkali metal halides, the largest drop
in es at a given concentration is found for Li electrolytes [G5, 29]. This reects
the disruptive eect of the small cation which causes reorientation of the solvent
molecules around it and a subsequent breaking of hydrogen bonds. The dielectric
decrement decreases with increase in cation atomic number for a given anion. On
the other hand, in the case of anions the dielectric decrement increases with
increase in anion atomic number for a given cation. Anions are less disruptive
of water structure, so that the main eect of changing the anion is a change in the
volume fraction of solution occupied by ions.
Representative plots of es as a function of concentration are shown in g. 4.10.
The principal feature depending on electrolyte concentration is the initial slope
which is called the dielectric decrement. In addition all plots are curved, suggesting that a limiting permittivity is reached at high electrolyte concentration. The
dependence of es on electrolyte concentration ce has been examined by Friedman
[30], who derived the following relationship:
es es0  de ce be c3=2
e

4:6:1

where es0 is the dielectric permittivity of the pure solvent, de , the dielectric decrement, and be , a curvature parameter. This equation describes the concentration
dependence of es quite well for most 11 electrolytes over a wide concentration
range. The curvature parameter is small for 11 electrolytes, usually falling in the
range 25 L3=2 mol3=2 . When be is set equal to 5 L3=2 mol3=2 , the values of de for
the alkali metal halides fall in a range from 14 to 22 L mol1 [31].

Fig. 4.10 Plots of the static permittivity of three 11 electrolyte solutions against electrolyte concentration. The ordinate scale is correct for the NaCl data; for KF, the data have
been shifted up by 10 units, and for KBr, down by 10 units for the sake of clarity.

POLAR SOLVENTS

179

EXAMPLE

Use the following permittivity data for aqueous NaClO4 solutions at 258C to
determine the best values of the parameters de and be for this electrolyte:
ce =M
es
0.5
1.0
1.5
2.0
3.0
4.0
5.0

70.41
63.56
58.17
53.44
47.28
40.29
35.21

The permittivity of pure water at 258C is 78.46. Thus, equation (4.6.1) can
be rearranged as follows:
78:46  es
de  be c1=2
e
ce

4:6:2

The parameters de and be are determined from a plot of (78:46  es =ce against
ce1=2 . The required data are given in the following table:
1=2
c1=2
e =M

1
78:46  es c1
e =M

0.707
1.000
1.225
1.414
1.732
2.000
2.236

16.1
14.9
13.5
12.5
10.4
9.5
8.7

These data are tted to a straight line by least squares. From the intercept,
de 19:4 M1 and be 5:1 L3=2 mol3=2 .
When ion pairing is present an additional relaxation is observed at low frequencies. A typical example is the MgSO4 system in water. The ion pair has a
dipole moment and therefore this species reorients in the alternating electrical
eld. The relaxation time associated with the reorientation is much longer than
that associated with the reorientation of water molecules. It depends not only on
reorientation of the ionpair dipole but also on the kinetics of its formation and
decomposition. For this reason, the parameter for the low-frequency relaxation
process is strongly concentration dependent.
Dielectric relaxation data for a 0.08 M Mg2 SO4 solution are shown in g. 4.11.
On the basis of an analysis of these data by Barthel and coworkers [29, 32], three
relaxation processes may be discerned. The rst one, involving the ion pair, occurs
between permittivity values of 82.9 and 75.2 and involves a relaxation time of 181
ps. The second process, which is attributed to the slow reorientation of water
clusters, takes place between the permittivity values of 75.2 and 8.4 with a relaxation time of 8.4 ps. Finally, the high-frequency process, which occurs between 8.4

180

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 4.11 Plot of ein against eout for dielectric relaxation data obtained with 0.08 M MgSO4
in water. The semicircles show the resolved Debye relaxation processes for (a) the ion pair;
(b) the slow reorientation of water clusters; (c) the fast process in water.

and 4.6 with a relaxation time of 1.5 ps, is attributed to the formation and breaking of hydrogen bonds.
Obviously, the dielectric behavior of systems with ion pairing is much more
complex than those without it. The presence of the ion pair gives the solution a
higher permittivity at lower frequencies than it otherwise would have. This feature
is important in understanding the equilibrium properties of these solutions. The
permittivity data for the low-frequency process may be used to determine the ion
pairing equilibrium constant and the rate constants for formation and breakup of
this species. Thus, dielectric relaxation experiments in electrolytes provide valuable information about ion association equilibria.
A variety of dielectric relaxation data are now available for both aqueous and
non-aqueous solutions. These results help one understand the properties of these
solutions in more detail. They are complementary to information obtained from
thermodynamic, spectroscopic, and conductivity experiments, and provide an
important basis for understanding solution structure.

4.7 The Dielectric Relaxation Parameters


According to the Debye model there are three parameters associated with dielectric relaxation in a simple solvent, namely, the static permittivity es , the Debye
relaxation time tD , and the high-frequency permittivity e1 . The static permittivity
has already been discussed in detail in sections 4.3 and 4.4 . In this section attention is especially focused on the Debye relaxation time tD and the related quantity, the longitudinal relaxation time tL . The signicance of these parameters for
solvents with multiple relaxation processes is considered. The high-frequency
permittivity e1 and its relationship to the optical permittivity eop is also discussed.

POLAR SOLVENTS

181

As dened, the Debye relaxation time is the reciprocal of a rst-order rate


constant. Thus, it is expected to depend on temperature according to the usual
Arrhenius relationship


HD
tD AD exp
4:7:1
RT
where AD is a pre-exponential factor and HD , the activation enthalpy associated
with the relaxation process. Values of HD are available for many polar solvents
and fall in the range from 5 to 25 kJ mol1 (see table 4.2). For unassociated polar
solvents the relaxation process is assumed to involve rotation of a molecular
dipole in the alternating electrical eld and is called rotational diusion. The
major barrier to this process is dipoledipole interactions. Thus, it was shown
that HD is a linear function of the enthalpy associated with dipoledipole interactions in aprotic solvents [6]. Although tD is not a molecular parameter, it is
related in a complex way to the molecular events which take place in a polar liquid
subjected to an alternating electrical eld [G2].
The temperature dependence of the longitudinal relaxation time L is also an
important quantity. For a Debye solvent, tL is given by the relationship
e
4:7:2
tL 1 tD
es
The enthalpy associated with the temperature dependence is dened as
HL R

@ ln tL
@ ln e1
@ ln es
HD R
R
@1=T
@1=T
@1=T

4:7:3

The temperature derivatives of the high- and low-frequency contributions to the


permittivity are easily estimated from experimental data (see table 4.2). In some
cases the temperature derivative of e1 is not available but one may assume that it
is approximately equal to the temperature derivative of eop .
Unfortunately, the Debye model provides only an approximate description of
aprotic solvents. It has been applied extensively to determine their relaxation
properties quite successfully, mainly because permittivity data are available
over a limited frequency range. As a result, the high-frequency parameter is
usually obtained by a long extrapolation. As experimental methods have become
available at frequencies above 50 GHz, it has been found that the behavior of
aprotic solvents is more complex [9].
Acetonitrile (AcN) can be described by the Debye model using data up to 40
GHz [9]. When the frequency range is extended to 90 GHz, the data can only be
tted if a distribution of relaxation times is assumed. Dimethylsulfoxide (DMSO)
and propylene carbonate (PC) have been studied up to 89 GHz [9]. These data can
be tted to the Debye model with two relaxation processes. DMSO is known to
form dimers in the bulk [28]. This association is undoubtedly the reason for its
complex relaxation behavior. The same is true for PC, a molecule with a very high
dipole moment.
The dielectric relaxation data for dimethylformamide (DMF) and dimethylacetamide (DMA) can be described by two Debye processes [9]. The lowfrequency, high-amplitude process is attributed to rotational diusion. For

182

LIQUIDS, SOLUTIONS, AND INTERFACES

these systems, the high-frequency relaxation is ascribed to hindered intramolecular rotation about the CN bond [9].
All protic solvents undergo multiple relaxation processes due to the presence of
hydrogen bonding. In the case of water and formamide (F), the data can be
described in terms of two Debye relaxations. For the alcohols and N-methylformamide (NMF), three Debye relaxations are required for the description. In
all of these solvents, the low-frequency process involves the cooperative motion of
hydrogen-bonded clusters. In the case of water and the alcohols the highfrequency process involves the formation and breaking of hydrogen bonds. The
intermediate process in the alcohols is ascribed to rotational diusion of monomers. Studies of dielectric relaxation in these systems have been carried out for the
n-alkyl alcohols up to dodecanol [8]. Values of the relaxation parameters for water
and the lower alcohols are summarized in table 4.5.
F and NMF are also highly structured solvents as a result of hydrogen bonding. The low-frequency relaxation process in these systems can be attributed to the
cooperative motion of hydrogen-bonded clusters. The process at the highest frequencies has a similar relaxation time to those observed in DMF and DMA.
Thus, it is probably due to intramolecular rotation about the CN bond in the
monomer. The intermediate relaxation observed in NMF is attributed to rotational diusion of a monomer. Relaxation parameters for F and NMF are also
summarized in table 4.5.
Estimation of the longitudinal relaxation time in solvents with multiple Debye
relaxation processes is not straightforward. In fact, tL is a function of time in
these systems [33, 34], and varies between two limiting values. For a solvent with
two relaxation processes, the low-frequency limit for tL is
e
tL0 1 f1 tD1 f2 tD2
4:7:4
es
where
fi

ei0  ei1
e s  e1

4:7:5

At high frequencies, the limiting value of tL is




e1 f 1
f2 1
tL1

es tD1 tD2

4:7:6

Table 4.5 Dielectric Relaxation Parameters for Some Protic


Solvents at 258C [5, 9]
Solvent

es e10

t1 =ps

e20

t2 =ps

e30

t3 =ps

e1

W
MeOH
EtOH
PrOH
F
NMF

78.45
32.63
24.35
20.44
109.5
186.0

8.32
51.5
163
329
37.3
128

6.18
5.91
4.49
3.74
7.08
6.13

1.02
7.09
8.97
15.1
1.16
7.93

4.90
3.82
3.20

4.60

1.12
1.81
2.40

0.78

4.49
2.79
2.69
2.44
4.48
3.20

POLAR SOLVENTS

183

The time characterizing transition between tL1 and tL0 is tm , which is given by
tm f1 tD1 f2 tD2

4:7:7

It is interesting to calculate these parameters for water on the basis of the data
given in table 4.5. For this solvent, the fractions f1 and f2 are 0.977 and 0.023,
respectively. As a result, the low-frequency value of tL , tL0 , is equal to 0.47 ps.
Because f1 is close to one, the inuence of the high-frequency process on tL0 is
minimal. At high frequencies, the limiting value of tL , tL1 , is 0.41 ps. For this
system the dierence between the limiting values of tL is very small and beyond
the limit of experimental detection under most circumstances. The time characterizing transition between tL1 and tL0 is 1.19 ps. Thus, for processes occurring at
frequencies greater than 10 THz, the appropriate value of tL is tL1 . For frequencies lower than 100 GHz, the corresponding value is tL0 .
When the solvent has three relaxation processes, the above relationships for tL
become
tL0

e1
f t f2 tD2 f3 tD3
es 1 D1

4:7:8



e1 f1
f
f 1
2 3
es tD1 tD2 tD3

4:7:9

and
tL1

Variation of tL between the high- and low-frequency limits is characterized by


two exponentially decaying functions with dierent transition times [34]. In the
case of the alcohols the dierence between these limits is signicant and can lead
to complex relaxation behavior in these solvents. For methanol, the highfrequency value of tL is 1.0 ps and the low-frequency value, 4.0 ps. For 1-propanol, the dierence is greater, the corresponding values being 5.3 and 36.5 ps,
respectively.
The high-frequency permittivity e1 reects the value of this property when
reorientation of the solvent dipoles no longer contributes to polarization of the
medium. As the frequency of the a.c. electrical eld increases, the ability of the
molecules to respond rapidly decreases. Eventually, the solvent dipoles become
frozen when the a.c. frequency is very high. This occurs typically for frequencies close to 1 THz, corresponding to relaxation times in the order of 1 ps.
Experimentally, these processes occur in the far infrared at frequencies of 30
cm1 or greater. The molecules now respond to the electromagnetic eld through
distortional and electronic polarization. Distortional polarization corresponds to
movement of the molecular nuclei with respect to one another and is equivalent to
molecular vibration. As the frequency of the electromagnetic eld increases into
the infrared, discontinuities are found in the permittivity of the liquid corresponding to the frequency at which a given molecular vibration occurs. The permittivity
after each of these vibrations is activated decreases until the distortional contribution to the permittivity is lost. Eventually in the visible region, the molecules
only respond via electronic polarization, that is, response of the electronic cloud
in the molecules to the alternating electrical eld. This response is normally

184

LIQUIDS, SOLUTIONS, AND INTERFACES

determined by measuring the refractive index of the liquid at the sodium D line
(589 nm) and thereby estimating eop . Because of the distortional contribution to
the permittivity, e1 is always larger than eop . For example, in the case of water,
e1 is 4.49 and eop , 1.78.
Relaxation parameters such as tD and tL are used in the analysis of the kinetics
of very fast processes in solution. As one might expect, movement of solvent
molecules can be inuential in determining the rates of these processes. Thus,
the study of dielectric relaxation not only provides valuable information about
solvent structure but also relaxation parameters relevant to fast solution kinetics.
This subject is discussed in more detail in chapter 7.

4.8 Ion Solvation in Polar Solvents


The variation in ion solvation with solvent nature is an interesting subject because
it is relevant to basic ideas about the structure of electrolyte solutions. According
to the classical Born model, the Gibbs energy of ion solvation depends on solvent
nature only through its static dielectric permittivity es . When this subject was
examined for aqueous solutions in chapter 3, it was concluded that local ion
solvent interactions are very important in determining the magnitude of the Gibbs
energy of solvation and that these interactions result in disruption of local solvent
structure. Therefore, it is interesting to examine ion solvation in a wide variety of
polar solvents in order to assess the relative importance of long-range electrostatic
and short-range chemical forces.
The most direct way of determining s G is by measuring the work associated
with transferring the electrolyte from the gas phase, where the ions are innitely
far apart from one another, to the liquid solution. However, from a practical
point of view, it is much simpler to solve this problem starting with the solid
electrolyte. Consider a simple 11 electrolyte MX which dissolves in solvent S:
MXcry !MXsl S

4:8:1

The Gibbs energy change associated with formation of the solution may be
written as
sl G sl G RT ln aM aX

4:8:2

where sl G is the value of sl G at unit activity on the molarity scale. When the
dissolution process (4.8.1) is at equilibrium, the electrolyte solution is saturated
and one may write
sl G RT lnaM aX sat RT ln Ksp

4:8:3

where Ksp is the thermodynamic solubility product. Following the usual thermodynamic conventions for electrolytes, sl G is the standard Gibbs energy change
associated with dissolution of solid electrolyte in a hypothetical 1 M solution in
which all real interactions are absent (see section 3.6). In practice, solubility
products are reported in the literature in terms of concentrations. Thus, determi-

POLAR SOLVENTS

185

nation of sl G usually requires that one estimate the mean activity coecient of
the electrolyte in the saturated solution. One way of avoiding this problem is to
use an electrochemical cell to determine Ksp with electrodes reversible to the
cation and anion of the electrolyte (see chapter 9).
In order to remove the contribution to sl G from the solid phase, values of
this quantity are compared in two dierent solvents. If one imagines that the same
salt is dissolved in two dierent solvents S1 and S2 , then one may estimate the
Gibbs energy of transfer of MX according to the process
MXsl S1 !MXsl S2

4:8:4

The corresponding standard Gibbs energy change is called the Gibbs energy of
transfer:
tr G sl G S2  sl G S1

4:8:5

tr G depends only on the dierences in the interaction of the ions with the two
solvents, the contribution from the solid phase having been lost in subtraction.
Values of sl G have been determined for many electrolytes in most of the
polar solvents considered in this chapter. Various reference solvents have been
considered for reporting tr G [3538] but that used in most recent work is water.
Thus, tr G gives the Gibbs energy associated with transferring one mole of the
electrolyte in the hypothetical standard state from water to the given non-aqueous
solvent. This quantity is positive for most simple 11 electrolytes because the
electrolyte is less soluble in the non-aqueous medium [36, 37].
Obviously, it is more interesting to have single ion quantities for the Gibbs
energy of transfer. This requires that an extrathermodynamic assumption be
made to achieve separate cation and anion contributions. Many assumptions
have been considered and evaluated in the literature [38, 39]. Only one is described
here and its use may be considered a convenient convention which leads to reasonable separation of the cationic and anionic contributions to tr G . By choosing an electrolyte with very large ions whose charge is buried in the center of the
ion, it can be assumed that the cation and anion have equal contributions to
tr G . The electrolyte used is tetraphenylarsonium tetraphenylborate (TATB)
which is sparingly soluble in water, but more soluble in non-aqueous media. As
a result, the values of tr G for this electrolyte are negative. The TATB assumption is expressed quantitatively through the equation
tr G TA tr G TB

tr G TATB
2

4:8:6

By choosing a series of electrolytes which includes salts containing the tetraphenylarsonium cation and the tetraphenylborate anion, the individual contributions
to tr G from the more common ions may be extracted.
EXAMPLE

The following data are for the Gibbs energy of transfer from water to propylene carbonate for 11 electrolytes at 258C [37]. Use these data to estimate the
corresponding quantities for the individual ions on the basis of the TATB
assumption.

186

LIQUIDS, SOLUTIONS, AND INTERFACES

Electrolyte
LiI
NaCl
KCl
KI
TAI
TATB

tr G =kJ mol1


43.7
53.1
44.4
23.4
19.2
72.0

From the value of tr G for TATB,


tr G TA tr G TB 72:0=2 36:0 kJ mol1

4:8:7

From the value of tr G for TAI,


tr G I 19:2 36:0 16:8 kJ mol1

4:8:8

From the data for the other iodides,


tr G Li 43:7  16:8 26:9 kJ mol1


tr G K 23:4  16:8 6:6 kJ mol

1

4:8:9
4:8:10

From the data for the chlorides,


tr G Cl 44:4  6:6 37:8 kJ mol1

4:8:11

tr G Na 53:1  37:8 15:3 kJ mol1

4:8:12

and

These results are slightly dierent than the values recorded in tables 4.6 and
4.7. The tabulated data are based on a larger collection of results for 11
electrolytes and therefore are better estimates of the single ion values.
Values of tr G for the alkali metal cations together with the value for the
tetraphenylarsonium ion are given in table 4.6 for the solvents considered in this
chapter. For the alkali metal ions, tr G is both positive and negative, the latter
values indicating that the ion is more stable in the non-aqueous environment. In
the case of the Na ion, tr G varies from 17 kJ mol1 in hexamethylphosphoramide (HMPA) to 36 kJ mol1 in nitrobenzene. It is clear that there is no
correlation between tr G and the static permittivity es or a related function of es ,
such as that found in the Born equation (3.4.6). The solvent with the highest
permittivity among those considered is NMF. Its value of tr G for Na is
negative but not as large as that seen for solvents like HMPA or DMSO.
Similarly, BuOH has a very low permittivity but its value of tr G is not as
large as that of NB. This point is further demonstrated by considering three
aprotic solvents with approximately the same values of es , namely, AcN, DMF,
and NM. The values of tr G for the Na ion in these solvents are 15.1, 9:6, and
32 kJ mol1 , respectively. This shows emphatically that chemical interactions are

POLAR SOLVENTS

187

Table 4.6 Gibbs Energy of Transfer for Monovalent Cations


from Water to a Non-Aqueous Solvent at 258C [39]
tr G /kJ mol1
Solvent

Li

Na

Rb

Cs

Ph4 As

(529)
4.4
11
11
11
10
20

(424)
8.2
14
17
19
8
7

(352)
9.6
16.4
17
20
4.3
6

(329)
9.6
16
19
23
5
8

(306)
8.9
15
17
19
6
7

24.1
21.2
25
20
23.9
33

10
25
36

22
10
15

35
38
48
27
23.8
6
23

10
15.1
21
16
12.1
9.6
13.4
17
15
36
31.6
15
14.6
3
14

4
8.1
19

11.7
10
13.0
16
11
21
15.4
11
5.3
4
13

4
6.3
15

8
9.7
10.4
10
8
19
11.0

1
9
10

4
6.0
13

7
10.8
13.0
7
10
18
5.6

7
10

32
32.8
35

40
38.5
37.4
39
40
36
32.6

36
36

Protic
1.
2.
3.
4.
5.
6.
7.

Wa
MeOH
EtOH
PrOH
BuOH
F
NMF

Aprotic
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.

AC
AcN
BzN
BuNb
DMA
DMF
DMSO
HMPA
NMP
NB
NM
PrN
PC
TMS
TMUb

Values in parentheses give the absolute Gibbs energy of solvation in water


estimated from experiment.
b
Estimated from polarographic halfwave potential data [40].

much more important in determining solvation in these systems than long-range


electrostatic eects.
Values of tr G for some halide ions, the perchlorate ion, and the tetraphenylborate ion are given in table 4.7. This quantity is always positive for the halide
ions, and is much larger in aprotic solvents than in protic systems. Thus, small
monoatomic anions are especially dicult to solvate when hydrogen bonding is
not available in the system. The same is not true for the perchlorate ion, which
actually is more stable in some aprotic solvents than in water. Because the negative charge in the ion is distributed over ve atoms, it dissolves more easily than
the Cl anion in all non-aqueous media. For this reason perchlorate salts are
often used to introduce cations into a non-aqueous solvent. Values of tr G for
the tetraphenylborate anion are always large and negative, and by denition equal
to the values for the tetraphenylarsonium cation.

188

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 4.7 Gibbs Energy of Transfer for Monovalent


Anions from Water to a Non-Aqueous Solvent at 258C
[39]
tr G /kJ mol1
Solvent

Cl

Br

I

ClO
4

Ph4 B

(304)
13.2
20.2
26
29
13.7

(278)
11.1
18.2
22
24
10.7

(243)
7.3
12.9
19
22
7.3

(165)
6.1
10
17
22
12

24.1
21.2
25
20
23.9
33

57
42.1
47

54.9
48.3
40.3
58
51
35
37.7

39.8
47

42
31.3
37

44.0
36.2
27.4
46
37
29
29

30
35

25
16.8
25

21
20.4
10.4
30
19
18
18.9

13.7
21

6
2
13

4
1
7
12
10
4.7

3

32
32.8
35

40
38.5
37.4
39
40
36
32.6

36.0
36

Protic
1.
2.
3.
4.
5.
6.
7.

Wa
MeOH
EtOH
PrOH
BuOH
F
NMF

Aprotic
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.

AC
AcN
BzN
BuN
DMA
DMF
DMSO
HMPA
NMP
NB
NM
PrN
PC
TMS
TMU

a
Values in parentheses give the absolute Gibbs energy of solvation in
water estimated from experiment.

Extensive data also exist for the enthalpy of transfer of 11 electrolytes from
water to non-aqueous solvents. These data are obtained in calorimetric experiments in which the enthalpy of solution is measured as a function of electrolyte
concentration. The value of the enthalpy of solution per mole at innite dilution is
obtained by extrapolation. The enthalpy of transfer is dened in the same way as
the Gibbs energy of transfer according to process (4.8.4). Thus, the standard
enthalpy of transfer is given by
tr H  sl H  S2  sl H  S1

4:8:13

The reference solvent in common use is water [39].


Several extrathermodynamic assumptions have been considered to separate
experimental values of tr H  into cationic and anionic contributions [35]. The
one commonly used is the TATB assumption, namely, that the contributions to

POLAR SOLVENTS

189

tr H  for the large tetraphenylarsonium and tetraphenylborate ions are equal.
This leads to the values shown in tables 4.8 and 4.9 for the alkali metal and halide
ions.
Values for tr H  for the alkali metal cations are negative in almost all cases.
Exceptions are those for Li and Na+ in NM, and Li in PC and TMS. It
follows that the interaction of these monoatomic monovalent cations is more
exothermic with most polar solvents than with water. On the other hand, the
enthalpy of transfer of the smaller anions, Cl and Br , is almost always positive.
This is a direct indication that these species are dicult to dissolve, especially in
aprotic solvents. In the case of I and ClO
4 , the enthalpy of transfer is usually
negative. Comparison of the enthalpy data with the Gibbs energy data recorded in
tables 4.6 and 4.7 shows that these quantities are very dierent. When both Gibbs
energies and enthalpies of transfer are available, one can calculate the entropy of
transfer [39].

Table 4.8 Enthalpy of Transfer for Monovalent Cations from Water to a


Non-Aqueous Solvent 258C [39]
tr H  =kJ mol1
Solvent

Li

Na

Rb

Cs

Ph4 As

(578)
21.7
20.2
18.4

6.0

(464)
20.7
19.4
18.8

16.5
22.5

(381)
19.0
19.6
18.3

17.9

(355)
16.5

17.8

(330)
14.1
11.8
12.7

17.7

2.2
0
1.5

0.5
7.6

8.0

25.4
27.1
57.4
26

25.8

2.8
12

13.3

41.2
32.4
29.2
50.6
41

11.5

10.5
16

22.9

35.7
35.4
46.6
47

18.5

22.5
26

24.6

36.1
38.1
43.8
55

17.7

24.9
28

26.1

34.6
33.0
45.0
50

16.6

27.5
26

11.1

13.7
17.2
10.6
25.8
17

6.9

13.1
11

Protic
1.
2.
3.
4.
5.
6.
7.

Wa
MeOH
EtOH
PrOH
BuOH
F
NMF

Aprotic
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.

AC
AcN
BzN
BuN
DMA
DMF
DMSO
HMPA
NMP
NB
NM
PrN
PC
TMS
TMU

a
Values in parentheses give the absolute enthalpy of solvation in water estimated from
experiment.

190

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 4.9 Enthalpy of Transfer for Monovalent Anions from


Water to a Non-Aqueous Solvent 258C [39]
tr H  /kJ mol1
Solvent

Cl1

Br

I

ClO
4

Ph4 B

(320)
8.4
10.4
8.4

3.5
14.2

(289)
4.5
5.5
2.5

1.5

(247)
1.0
0.7
1.5

6.8

(176)
3.1
2.7
0

20
11.8

0.9
0
1.5

0.5
7.6

19.3

35.6
17.9
20.0
38.2
27

21.2

26.2
27

8.0

17.2
0.6
4.6
17.7
13

7.1

15.2
13

7.6

0.7
15.0
11.5
5.8
2

7.8

1.6
8

16.0

15.3
23.4
18.2
20.7
11

19.2

16.3
20

11.1

13.7
17.2
10.6
25.8
17

6.9

13.1
11

Protic
1.
2.
3.
4.
5.
6.
7.

Wa
MeOH
EtOH
PrOH
BuOH
F
NMF

Aprotic
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.

AC
AcN
BzN
BuN
DMA
DMF
DMSO
HMPA
NMP
NB
NM
PrN
PC
TMS
TMU

a
Values in parentheses give the absolute enthalpy of solvation in water estimated
from experiment.

Using the absolute values of the Gibbs energy of solvation for the individual
ions in water one can calculate the absolute value of this quantity in any solvent
using the relationship
s GS s GW tr G

4:8:14

where s GS is the Gibbs energy of solvation in solvent S and s G(W) the


corresponding quantity in water. According to the Born model for ion solvation
presented in section 3.4, the Gibbs solvation energy for a given ion depends on
solvent nature only through the dielectric permittivity es . Specically, this model
predicts that s G(S) should be linear in (1  1=es ) provided the ionic radius ri
does not depend on solvent nature. However, plots based on the data in tables 4.6
and 4.7 for simple cations and anions show no correlation between s G(S) and
(1  1=es ). These results emphasize that a simple electrostatic model cannot
account for the variation in the Gibbs energy of solvation with solvent nature.

POLAR SOLVENTS

191

As will be seen in the following section, the chemical nature of the interaction
between the ion and the solvent must be considered in order to understand this
variation.
The data in tables 4.64.9 are very helpful in predicting the solubility of a given
electrolyte in a solvent. In addition, they give an indication of the extent to which
ion pairing is important. If the solvent interacts strongly with the ion, then its
tendency to form ion pairs is reduced. Data are available for more ions than those
considered here, and these can be consulted to assess the properties of other
electrolytes in a given solvent [39, 40].

4.9 Polar Solvents as Lewis Acids and Bases


Examination of the variation in thermodynamic properties of electrolytes in polar
solvents shows conclusively that continuum electrostatic models are not able to
account for the experimental data. As a result, chemists have looked for other
ways of explaining the variation in these quantities with solvent nature. Since ions
are stabilized by the dipolar character of the solvent molecule, a method of
measuring the ability of a given solvent to solvate cations and anions was sought.
Cations are stabilized by the electronegative end of the solvent dipole. Thus, the
important property of the solvent molecule is its ability to donate a pair of
electrons, that is, to act as a Lewis base. On the other hand, anions are stabilized
by the positive end of the solvent dipole. The relevant molecular property is
solvent acidity or the ability to accept a pair of electrons. In the case of Lewis
acidity, the ability to form hydrogen bonds is also a contributing factor. The fact
that the chemical nature of the ends of the molecular dipole is quite dierent
means that a given solvent can have a very dierent Lewis acidity and basicity.
Early work by Dimroth and Reichardt [41, 42] led to the development of a
polarity scale ET based on a solvatochromic dye. This dye, namely, 4-(2,4,6triphenyl-pyridinium)-2,6-diphenylphenoxide undergoes a pp transition in the
visible or ultraviolet which is accompanied by a large decrease in the molecular
dipole moment (see g. 4.12). In the ground state, the dye interacts strongly with
the solvent through the electronegative oxygen atom. The wavelength associated
with the pp transition depends strongly on the nature of the solvent and is
clearly related to solvent acidity, that is, to the solvents ability to solvate the
electronegative oxygen atom in the ground state. Thus, the pp transition is
observed at 810 nm in a non-polar solvent such as diphenyl ether, whereas it
occurs at 453 nm in water. ET is dened on the basis of the energy associated
with this transition in kJ mol1 . It provides an important empirical parameter for
measuring solvent acidity (see table 4.10).
Another scale for measuring solvent acidity was formulated by Mayer et al.
[43]. It is called the solvent acceptor number (AN) and is based on the relative
values of the 31P NMR chemical shifts produced by a given solvent with a strong
Lewis base, triethylphosphine oxide (g. 4.13). The data were normalized so that
the acceptor number of hexane is zero and that for the 1:1 adduct with the strong
Lewis acid, SbCl5, 100 when dissolved in 1-2 dichloroethane. The attractive feature of this scale is that it varies over a wide range for the polar solvents con-

192

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 4.12 Chemical structure


of the solvatochromic dye
used to dene the ET
polarity scale: left, ground
state; right, excited p state.

sidered here, namely, from 10.6 for hexamethylphosphoramide to 54.8 for water
(table 4.10).
As one would expect, there is a strong linear correlation between the parameters ET and AN, the relationship being

Table 4.10 Empirical Parameters for Solvent


Acidity and Basicity
Acidity
Solvent

Basicity

AN

ET

DN

Bsc

54.8
41.5
37.9
37.3
36.8
39.8
32.1

264.0
231.8
217.1
212.1
210.0
236.8
226.4

18.0
19.0
19.2
19.8
19.5
24
27

591
589
589
589b
589
598
604

12.5
18.9
15.5
15.2a
13.6
16.0
19.3
10.6
13.3
14.8
20.5
22.7a
18.3
19.2
10.7a

176.6
190.8
173.6
180.3
182.8
183.3
188.7
171.1
176.6
172.4
193.7
195.0
184.1
171.5
171.5

17.0
14.1
11.9
16.6
27.8
26.6
29.8
38.8
27.3
4.4
2.7
16.1
15.1
14.8
31

569
573
572
573b
608
602
613
633
604b
522
530
572b
554
562
596

Protic
1.
2.
3.
4.
5.
6.
7.

W
MeOH
EtOH
PrOH
BuOH
F
NMF

Aprotic
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
a

AC
AcN
BzN
BuN
DMA
DMF
DMSO
HMPA
NMP
NB
NM
PrN
PC
TMS
TMU

Estimated on the basis of equation (4.9.1).


Estimated on the basis of equation (4.9.2).

POLAR SOLVENTS

193

Fig. 4.13 Lewis base, triethylphosphine oxide, used to


dene the AN scale.

ET 150:6 1:954 AN

4:9:1

with a correlation coecient of 0.964. The slope of this relationship demonstrates


that the variation in ET is only 47% of that in AN, so that AN is the preferred
parameter to assess solvent acidity. Equation (4.9.1) can be used to estimate
values of AN which were missing from the original compilation [43]. These are
also given in table 4.10.
A popular method of estimating solvent basicity is based on the donor number
scale, DN, introduced by Gutmann [44, 45]. The donor number is dened as the
value of the heat of reaction of the polar solvent with the strong Lewis acid SbCl5
when these reactants are dissolved in 1,2-dichloromethane (g. 4.14). The scale
suers from the problem that DN cannot be measured directly for protic solvents
because of the instability of SbCl5 in these systems. However, values of DN for
these solvents have been estimated by a variety of other techniques [46].
Another method of estimating solvent basicity makes use of the solvatochromism of a Cu2 complex, namely Cu(II) N;N;N 0 ;N 0 -tetramethylethylenediamine
acetoacetonate [47]. This parameter which is designated Bsc is especially convenient because it may be measured directly for all the solvents considered here,
both protic and aprotic. The relationship between Bsc and DN is
Bsc 525:2 2:89DN

4:9:2

with a correlation coecient of 0.942. Unfortunately, experimental values of Bsc


are not available for all the solvents considered here but they may be estimated
using equation (4.9.2).
It was pointed out earlier that the Gibbs energy of transfer of simple monatomic ions such as Na and Cl1 is not related in any simple way to the dielectric
permittivity of the solvent. On the other hand, tr G for the alkali metal cations is
correlated with solvent basicity. A plot of this quantity for the Na ion against the
solvents donor number DN is shown in g. 4.15. Although the correlation is not
excellent, it shows a clear trend in which tr G becomes more negative as DN
increases. This is exactly what one expects because the ability of the solvent to
stabilize the cation in solution increases with increase in solvent basicity.
On the basis of the MSA, the molar Gibbs solvation energy for a monovalent
ion i in solvent S is

Fig. 4.14 Lewis acid, antimony pentachloride, used to


dene the DN scale.

194

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 4.15 Plot of the Gibbs energy of transfer of Na from water to various non-aqueous
solvents against the Gutmann donor number DN.

s Gi S




NL e20
1
1
1
e s r i ds
8pe0

4:9:3

where NL is the Avogadro constant, e0 , the fundamental charge, e0 , the permittivity of free space, es , the solvents dielectric permittivity, ri , the ions radius, and
ds , the MSA parameter correcting ri . The latter quantity depends not only on the
nature of the solvent but also on whether the ion is a cation or an anion. Dening
1/ds as Bs or solvent basicity, for the case of a monovalent cation, equation (4.9.3)
may be rewritten as



NL e20
1
Bs
4:9:4
s GM S
1
es 1 Bs ri
8pe0
This shows that the Gibbs solvation energy changes with solvent nature due to
changes in es and Bs . Since the factor (1  1=es ) is close to unity for the polar
solvents discussed here, and assuming that Bs ri does not change signicantly with
respect to one, then the main reason for the correlation seen in g. 4.15 is the
change in Bs . Thus, the reciprocal of the MSA parameter for cations is directly
related to solvent basicity [48, 49].
Values of Bs estimated using the data for Na ion given in table 4.6 are plotted
against the Gutmann DN in g. 4.16. A good linear correlation is found with a
correlation coecient of 0.921. The equation relating Bs to DN is
Bs 16:30 0:314DN

4:9:5

Thus, Bs provides an alternate empirical scale for solvent basicity.


In the case of the halide anions, the Gibbs energy of transfer is correlated with
solvent acidity. A plot of tr G for the chloride anion is shown as a function of
the Gutmann AN in g. 4.17. A very good correlation is found based on the data

POLAR SOLVENTS

195

Fig. 4.16 Plot of the MSA parameter Bs estimated in various solvents for the Na ion
(equation (4.9.4)) against the Gutmann donor number DN.

which are available for 18 solvents (r 0:954). According to the MSA, the Gibbs
solvation energy is given by equation (4.9.3) with the provision that the parameter
ds depends on the nature of the solvent but is not the same as that found for the
alkali metal cations [48, 49]. Dening 1/ds as As or solvent acidity for the case of a
halide anion, equation (4.9.3) can be rewritten as
s GX S




NL e20
1
As
1
es 1 As ri
8pe0

4:9:6

Fig. 4.17 Plot of the Gibbs energy of transfer of Cl from water to various non-aqueous
solvents against the Gutmann acceptor number AN.

196

LIQUIDS, SOLUTIONS, AND INTERFACES

As lls the role of an acidity parameter because the factors (1  1=es ) and As ri do
not vary markedly for the polar solvents considered in the present analysis. As a
result, s GX S correlates well with the acidity parameter AN.
Values of As estimated using the data for Cl1 ion given in table 4.7 are plotted
against the Gutmann acceptor number in g. 4.18. A very good linear correlation
with a correlation coecient of 0.978 is obtained. The relationship between As
and AN is
As 7:826 0:172AN

4:9:7

As provides another empirical scale for solvent acidity.


The above treatment may be extended to the analysis of the Gibbs energy of
transfer of simple electrolytes and related thermodynamic quantities. Because the
electrolyte contains both cations and anions, the thermodynamic property is
expected to depend on both the acidity and basicity of the solvent. A simple
way of expressing this dependence is
Q Q0 as AN bs DN

4:9:8

where Q is the solvent-dependent thermodynamic quantity, Q0 , its value in a


solvent with zero acceptor number and zero donor number, as , the response to
solvent acidity and bs , the response to solvent basicity [50]. Values of Q0 , as , and
bs may be determined using a three-parameter least-squares t to express Q as a
linear function of both AN and DN. Graphical presentation of the results of this
t requires using a three-dimensional plot.
Results of analyzing Gibbs energy of transfer data on the basis of equation
(4.9.8) for ve alkali metal halides and TATB from water to various non-aqueous
solvents are summarized in table 4.11. Acceptable ts to equation (4.9.6) are
obtained for these systems, the correlation coecient r decreasing with increase
in the size of the alkali metal cation and halide anion. However, there is a problem
in assessing the properties of the t on the basis of the response factors as and bs .

Fig. 4.18 Plot of the MSA parameter As estimated in various solvents for the Cl ion
(equation (4.9.5)) against the Gutmann acceptor number AN.

POLAR SOLVENTS

197

Table 4.11 Analysis of the Dependence of the Gibbs Energy of Transfer of 11


Electrolytes [36, 37] on Solvent Acidity and Basicity (Equation (4.9.8))

Salt
LiCl
NaCl
KCl
KBr
CsBr
TATB*

No. of
Solvents

Q0
/kJ mol1

as

bs

as

9
10
8
10
10
12

133.1
106.2
87.9
74.2
67.4
94.6

1:48
1:31
1.13
0.87
0.82
1.60

2:82
1:86
1.33
1.38
1.15
0.35

0.55
0.62
0.62
0.50
0.53
0.88

bs

Stand.
Dev.
/kJ mol1

Corr.
Coe.
r

0.45
0.38
0.38
0.50
0.47
0.12

2.6
2.8
4.2
6.1
9.7
6.9

0.996
0.993
0.987
0.963
0.894
0.959

*TATB refers to (C6 H5 )4 As (C6 H5 )4 B.

Since the range over which AN and DN vary depends on the solvents chosen in
the study, the relative importance of solvent acidity and basicity in determining
the Gibbs energy of transfer is not easily assessed.
By calculating relative partial regression coecients, the role of solvent acidity
and basicity in determining the thermodynamic quantity can be clearly seen [50].
In order to do this, one must estimate the variance for the independent and
dependent variable involved in the multiparameter analysis. For the parameter
Q, the variance is dened as
!2
X
X
2
nQ
Qi 
Qi =n
4:9:9
i

where the Qi s are the individual values of Q in a data set containing n dierent
values. The variances of AN and DN, nAN and nDN , respectively, are calculated in
a similar way. The partial regression coecients are dened as
a0s jas jnAN =nQ 1=2

4:9:10

b0s jbs jnDN =nQ 1=2

4:9:11

and

The parameters a0s and b0s are now normalized to the same scale so that their
relative values indicate the relative importance of solvent acidity and basicity in
the given analysis. A more direct way of assessing this importance is in terms of
relative partial regression coecients as and bs , which are dened as follows:
a s

a0s

a0s
b0s

4:9:12

a0s

r0s
b0s

4:9:13

and
bs

198

LIQUIDS, SOLUTIONS, AND INTERFACES

The parameter as gives the fraction of the explained variation in the parameter Q,
which is due to solvent acidity. In the same way, b s gives the corresponding
fraction due to solvent basicity.
The values of as and bs recorded in table 4.11 show that solvent acidity is
usually more important than solvent basicity in determining solvation of the
electrolytes considered. The result for TATB for which as 0:88 and bs 0:12
is especially surprising. According to the TATB assumption used to estimate
single ion Gibbs energies of transfer, these quantities should each be equal to
0.50. If results for the three protic solvents W, MeOH, and F are removed from
the data set, and the analysis performed with the remaining nine aprotic solvents,
the values of as and bs are then equal to 0.50. This result suggests that the TATB
assumption is valid for aprotic solvents but not very good for protic solvents with
strong hydrogen bonding [48].
A more general relationship for analyzing solvent eects for thermodynamic
quantities was given by Koppel and Palm [51]. They extended equation (4.9.9) to
include non-specic solvent eects related to solvent permittivity and polarizability. Their equation can be written as
Q Q0 as AN bs DN gs X ds Y

4:9:14

where X is the solvents polarity, Y, its polarizability, and gs and ds , the corresponding response factors. Solvent polarity is dened to be
X

es  1
es 2

4:9:15

and is directly related to the molar polarization dened in Debyes theory of the
dielectric permittivity of polar uids (see equation (4.3.20)). The polarizability Y
is given by
Y

eop  1
eop 2

4:9:16

According to the LorentzLorenz equation (4.3.21) for the molar refraction at


optical frequencies, Y is directly proportional to the molecular polarizability ap .
The KoppelPalm equation has also been applied to the analysis of solvent eects
on thermodynamic quantities related to the solvation of electrolytes [48, 49]. In
the case of the systems considered in table 4.11, addition of the parameter X to the
linear equation describing the solvent eect improves the quality of the t to the
experimental data, especially in the case of alkali metal halide electrolytes involving larger ions. The parameter Y is not important for these systems but does
assist in the interpretation of other thermodynamic quantities which are solvent
dependent [48, 49]. Addition of these parameters to the analysis is only possible
when the solvent-dependent phenomenon has been studied in a large number of
solvents.
In conclusion, solvent acidity and basicity are useful parameters for the interpretation of solvent eects related to the solvation of electrolytes in polar media.
This role demonstrates the importance of the chemical nature of the interaction
between the ion and solvent molecule. Chemical interactions cannot be rationalized simply in terms of concepts from electrostatics based on point charges and

POLAR SOLVENTS

199

point dipoles. Although the parameters used to assess solvent acidity and basicity
are empirical they are related in a direct way to the molecular description of ion
solvation according to the MSA.

4.10 Concluding Remarks


Attention in this chapter has been focused on the dielectric properties of polar
solvents and how they relate to the solvation of electrolytes. The important
problem discussed is how one uses statistical mechanics to derive the solution
permittivity from the molecular properties of polar liquids, namely, the dipole
moment and polarizability. In the classical or continuum approach developed
by Debye, Onsager, Frohlich, and Kirkwood, it became apparent that description of the molecular properties within a spherical cavity in the liquid required
the introduction of a correlation parameter gK . This parameter takes into
consideration the fact that the orientation of molecular dipoles with respect
to one another is not just determined by dipoledipole interactions but also by
chemical considerations such as hydrogen bonding. This fact is especially
apparent for liquid water in which the presence of strong hydrogen bonding
results in a rather high solvent permittivity. In the molecular model based on
the MSA, an additional parameter is required namely the molecular diameter in
a spherical representation of the individual molecule. This model is only successful when the molecular sphere with its embedded point dipole also is
sticky in a given direction. The stickiness factor plays the same role as the
correlation parameter gK in the classical approach. It accounts for chemical
interactions such as hydrogen bonding and the eects of non-sphericity in the
real system. The success of the MSA model is that it predicts values of gK
which are consistent with structural information about the liquid obtained
spectroscopically.
Dielectric relaxation experiments provide valuable information about the properties of polar solvents in an alternating electrical eld. The important parameter
characterizing the ability of the solvent dipole to respond to the changing eld is
the Debye relaxation time. Solvents with hydrogen bonding have several relaxation times, one of which corresponds to the rotational diusion of clusters of
molecules. The information provided by these experiments helps one to understand the role of the solvent in fast reactions occurring in solution. More about
this aspect of solvent eects is discussed in chapter 7. When these experiments are
conducted in electrolyte solutions one is able to assess ion pairing by examining
relaxation data at lower frequencies.
Ion solvation in polar solvents is also an important aspect of the subject matter
considered here. This is traditionally studied by measuring the Gibbs energy and
enthalpy of transfer of a variety of electrolytes from water to another polar
solvent. Single ion quantities are then derived on the basis of the TATB assumption. Study of these quantities for simple monoatomic ions like the alkali metal
cations and the halide anions leads to the conclusion that specic molecular
properties, namely, Lewis acidity and basicity, are important in ion solvation.
On the other hand, the dielectric permittivity, a non-specic bulk property,

200

LIQUIDS, SOLUTIONS, AND INTERFACES

does not play an important role. The analysis presented points out the importance
of the chemical structure of the solvent in stabilizing ions in the electrolyte solution. Thus, the conclusions reached here are in accord with those from chapter 3.
Physical laws such as Coulombs law and bulk parameters such as the permittivity
help one to understand long-range ionion interactions. However, to understand
close-range interactions, one must understand the chemical properties of the
solvent. In order to assess Lewis acidity and basicity, empirical parameters such
as the Gutmann acceptor number and donor numbers have proven to be quite
useful.
Ionsolvent interactions are conveniently studied by several spectroscopic techniques. These provide information about the structure of the solvent around the
ion including the solvation number, and the strength of the ionsolvent bond.
Information about these techniques is presented in the following chapter.

General References
G1. Bottcher, C. J. F.; Bordwijk, P. Theory of Electric Polarization, 2nd ed.; Elsevier:
Amsterdam, 1978.
G2. Hill, N. E.; Vaughn, W. E.; Prince, A. H.; Davies, M. Dielectric Properties and
Molecular Behaviour; Van Nostrand: London, 1969.
G3. Politzer, P., Murray, J. S. Quantitative Treatments of Solute-Solvent Interactions;
Elsevier: Amsterdam, 1994.
G4. Riddick, J. A.; Bunger, W. B.; Sakano, T. K. Organic Solvents, 4th ed.; Wiley: New
York, 1986.
G5. Barthel, J.; Buchner, R.; Munsterer, M. Electrolyte Data Collection, Part 2: Dielectric
Properties of Water and Aqueous Electrolyte Solutions; Dechema: Frankfurt-amMain, 1995.

References
1. Debye, P. Polar Molecules; Chemical Catalog Co.: New York, 1929.
2. Marcus, Y. Properties of Solvents; Wiley: New York, 1998.
3. Karapetyan, Yu, A.; Eychis, V. N. Physico-chemical Properties of Non-Aqueous
Electrolyte Solutions (in Russian); Khimia: Moscow, 1989; Chapter 1.
4. Lide, D. R., Ed. Handbook of Physics and Chemistry, 84th ed.; CRC Press: Boca
Raton, FL, 20032004.
5. Barthel, J.; Bachhuber, K; Buchner, R.; Hetzenauer, H. Chem. Phys. Lett. 1990, 165,
369.
6. Fawcett, W. R. Chem. Phys. Lett. 1990, 174, 167.
7. Castner, E. W., Jr.; Bagchi, B.; Maroncelli, M.; Webb, S. P.; Ruggiero, A. J.; Fleming,
G. R. Ber. Bunsen-Ges. Phys. Chem. 1988, 92, 363.
8. Garg, S. K.; Smyth, C. P. J. Phys. Chem. 1965, 69, 1294.
9. Barthel, J.; Bachhuber, K.; Buchner, R.; Gill, J. B.; Kleebauer, M. Chem. Phys. Lett.
1990, 167, 62.
10. Calderwood, J. H.; Smyth, C. P. J. Am. Chem. Soc. 1956, 78, 1295.
11. Krishnaji A.; Mansingh, A. J. Chem. Phys. 1964, 41, 827.
12. Davies, G. J.; Evans, G. J.; Evans, M. W. J. Chem. Soc., Faraday Trans. 2, 1979, 75,
1428.
13. Brownsell, V. L.; Price, A. H. J. Phys. Chem. 1970, 74, 4004.
14. Elie, V. Bull. Chem. Soc. Belges 1984, 93, 839.
15. Behret, H.; Schmidthals, F.; Barthel, J. Z. Phys. Chem. NF 1975, 96, 73.

POLAR SOLVENTS

16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.

201

Dachwitz, E.; Stockhausen, M. Ber. Bunsen-Ges. Phys. Chem. 1985, 89, 959.
Gauman, T. Helv. Chim Acta 1958, 41, 1933.
Wilhelm, E.; Battino, R. J. Chem. Phys. 1989, 55, 4012.
Lorentz, H. The Theory of Electrons; Dover: New York, 1952.
Balakier, G. Pol. J. Chem. 1980, 54, 2297.
Onsager, L. J. Am. Chem. Soc. 1936, 58, 1486.
Kirkwood, J. G. J. Chem. Phys. 1939, 7, 911.
Frohlich, H. Theory of Dielectrics; Oxford University Press: London, 1949.
Wertheim, M. S. J. Chem. Phys. 1971, 55, 4291.
Wertheim, M. S. Mol. Phys. 1973, 25, 211; 1973, 26, 1425.
Blum, L.; Fawcett, W. R. J. Phys. Chem. 1993, 97, 7185; 1996, 100, 10423.
Reid, D. S.; Vincent, C. A. J. Electroanal. Chem. 1968, 18, 427.
Fawcett, W. R.; Kloss, A. A. J. Chem. Soc., Faraday Trans. 1996, 92, 3333.
Barthel, J.; Buchner, R. Pure Appl. Chem. 1991, 63, 1473.
Friedman, H. J. Chem. Phys. 1982, 76, 1092.
Fawcett, W. R.; Tikanen, A. C. J. Phys. Chem. 1996, 100, 4251.
Barthel, J.; Hetzenauer, H.; Buckner, R. Ber. Bunsen-Ges. Phys. Chem. 1992, 96, 988.
Hynes, J. T. J. Chem. Phys. 1986, 90, 3701.
Fawcett, W. R. Chem. Phys. Lett. 1992, 199, 153.
Krishnan, C. V.; Friedman, H. L. In Solute-Solvent Interactions; Coetzee, J. F.,
Ritchie, C. D., eds.; Marcel Dekker: New York, 1976; Vol. 2, Chapter 9.
Cox, B. G.; Hedwig, G. R.; Parker, A. J.; Watts, D. W. Aust. J. Chem. 1974, 27, 477.
Cox, B. G.; Waghorne, W. E. Chem. Soc. Rev. 1980, 9, 381.
Alexander, R.; Parker, A. J.; Sharp, J. H.; Waghorne, W. E. J. Am. Chem. Soc. 1972,
94, 1148.
Marcus, Y.; Kamlet, M. J.; Taft, R. W. J. Phys. Chem. 1988, 92, 3613.
Gritzner, G. Pure Appl. Chem. 1990, 62, 1839.
Dimroth, K.; Reichardt, C. Liebigs Ann. Chem. 1969, 727, 93.
Reichardt, C. Solvents and Solvent Eects in Organic Chemistry, 2nd ed.; VCH
Publishers: New York, 1988.
Mayer, U.; Gutmann, V.; Gerger, W. Monatsh. Chem. 1975, 106, 1235.
Gutmann, V.; Wychera, E. Inorg. Nucl. Chem. Lett. 1966, 2, 257.
Gutmann, V. Coord. Chem. Rev. 1976, 19, 225.
Marcus, Y. J. Solution Chem. 1984, 13, 599.
Sandstrom, M.; Persson, I.; Persson, P. Acta Chem. Scand. 1990, 44, 653.
Fawcett, W. R. J. Phys. Chem. 1993, 97, 9540.
Fawcett, W. R. In Quantitative Treatments of Solute/Solvent Interactions; Politzer, P.
Murray, J. S., eds.; Elsevier: Amsterdam, 1994; Chapter 6.
Krygowski, T. M.; Fawcett, W. R. J. Am. Chem. Soc. 1975, 97, 2143.
Koppel, I. A.; Palm, V. A. In Advances in Linear Free Energy Relationships; Chapman,
N. B., Shorter, J., eds.; Plenum: London, 1972; Chapter 5.

Problems
1. Show that there is a relationship between the molar volume (table 4.1) and
molecular diameter (table 4.3) for the solvents considered in these compilations. Check to see whether the slope of the least-squares line has the expected
value.
2. The following data were obtained for dilute solutions of nitromethane in
carbon tetrachloride at 208C.

202

LIQUIDS, SOLUTIONS, AND INTERFACES

Mole fraction
NM

Density
r/kg m3

Relative
Permittivity

Refractive
Index

0
0.0343
0.0486
0.0693
0.1202

1594.0
1584.1
1580.6
1573.8
1557.1

2.238
2.710
2.958
3.257
4.038

1.4605
1.4582
1.4569
1.4559
1.4529

Using the method outlined in section 4.3A, estimate the molar polarization
and refraction in the limit of innite dilution. Use these results to estimate the
dipole moment and polarizability of NM and compare with the results in
table 4.3.
3. Estimate the Kirkwood polarization parameter for dimethylsulfoxide using
the MSA model described in section 4.4. Your result should agree with that
given in table 4.4.
4. Given the following dielectric relaxation data for methanol, nd the values of
the es , e1 , and tD , assuming there is only one relaxation process.
Frequency
/MHz

In-Phase
e0

Out-of-Phase
e00

5
1520.5
2016
4183
5216
7122

32.30
27.45
25.04
15.42
13.45
9.57

0
10.30
11.55
13.10
12.12
10.40

5. The following data were obtained for the permittivity of aqueous solutions of
LiBr.
Conc./M

es

0.5
1.0
1.5
2.0
3.0
4.0
5.0

69.29
62.75
56.53
51.85
42.56
35.66
30.44

Determine the best value of de and be in equation (4.6.1) using a least-squares


procedure, and assuming that es for pure water is 78.46. Compare these
values with the results for NaCl (equation (3.9.24)) and comment.
6. The following data are available for methanol assuming one relaxation
process:

POLAR SOLVENTS

Temperature/8C

es

e1

tD /ps

43.4
37
25
0
30

50.6
47.9
44.4
37.7
31.9

6.9
6.7
6.9
6.4
6.0

333
263
186
95
47

203

Estimate the longitudinal relaxation time at 25, 0, and 258C. Estimate the
activation enthalpy associated with both tD and tL .
7. The following data have been obtained for the free energy of transfer of Li
and Br ions from water to the given non-aqueous solvent. Analyze the
dependence of tr G on solvent using the equation Q Q0 as AN bs DN.
tr G =kJ mol1
Solvent

Li

Br

AN

DN

H2 O
MeOH
PC
DMF
AcN
NM
NB
DMSO

0
4.4
23.8
10
25
48
38
15

0
11.1
30.0
36.2
31.3
30
29
27.4

54.8
41.5
18.3
16.0
18.9
20.5
14.8
19.3

18.0
19.0
15.1
26.6
14.1
2.7
4.4
29.8

Determine the relative contributions of solvent acidity and basicity to the


observed variation in tr G . Compare the t with the above equation to a
simple linear t involving the more important parameter. Is the addition of
the second parameter justied?
8. The following data are reported for the Gibbs energy of transfer of the salts
LiCl and KBr. Perform the analysis used in question 7 with these data. What
do you conclude about the suitability of equation (4.9.8)?
tr G =kJ mol1
Solvent

LiCl

KBr

H2 O
MeOH
F
NMF
DMF
AN
DMSO
PC
NB
NM

0
16.7
5.86
13.8
31.0
66.1
20.1
61.9

0
20.5
2.93

22.6
38.5
13.4
35.6
57.2
44.1

Spectroscopic Studies of Liquid


Structure and Solvation

Gabor Palinkas

Erika Kalman

Gabor Palinkas was born in Budapest, Hungary, in 1942. He entered Eotvos


Lorand University in Budapest, graduating with a Ph.D. in physics in 1968. He
then joined the Laboratory of Structural Chemistry of the Hungarian Academy
of Sciences, where he undertook X-ray diraction studies of water and aqueous
electrolyte solutions. In 1973 he began a collaboration with Erika Kalman to
develop electron diraction methods for studying the structure of liquids. Their
work resulted in the rst experimental derivation of the pair correlation
functions in liquid water using existing neutron, X-ray, and electron diraction
data. He expanded his interests in 1975 to include molecular dynamics
simulations of these systems in a collaboration with Professor Karl Heinzinger
at the Max Planck Institute in Mainz, Germany. He has published extensively
in the area of solution structure, both aqueous and non-aqueous. He is
currently Director of the Chemical Research Center of the Hungarian Academy
of Sciences, and holds the position of Professor at the Technical University in
Budapest.
Erika Kalman was born in Budapest in 1942, where she grew up and went
to school. She attended university in Dresden, Germany and obtained a Ph.D.
in chemistry in 1970 after studying in the laboratory of Professor Kurt
Schwabe. She then returned to Budapest to begin work on the study of liquid
structure at the Hungarian Academy of Sciences. In 1973 she began a very
fruitful collaboration with Gabor Palinkas. She spent a sabbatical year in the
United States in 1975, where she worked in the laboratories of Harold
Friedman at Stony Brook and Alan Narten at Oak Ridge National
Laboratories. In the mid 1980s she helped edit an important series of books on
204

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

205

the chemical physics of solvation. She has expanded her interests in recent
years to include studies of corrosion and nanochemistry. She currently directs
the Surface Chemistry and Corrosion Research group at the Chemical
Research Center of the Hungarian Academy of Sciences and holds the position
of Professor at the Technical University in Budapest.
Erika Kalman and Gabor Palinkas were married in 1974 and have two
children.

5.1 What Spectroscopic Techniques Are Available?


Spectroscopy involves the study of the interactions of electromagnetic radiation
with matter. In the case of liquids, radiation of a wide range of frequencies, and
thus energies, has been used, all the way from radio-frequency waves to X-rays.
Experiments involving neutrons, which are associated with very short wavelengths, are also important. In the spectroscopic experiment the incident radiation
may be either absorbed or scattered and the experimental information is obtained
by examining the intensity and direction of the radiation after it has passed
through the sample.
Several spectroscopic techniques will be considered in this chapter. X-ray and
neutron diraction techniques are powerful tools for studying the structure of
liquids and have been introduced in chapter 2. They may also be used to study the
structure of solutions and determine distribution functions for both the solute and
solvent. The feasibility of these experiments depends on the number of dierent
nuclei involved in the system. UV-visible spectroscopy is mainly used to study
electronic transitions in polyatomic species. These species are often complex ions
formed between the electrolyte and the solvent, or between the cation and one or
more anions. Vibrational spectroscopy involves electromagnetic radiation of
lower energy, usually in the infrared region. It is used to study intramolecular
vibrational modes and how they are altered by the environment in solution. It can
also be used to study the bonds formed between solute and solvent in the solvation process. Finally, nuclear magnetic resonance spectroscopy and its application
to the study of solvation will be discussed. This is a particularly powerful technique because it provides information about the environment of a given nucleus,
and experiments specic to a given nucleus can be carried out provided the
nucleus has a non-zero magnetic moment. Several other spectroscopic techniques
are commonly used [G1] but those considered here provide a representative
picture of what can be learnt from those experiments.
One should remember that the atoms and molecules in liquids are not motionless but in a state of ux determined by the intermolecular interactions and
temperature. From the study of microwave spectroscopy discussed in chapter 4,
it was found that rotational diusion processes in liquids are characterized by
relaxation times the order of a few picoseconds. When a liquid is irradiated with
UV or visible radiation which involves frequencies greater than 1015 Hz, the atoms
and molecules appear to be motionless because the frequency of the electromagnetic radiation is much greater than that associated with molecular motion
(1012 Hz and lower). The same is true for infrared spectroscopy except in the

206

LIQUIDS, SOLUTIONS, AND INTERFACES

far infrared where the frequency of the probing radiation is sometimes close to
that of the dynamic processes in the liquid. In the case of NMR spectroscopy,
radio-frequency radiation is used to study the relaxation processes of a given
nucleus in a magnetic eld. Since most relaxation processes in solution take
place at higher frequencies than the resonant frequencies in NMR, only the
average environment of a given nucleus in solution is involved in the experimental
observations.
In this chapter much of the discussion involves electrolyte solutions in both
aqueous and non-aqueous media. The role of spectroscopy in elucidating the
chemical interactions which cannot be understood on the basis of classical
electrostatics is emphasized. More details about each of the four spectroscopic
techniques and their application are now given.

5.2 X-Ray and Neutron Diffraction Studies


The important experimental features of X-ray and neutron diraction were discussed earlier in chapter 2. The incident radiation is characterized by an intensity
I0 and a wavelength l. In the case of neutrons the wavelength is calculated from
the momentum of the particles using the de Broglie equation. The neutron diffraction experiments discussed earlier involved monochromatic particles, that is,
neutrons with the same velocity and thus the same kinetic energy. Another type of
neutron diraction experiment involves neutrons with a range of energies. This is
called a time-of-ight experiment, and it requires detectors which respond to
particles of dierent energies at dierent scattering angles.
The quantity of interest in a diraction experiment is the intensity I(y)
observed at a scattering angle y or at wave number kD dened as
kD

4p siny=2
l

5:2:1

where kD has the dimension of reciprocal length. The scattered intensity at angle y
arises from three sources, namely, coherent, incoherent, and multiple scattering.
As was seen earlier in section 2.5, the structure function FT(kD) for the liquid
sample is determined from the coherent scattering. The relationship between
FT(kD) and the individual partial structure factors S ij(kD) for any two dierent
atoms i and j in the liquid is
!2
XX

 X
FT kD
2  dij ci cj fi kD fj kD S ij kD  1 =
ci fi kD
5:2:2
ij

The ultimate goal of the diraction experiment is to determine each contribution


S ij (kD) to the structure function FT(kD). Then one can determine the individual
pair correlation functions gij(r) by Fourier transformation.
As pointed out in section 2.5, there are signicant dierences between results
from X-ray and neutron diraction experiments because of the way these species
are scattered by the atoms of the liquid. In the case of X-rays the scattering is due
to the electrons around each nucleus, and the scattering amplitude increases with

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

207

the atomic number of the atom. This means that when X-rays interact with liquid
water, they are signicantly scattered only by the oxygen atoms. As a result one
partial structure factor, namely, S OO(kD), makes a contribution to FT(kD). On the
other hand, in a neutron diraction experiment neutrons are scattered by both the
proton 1 H, and the oxygen atom 18 O.
X-ray and neutron diraction experiments dier signicantly in another
important way. In an X-ray experiment the scattering amplitude for atom i,
fi (kD), depends strongly on the reciprocal distance or wave number kD. As kD
increases fi (kD) decreases monotonically [1]. This means that the disentanglement
of the individual partial structure factors S ij(kD) requires knowledge of fi (kD). On
the other hand, in a neutron diraction experiment fi (kD) is independent of kD
and depends only on the nature of the atom and its nuclear components. As a
result, fi (kD) is given dierent names in these experiments. In an X-ray experiment, fi (kD) is usually referred to as the form factor, whereas fi (kD) in a neutron
diraction experiment is called the coherent scattering length [1].
Because of the important dierences between the two diraction experiments,
the strategies used in carrying out these studies are not the same. X-ray experiments are certainly more common since the equipment used is easily obtained.
Neutron experiments are carried out at a nuclear reactor site or at an accelerator
with the appropriate facilities. In the following sections, some results from diffraction experiments are presented with emphasis on the structural information
which has been obtained regarding ion solvation in electrolyte solutions.
A. X-Ray Diffraction Studies of Electrolyte Solutions
X-ray diraction has been used extensively to study the structure of aqueous
electrolyte solutions [G1]. When an electrolyte with monoatomic ions is dissolved
in water the number of dierent atoms in the system is four, namely, M and X,
from the electrolyte, and H and O from water. As a result there are ten independent partial structure factors. They are S OO, S OM, S OX, S OH, S HH, S HM, S HX,
S MM, S MX, and S XX. In a more complex system with n dierent atoms, the
number of independent partial structure factors is nn 1=2. In an X-ray
experiment, all partial structure factors involving the H atom are not important
so that the number is reduced from ten to six. Of these, two more may be
neglected, namely, those involving only cations or anions, that is, S MM and
S XX. Obviously, ions of the same sign tend to be as far as possible away from
each other. Finally, if ion pairing is negligible, S MX may also be neglected. Thus,
three signicant partial structure factors, namely, S OO, S OM, and S OX usually
contribute to the observed structure function FT(kD).
Because the scattering amplitudes fi (kD) vary with reciprocal distance, a normalized structure function H(kD) is usually dened in reporting X-ray diraction
data. Thus,
HkD FT kD =MkD

5:2:3

where M(kD) is chosen to change the scale to that characteristic of one molecule
and remove some of the breadth due to the electron distribution in the molecule
[2]. A convenient choice in the case of electrolyte solutions is

208

LIQUIDS, SOLUTIONS, AND INTERFACES

MkD

!2
xi fi kD

5:2:4

where xi is the mole fraction of atom i [3]. The value of kDH(kD) oscillates in an
irregular fashion and with decreasing amplitude. These data have been analyzed
on the basis of the rst-neighbors model [3] according to which
HkD xM HOM kD xX HOX kD xW HOO kD

5:2:5

where xM, xX, and xW are the mole fractions of cationwater aggregates, anion
water aggregates, and free water, respectively, and Hij is the normalized structure factor for atoms i and j. Accordingly, there are two states for water molecules, those bound in hydration shells and those in the normal (free) water
structure. In addition, the hydration shells only involve nearest neighbors which
are arranged in a very symmetrical fashion. Using this model, Palinkas et al. [3]
resolved the data for FT(kD) to obtain a model for alkali and alkaline earth metal
halide solutions. In this way they developed a model for ion hydration in these
systems. Their results are shown for 2 m solutions of the alkali metal chlorides in
gs 5.1 and 5.2. It is clear from these data that gOM(r) has a well-dened maximum at a value of r which is greater than 200 pm. In addition, the position of the
maximum shifts to higher values as the atomic mass of the alkali metal cation
increases. On the other hand, the position of the maximum for Cl on the gOX(r)
function is approximately independent of cation nature and occurs at 314 pm.

Fig. 5.1 Values of the normalized


structure factor kDH(kD) for 2 m
solutions of the alkali metal chlorides in
water as a function of reciprocal distance
kD [3]. The data for KCl, NaCl, and
LiCl have been shifted vertically by 20,
40, and 60 nm1, respectively, for the
sake of clarity.

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

209

Fig. 5.2 Pair correlation functions for


the cationwater, gOM(r), and anion
water interactions, gOX(r), in 2 m
aqueous solutions of the alkali metal
halides [3]. The data for NaCl, KCl, and
CsCl have been shifted vertically by 5,
10, and 15 units, respectively, for the
sake of clarity.

Many X-ray diraction studies of electrolyte solutions have been carried out in
aqueous solutions [G1, 4, 5]. Values of the most probable distance, roi, between
the oxygen atom in water and a number of monoatomic ions are summarized in
table 5.1. In the case of the cations, this distance reects the radius of the cation
plus the eective radius of the water molecule measured in the direction of the
lone pairs on oxygen. In the case of alkali metals, the eective radius of water
increases from 122 pm for Li to 131 pm for Cs when the Shannon and Prewitt
radii are assumed for the cations (see section 3.2), the average value being 127 pm.
This result can be attributed to the observation that the coordination number for
water molecules around an alkali metal or alkaline metal earth cation changes
with cation size and electrolyte concentration. In the case of the Li ion, this
number decreases from six in very dilute solutions to four in concentrated solutions [5]. Because of the electrostatic character of the interaction between the
cation and water molecules, these molecules exchange rapidly with other water
molecules in their vicinity. For this reason, the solvation coordination number
should be considered as an average.
In the case of transition metal cations, the coordinated water molecules are
covalently bonded to the cation, and the coordination number can be interpreted
as xed in the absence of other ligands. If the cations Mn2, Fe2, Co2, and Ni2
are assumed to be in the high spin state, then the eective radius of coordinated
water molecules in these systems is 123 pm on the basis of the X-ray data.
Interpretation of the roi data for monoatomic anions is much more dicult
because of the fact that anions are solvated in water via hydrogen bonding (see

210

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 5.1 Most Probable Distance roi Between the Oxygen


Atom in Water and Monoatomic Ion i in Aqueous Electrolyte
Solutions [5]
Ion

Distance roi / pm

Coordination Number

Solution

Li
Na
K
Cs
Ag

210
242
280
315
242

6
6
6
6
4

2.2 M LiI
2 M NaCl
2 M KCl
2 M CsCl
3.3 m AgNO3

Mg2
Ca2
Sr2

212
244
264

6
6
8

1.1 M MgCl2
2 m CaBr2
1.6 m SrCl2

Al3
In3

187
215

6
6

3.8 m Al(NO3)3
5.0 m In(ClO4)3

Mn2
Fe2
Co2
Ni2
Cu2

220
212
210
207
194

6
6
6
6
4

2 m MnSO4
2.2 m Fe(ClO4)2
3.7 m Co(ClO4)2
3 m NiCl2
2.8 m Cu(ClO4)2

F
Cl
Br
I-

262
310
334
363

4.5
6
6
6.9

4.2 m KF
3 m CoCl2
2 m CaBr2
2.2 m LiI

g. 3.1). Thus, the ionoxygen atom distance cannot be interpreted in a simple


way as it is for cations [5].
X-ray diraction studies have also been carried out in non-aqueous electrolyte
solutions. In the case of methanol, there are two atoms which scatter X-rays,
namely, carbon and oxygen. When a monoatomic electrolyte is added the number
of scattering atoms increases to four. As a result, such a system has ten partial
structure factors. If the ionion correlations are neglected this reduces to seven. A
system which has been analyzed in some detail is MgCl2 in methanol [6, 7].
Analysis of the data gives a MgO distance of 207 pm and a ClO distance of
318 pm for coordination numbers of six [6].
As the number of atoms in the solvent molecule increases disentanglement of
the partial structure factors becomes more dicult. One way of making the analysis easier is to use dierent isotopes of the atoms involved. This technique has
been applied with success in neutron diraction experiments which are described
in the following section.
B. Neutron Diffraction Studies of Electrolyte Solutions
In the case of neutron diraction, the radiation is scattered by the atomic nuclei,
not by the electrons [1]. As a result, the scattering amplitude fi (kD) is determined
by the nucleons and depends in a complex way on their total number. This means

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

211

that isotope eects are very important in developing experimental strategies, and
that very light atoms such as hydrogen and deuterium have signicant values of
fi (kD) [8, 9]. As discussed earlier there are ten partial structure factors which can
contribute to the structure function Fi (kD) for a monoatomic electrolyte MX
dissolved in water. By using isotope substitution techniques, six of these can be
factored out, and only two of the remaining contributions are normally signicant.
Consider as an example the studies of LiCl in D2O by neutron diraction [8].
The isotopes 6Li and 7Li have very dierent scattering amplitudes, so that the
structure functions Fi (kD) are not the same for solutions of 6LiCl and 7LiCl.
Moreover, the scattering amplitude fi (kD) is independent of kD, that is, of scattering angle y, and depends only on the nature of atom i. By subtracting the
overall structure functions obtained in the presence of dierent Li isotopes, the
contributions from partial structure factors not depending on Li are removed.
Thus,
FT kD ; Li FT kD ; 7 Li  FT kD ; 6 Li

5:2:6

depends only on the partial structure factors S LiO, S LiD, S LiLi, and S LiCl.
Furthermore, it is assumed that solution structure is independent of isotopic
nature, so that the partial structure factors for 7Li are exactly the same as those
for 6Li. Two of the above partial structure factors are negligible, namely those for
LiLi interactions, and LiCl interactions assuming that ion pairing is not signicant. Fourier transformation of FT(kD, Li) gives the overall correlation function GLi(r) which depends on the pair correlation functions gLiO and gLiD. A plot
of GLi(r) against distance r determined for LiCl in D2O is shown in g. 5.3. Two
clearly resolved peaks are seen. The rst corresponds to the most probable distance between the Li ion and the oxygen on the nearest water molecules (195 pm)
and the second to the corresponding distance between the Li ions and D atoms
(255 pm). If the same dierence is determined for 6LiCl and 7LiCl solutions in
light water, the dierence pair correlation function depends on gLiO and gLiH.

Fig. 5.3 The rst-order


dierence function GLi(r) for
LiCl in D2O as a function of
interatomic distance r. (From
reference 8, with permission.)

212

LIQUIDS, SOLUTIONS, AND INTERFACES

Using the data obtained in light and heavy water, the individual pair correlation
functions can be separated. For the data in D2O, one has
GLi 2cLi cO fLi fO gLiO  1 2cLi cD fLi fD gLiD  1

5:2:7

where the independence of fi from kD has been noted. Similarly in H2O, one has
GLi 2cLi cO fLi fO gLiO  1 2cLi cH fLi fH gLiD  1

5:2:8

These are two equations in the unknowns gLiO and gLiD, assuming that gLiD and
gLiH are exactly the same [8, 9]. Thus, the two pair correlation functions may be
obtained separately. This method requires that careful and precise experiments be
carried out.
Another type of isotope experiment can be used to determine the eect of the
electrolyte on water structure. If one compares the overall pair correlation functions for a given LiCl concentration in H2O and D2O one obtains the dierence
function GLi(r). This function depends on the values of gij(r) which are due to
the two H isotopes. They are gOH, gLiH, gClH, and gHH, where the subscript H
designates both 1H and 2H. To a good approximation, one expects to nd changes
only in gHH with change in electrolyte concentration. Experiments have shown
[10] that the pair correlation function gHH in 1 m LiCl is almost the same as that in
pure water, thereby demonstrating that the hydrogen bonding in the solution is
very little perturbed by the added electrolyte. However, when the electrolyte
concentration is increased to 10 m, there is a signicant change in gHH, indicating
that the number of hydrogen bonds in the very concentrated solution is about
70% lower than in pure water.
Using the second dierence technique the partial pair correlation functions
gClH and gClO have been determined for the Cl ion in water [11]. The experiments
involve rst determining the dierence function GCl(r) using chloride salts rich
in 35Cl or 37Cl. Then each of these experiments is done in either H2O or D2O to
achieve separation of the gClH and gClO partial pair correlation functions. The
results conrm that the orientation of the water molecule with respect to the Clion is that shown in g. 3.1.
It is useful to consider the general characteristics of the partial pair correlation
function for a metal ion coordinated to water molecules. Given suciently precise
data and metal isotopes with dierent scattering fractions fi(kD), the pair correlation function gMO is the ultimate goal of experiments designed to study ion
solvation. The shape of gMO for the cases of strongly and weakly coordinated
water molecules is shown in g. 5.4. When the water is tightly bound to the metal
ion, the rst peak in gMO(r) is high and sharp, reaching values greater than 2. The
position of the peak gives the MO distance. By integrating gMO(r) up to the rst
minimum at rs, one obtains an estimate of the coordination number for the ion
(see equation (2.10.1)). For Ni2 in water, this number is 6 as one would expect [8,
9]. In addition, the average residence time for such a water molecule is quite long,
specically, the order of 10 ms. When the water molecules are weakly bound to the
central metal ion the appearance of the partial pair correlation function gMO(r)
changes signicantly (see g. 5.4). The rst peak on this curve is lower and
broader and the subsequent minimum much less deep. Cations with this type of

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

213

Fig. 5.4 Generic radial distribution functions gMO for the metal ion Mn in water for cases
of (a) strong coordination and (b) weak coordination. rMO is the optimum metal ion
oxygen distance in the solvated species. The coordination number is estimated by integrating the distribution function out to the minimum at rs. (From reference 8, with permission.)

gMO are less strongly hydrated and have water residence times in the rst solvation layer which are of the order of 10 ps.
Not only does neutron diraction allow one to determine ionic size and hydration numbers in solution but it can also be used to assess changes in hydration
with concentration. In the case of Li, the hydration number is 6 in dilute solutions but it drops to values below 4 in very concentrated solutions. Similar conclusions have been reached regarding divalent cations such as Ca2 for which the
ionsolvent interactions are mainly electrostatic in nature. For this system the
hydration number decreases from 10 in 1 M CaCl2 to 6 in a 4.5 M solution of the
same salt.
The important limitation of neutron diraction experiments is that the necessary isotopes are often not available so that the dierence technique described
here cannot be applied. Thus, neutron diraction studies have been carried out to
study solvation of Li and K cations but not Na. In the latter case, X-ray
techniques, which do not provide information about hydrogen bonding, are used.
In summary, diraction techniques provide a powerful means of investigating
the structure of electrolyte solutions. They give information about the pair correlation functions which can be directly related to modern theoretical techniques
such as molecular dynamics calculations. This information can also be used to
improve the statistical thermodynamic models of electrolyte solutions discussed in
chapter 3.

5.3 Nuclear Magnetic Resonance Spectroscopy in


Solutions
Nuclear magnetic resonance (NMR) spectroscopy is based on the magnetic properties of the nuclei which make up the molecules and ions in solution. Each
nucleus has a spin quantum number I which depends on the number of protons

214

LIQUIDS, SOLUTIONS, AND INTERFACES

and neutrons in the nucleus and the way in which the spins of these nucleons
interact. The spin quantum number can have integral or half-integral values so
that I may equal 0, 1/2, 1, 3/2, . . . NMR spectroscopy was rst applied to protons
(1H) for which I is equal to 1/2. In the case of deuterium, which has one proton
and one neutron, the nuclear spin quantum number is 1. Atoms with an even
number of protons and an even number of neutrons have I equal to zero; examples are 12C, 16O, and 32S. The magnetic properties of some nuclei which have
been studied experimentally are summarized in table 5.2.
The magnetic energy level is degenerate with a total of 2I 1 quantum states.
In the presence of an external magnetic eld these quantum states have dierent
energies, each with a quantum number mM. For example, the proton for which
I 1/2 has two energy levels with mM 1/2 or 1/2, and the deuteron for which
I 1 has three energy levels with mM 1, 0, or 1.
Another important property of a magnetic nucleus is its magnetogyric ratio
gM , which is also given in table 5.2. This gives a measure of how strongly or
weakly the nucleus interacts with an external magnetic eld, and can be considered as the magnetic analog of the extinction coecient in optical spectroscopy.
Using this quantity and the spin quantum number one can calculate the magnetic
moment for the nucleus, which is given by
lM

gM Ih
2p

5:3:1

In the presence of a magnetic eld B0 the energy levels split according to the
individual values of lM. The dierence in energy or energy gap between these
levels is given by
hn

lM B0 gM hB0

I
2p

5:3:2

and depends on the strength of the magnetic eld. This is illustrated for the proton
in g. 5.5.
Table 5.2 Magnetic Properties of Some Nuclei
Nucleus
1

H
H
7
Li
13
C
14
N
17
O
19
F
23
Na
35
Cl
33
S
2

Spin Quantum Number I

Magnetogyric Ratio gM  107 =rad T1 s1

1/2
1
3/2
1/2
1
5/2
1/2
3/2
3/2
3/2

26.75
4.11
10.40
6.73
1.93
3.63
25.18
7.08
2.64
2.05

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

215

Fig. 5.5 Energy level splitting for a proton


(I 1=2) in an applied magnetic eld B0.

EXAMPLE

Calculate the magnetic moment for a proton from its magnetogyric ratio.
What is the frequency corresponding to the energy gap in a magnetic eld of
4.69 T?
The magnetic moment lM is
lM

26:75  107  1=2  6:626  1034


1:41  1026 J T1
2p

5:3:3

The energy gap is


hn

1:413  1026  4:69


1:325  1025 J
1=2

5:3:4

This corresponds to a frequency of 200 MHz.


From a classical point of view a nucleus which possesses a magnetic moment
(I 6 0) can be considered as a spinning charged particle. If I 1=2, the nucleus
behaves as a spinning charged sphere; if I is larger, then the nucleus is equivalent
to a non-spherical spinning charge, and, in addition, possesses a quadrupole
moment.
When a magnetic nucleus is placed in a magnetic eld B0 it tends to adopt the
direction of the eld. However, because of its spin, it is not aligned exactly with
the external eld but instead at an angle to it, as shown in g. 5.6. The net result is
that the magnetic moment vector lM precesses about the magnetic eld vector
B0. The angular velocity for this precession is called the Larmor precessional
frequency and is given by
oL gM B0

5:3:5

If oL is expressed as a normal frequency n, it is clear that n is given by equation


(5.3.2).
Now consider the eect of a small additional magnetic eld B1 applied perpendicular to the main eld B0 . If the eld B1 rotates around B0 at the Larmor
precessional frequency oL , a torque is produced on vector lM which acts to

216

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 5.6 Magnetic moment vector lM


precessing about the applied eld vector B0 (a);
the same system with addition of a rotating
magnetic eld B1 perpendicular to B0 (b).

change the angle y (g. 5.6). On the other hand, for other frequencies, the interaction between lM and B1 varies depending on the relative phases of the two
motions and there is no sustained eect. When B1 rotates at the Larmor frequency
the nuclear magnetic moment can absorb energy and assume a higher energy level
in which lM points in the opposite direction. The absorption of energy by the
nucleus under these circumstances is called nuclear magnetic resonance.
In the NMR experiment the sample containing the magnetic nuclei is exposed
to a xed magnetic eld B0 and a rotating eld B1 , as described above. The
frequency of the rotating eld is swept through a range of values including the
Larmor frequency for the nucleus in question. The absorption of energy at this
frequency is observed when a plot of energy absorbed against frequency is made.
This is the NMR spectrum. The rotating magnetic eld is generated using a
linearly oscillating eld of radio frequency. The linearly oscillating eld can be
resolved into two rotating magnetic elds of equal magnitude but opposite rotational directions. Only the component rotating in the same direction as lM interacts with the nuclei.
The above experiment is called a frequency sweep experiment. Equivalent
results are obtained if the radio frequency is held constant and the magnetic
eld B0 is changed. This is called the eld sweep technique.
The relative populations of the separate energy levels for a nucleus in a magnetic eld and the relaxation processes from a higher energy level to a lower one
are also of fundamental interest. On the basis of Boltzmanns law and equation
(5.3.2) the ratio of the number of nuclei in the higher energy level to that in the
lower level for a proton (I 1=2) is


Nu
gM hB0
5:3:6
exp
N1
2pkB T
Since the energy gap between these levels is small with respect to kB T for typical
values of B0 , the exponential can be replaced by the rst two terms in its expansion as an innite series. Thus,

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

Nu
g hB
1 M 0
N1
2pkB T

217

5:3:7

EXAMPLE

Estimate the ratio of Nu =N1 for protons in a magnetic eld of 4.69 T at 258C.
The energy gap between the two levels is
hn

26:75  107  6:626  1034  4:69


1:325  1025 J
2p

5:3:8

The value of kB T at 258C is


kB T 1:381  1023  298:2 4:118  1021 J

5:3:9

Therefore the ratio Nu =N1 is


Nu
1:325  1025
1
1  3:22  105
N1
4:118  1021

5:3:10

Thus the dierence in population for these two levels corresponds to 32.2 ppm.
There are two kinds of relaxation processes in NMR, namely, spinlattice and
spinspin relaxation. The lattice is the general collection of atoms and molecules
surrounding the nuclei which interact with the magnetic eld. The lattice system is
involved in vibrational and rotational motion reecting the thermal energy of the
system. Interaction between a nucleus which has absorbed energy from the magnetic eld and the lattice causes this nucleus to return to the ground state, thereby
transferring energy which increases the vibrational and rotational motion of the
lattice. This is spinlattice relaxation which is a rst-order process characterized
by a relaxation time T1 . It is also called longitudinal relaxation because it is
associated with change in the component of the magnetization vector of the
nucleus Mz in the direction of the applied magnetic eld B0 . The relaxation
time T1 depends on the magnetogyric ratio of the nucleus gM and thus on the
Larmor frequency at which it absorbs energy. It also depends on the characteristics of the lattice. The fact that T1 is nite results in broadening of the lines in the
NMR spectrum. In liquids, values of T1 fall in the range from 102 to 102 s. The
relationship between the width of the NMR line and T1 is
n

1
2pT1

5:3:11

The other mechanism by which the system returns to equilibrium after absorption of energy is spinspin relaxation. This is attributed to interaction of the spin
vectors on adjacent nuclei. The precessing moment on nucleus 1 sets up an oscillating eld at nucleus 2; this eld momentarily comes into phase with that of the
other nucleus which absorbs energy from nucleus 1. The resulting transfer of
energy between the nuclei is called spinspin relaxation. The other mechanism
of line broadening associated with spinspin relaxation is due to the local inhomogeneity of the magnetic eld B0 . Because the environment of each nucleus
contains other magnetic nuclei, the local value of B0 , Blocal , is slightly dierent.
As a result there are a range of Larmor frequencies for the responding nuclei

218

LIQUIDS, SOLUTIONS, AND INTERFACES

depending on the range of values of Blocal . Spinspin relaxation can also be


described in terms of the magnetization vectors in the x; y-plane perpendicular
to the main magnetic eld B0 . These vectors Mx and My achieve nite values after
the absorption of energy by the magnetic nuclei. They decay to zero, their equilibrium values, with a rate constant 1=T2 . Thus, spinspin relaxation is also called
transverse relaxation. Both longitudinal and transverse relaxation of the magnetization vectors Mx , My , and Mz are illustrated in g. 5.7.
An understanding of relaxation processes in the resonance process allows one
to explain the line shapes observed experimentally. As will be seen in chapter 7,
chemical reactions, for example, proton transfer reactions, can lead to band
broadening in the NMR spectrum. Thus, this feature of the spectra has very
important applications in the study of fast chemical reactions in solution.
In the discussion of the Larmor frequency above, the eect of the magnetic
environment on the absorbing nucleus was ignored. The eectiveness of NMR
spectroscopy in chemistry is denitely a result of the sensitivity of the absorbing
nucleus to the nature of the nuclei in its immediate environment. Consider for
example the case of ethanol, C2H5OH. One may distinguish three dierent protons with respect to environment, namely, the proton in the OH group, the
protons in the methyl group, and the protons in the CH2 or methylene group.
Each of these species experiences a dierent magnetic environment, so that the
NMR spectrum of ethanol has three absorption peaks at low resolution. The
shielding eect of the environment is expressed quantitatively in terms of the
shielding constant s. Thus, if oL is the Larmor angular frequency in the absence
of a magnetic environment, the angular velocity in the presence of this environment is
o gM B0 1  s

5:3:12

Fig. 5.7 Illustration of the magnetization vectors Mx , My , and My for a system (a) in the
presence of an external magnetic eld B0 in the z-direction but no transverse eld B1 ; (b)
after application of B1 in the (x; y)-plane and absorption of energy; and (c) after partial
relaxation back to the equilibrium conguration in (a).

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

219

The observed peaks in the NMR spectrum are usually cited in terms of chemical
shifts measured with respect to the peak for a reference compound. In the case of
1
H spectra this compound is usually tetramethylsilane, (CH3)4Si, which is added
to the sample placed in the spectrometer. The protons in this reference are all
equivalent and therefore give one NMR peak. The chemical shifts for the other
peaks observed are dened as


o  or
d 10
or
6

5:3:13

where or is the angular frequency at which the reference peak is observed. Values
of d are given in parts per million through the factor 106. Positive contributions to
s are termed diamagnetic, whereas negative contributions are paramagnetic.
The description of NMR spectroscopy given here is applicable to a continuous
wave instrument in which the radio-frequency is swept continuously over the
appropriate range. Most modern instruments are pulsed or Fourier transform
spectrometers (FT-NMR). In the pulsed instrument, the sample is irradiated
with periodic pulses of radio-frequency energy that are directed through the
sample at right angles to the magnetic eld. The short pulse, which lasts the
order of 10 ms, results in a change in the net magnetization of the sample system
away from the z-direction of the permanent magnetic eld. When the pulse ends,
the magnetization relaxes back to its equilibrium position in a process called free
induction decay (FID). The FID signal is detected by the spectrometer and stored
digitally. By repeating this process many times, the signal-to-noise ratio of the
FID is improved. Finally, the average FID which gives the NMR spectrum in the
time domain is Fourier transformed to give the frequency domain spectrum.
In the early stages of NMR spectroscopy, most work involved studies of protons in organic compounds. However, instruments are now available for studying
a wide variety of other nuclei. In this chapter, attention is focused on NMR
studies of ion solvation. Work carried out in both aqueous and non-aqueous
solutions is considered in the following sections.

5.4. NMR Studies of Ion Solvation in Water


One of the most important applications of NMR spectroscopy is the determination of the solvation number of ions in aqueous solutions. This can be accomplished in some cases using 1H NMR or using 17O NMR in isotopically enriched
water. An example involving the highly charged Al3+ ion is shown in g. 5.8. The
proton spectrum of an aqueous solution of Al(ClO4)3 at a temperature of 46:38C
shows two peaks, a large one corresponding to the protons in bulk water, and a
lower one shifted downeld corresponding to the protons associated with the
Al3+ ion. By integrating the area under these peaks one can determine the solvation number of Al3+ which is 6. As the temperature is raised, both lines broaden
and move toward coalescence due to proton exchange processes, so that at
26:48C the absorption due to coordinated water molecules is scarcely visible
[G1, G3].

220

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 5.8 Proton NMR spectra of


aqueous 2.1 m Al(ClO4)3 at (a) 46:38
and (b) 26:48C. (From reference
G1, with permission.)

The above experiment only works when the rate of exchange of the solvent is
slow with respect to the frequency separation between the coordinated and bulk
water molecules. If this frequency is 1000 Hz, then the relaxation time characterizing solvent exchange should be signicantly greater than 1 ms. This is the case
for highly charged main group cations or for most transition metal ions for which
water is a ligand. Data for some diamagnetic cations are summarized in table 5.3.
It can be seen that d increases roughly with the ratio zi =ri , that is, with the ratio of
ionic charge to ionic radius. However, this is not a complete explanation, as can
be seen from the Al3+, Ga3+, In3+ series. The downeld shift also increases with
the polarizability of the ion.
Paramagnetic cations such as Mn2+, Fe2+, Co2+, and Ni2+ cause a much
larger downeld chemical shift of the protons in coordinated water molecules. In
some cases 1H NMR data can be used to study hydration for these systems in 17Oenriched water. Since the gyromagnetic ratio for 17O is much less than that for 1H
the downeld chemical shift in hertz is not as large. 17O NMR spectroscopy has
the advantage that 17O exchange processes between adjacent water molecules are
much slower than the corresponding 1H exchange processes. As a result, one
source of line width broadening is greatly reduced.
When the rate of solvent exchange around the ion is fast, only one line is seen
in the NMR spectrum. In this case, the 1H nucleus in the solvent may experience
all possible environments in the solution within the time corresponding to the
Table 5.3 1H NMR Data for Water in the Primary
Solvation Shell of Diamagnetic Cations
Cations

Cation Chemical Shifta / ppm

Solvation Number

Be2+
Mg2+
Al3+
Ga3+
In3+
(Water)

8.04
5.55
8.74
8.98
7.22
4.13

4
6
6
6
6

Measured at low temperatures with respect to ethane gas as reference.

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

221

radio frequency of the NMR experiment. Such a situation holds in a solution of


NaCl. To a good approximation, the proton in the water molecule experiences
three environments, that near the cation, that near an anion, and that in the bulk
solvent far away from either ionic component. The experimentally observed chemical shift is an average for the protons in each of these environments. As a result
the observed chemical shift changes with electrolyte concentration [12, 13].
Proton chemical shifts observed on addition of simple electrolytes to water are
given in table 5.4. They depend on the nature of the electrolyte and can be either
positive or negative. In the limit of dilute solutions the shifts are linear in concentration, reecting the fact that solventsolvent interactions are being replaced
by ionsolvent interactions. The non-linearity at higher concentrations is attributed to ion pair formation. Two phenomena contribute to the observed chemical
shift. One involves the breaking of hydrogen bonds, which leads to a positive
shift. The other involves polarization of the water molecule in the eld of the ion,
which gives a negative shift. The former eect predominates for most electrolytes.
Obviously, the chemical shifts given in table 5.4 depend on both cation and
anion, and it is interesting to try to separate their contributions. The eect of the
cation was studied by Davies et al. [13], who measured the limiting slope of the
chemical shift against concentration plots for a series of alkali metal and alkaline
earth metal chlorides (see g. 5.9). When the molal chemical shift is plotted
against the polarizing strength of the cation estimated as the charge/radius
ratio, z=r, one nds that the most positive shifts in these series are for K+ and
Ba2+. As z=r increases the molal shift becomes more negative due to the increase
in polarizing strength of the cation. In the alkali metal series, this trend changes
direction at K+, the molal shifts for Cs+ and Rb+ being less positive than one
would expect on the basis of a simple linear correlation. This probably reects the
polarizability of the largest cations which should also be considered in estimating
cationic polarizing strength.
The trends for the alkali metals and alkaline earth metals are separated by
0.033 ppm. As argued by Davies et al. [13], this dierence gives the eect of the
extra Cl ion which is in the alkaline earth metal solution (MCl2). By shifting the
dependence for the alkaline earth metal chloride solutions down by two times
0.033 ppm, and that for the alkali metal chlorides down by 0.033 pm, one trend is

Table 5.4 Molal Chemical Shifts for the Proton Resonance of Water in Electrolyte
Solutions at 258C [13]
Electrolyte
NaF
KF
LiCl
NaCl
KCl
RbCl
CsCl
a

Chemical Shifta d / ppm kg mol1


0.021
0.008
0.047
0.096
0.111
0.092
0.080

With respect to that for pure water.

Electrolyte
NaBr
NaI
NaCN
NaNO3
NaBF4
NaSCN
NaClO4

Chemical Shifta d / ppm kg mol1


0.128
0.175
0.113
0.081
0.123
0.143
0.140

222

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 5.9 Molal chemical shifts for the alkali metal and alkaline earth metal chlorides in
aqueous solution plotted against the polarizing strength of the cation estimated as z=r
(Pauling scale). The data shown as () have been corrected for the contribution of Cl ,
and represent estimates of the cation contribution (see text).

found for both series. This analysis gives an approximate method of separating
cation and anion eects. In assessing it, one should remember that the anion
interacts directly with the proton whose magnetic resonance is being measured,
whereas the cation interacts indirectly through the oxygen atom in the water
molecule. The eect of the halide ions for a given alkali metal ion is such that
the molal chemical shift becomes increasingly more negative with increase in
polarizing strength. Anions are known to have very little disruptive eect on
water structure, so that the trend observed mainly reects the polarization of
the proton by the anion.
Another way of studying solvation eects for simple diamagnetic ions is to
measure chemical shifts for the solute ion. In the case of aqueous solutions of
Na+ electrolytes, experiments have shown that the 23Na+ chemical shift is proportional to the mole fraction of the electrolyte over a wide concentration range
[14, 15], so that it may be expressed as
d d e xe

5:4:1

where de is the value of the chemical shift characterizing the given electrolyte at
unit mole fraction and xe , the mole fraction of the electrolyte. Similar results are
available for 39K [16] and other alkali metal cations [14]. These results shed
considerable light on the nature of the interactions of these simple cations with
their environment.
Values of de for seven Na+ electrolytes are summarized in table 5.5. A positive
shift occurs when the interaction of the Na+ cation with the anion is less than that
with a water molecule. This situation occurs in NaClO4 solutions over a very wide
range of concentrations. At a mole fraction of 0.25, every Na+ ion is accompa
nied by one ClO
4 and three molecules of water in solution, so that ClO4 ions are

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

223

Table 5.5 Value


of de for various
11 electrolytes
containing 23Na+
[15]
Electrolyte
NaClO4
NaNO3
NaBPh4
NaCl
NaBr
NaI
NaOH

de /ppm
24
19
0
7
10
13
22

expected to be in the immediate environment of the cation. The NMR results


show that there is no signicant interaction between the electron clouds of these
two ions. As the basicity of the donor ion or molecule increases, the chemical shift

becomes more negative according to the following series: ClO
4 < NO3




< H2 O < Cl < Br < I < OH . This series also follows an increasing tendency to form ion pairs. Thus, in the case of Na+ and I , signicant overlap
can occur between the electron clouds of these ions, so that I shields the 23Na+
nucleus more eectively than a water molecule. As a result there is a moderate
tendency to form ion pairs in concentrated NaI solutions.
Studies of the nuclear resonances of 35Cl, 81Br, and 127I have also been carried
out in various alkali metal halide solutions [17]. The magnitude of the chemical
shift increases with electrolyte concentration and also with atomic number of the
anion. In the case of the alkali metal ions the chemical shift becomes more positive
in the series Na < K < Li < Rb < Cs . The results were attributed to direct
interaction between the cation and anion in solutions containing K+, Rb+, and
Cs+. With the smaller cations, interactions between the halide ion and the water
molecules solvating the cation are more important.
The above discussion provides a brief introduction to the NMR spectroscopy
of solvation in water. Much more has been learnt about the kinetic aspects of
solvation by studying relaxation times associated with the magnetic resonance
lines. Detailed information is available in several reviews [G1, 18, 19]. Clearly,
NMR spectroscopy is a powerful tool in the study of ionsolvent and ionion
interactions in aqueous solutions and has helped greatly to improve the understanding of electrolyte solutions at the microscopic level.

5.5 NMR Studies of Ion Solvation in Non-Aqueous


Solvents
It is not surprising that 1H NMR was also applied to the study of cation solvation
in non-aqueous media. Most solvent molecules contain protons, but in the case of

224

LIQUIDS, SOLUTIONS, AND INTERFACES

aprotic solvents these protons often do not interact directly with the ions of the
electrolyte. Proton NMR has been used to determine solvation numbers of highly
charged cations such as Al3+ in solvents such as methanol, dimethylformamide,
and dimethylsulfoxide [G3]. Since the solvent molecules are tightly bound to the
cation, their exchange with molecules in the bulk is slow and two peaks are seen in
the NMR spectrum, one corresponding to the solvent molecules coordinated to
the cation and the other to free solvent molecules. By comparing peak areas, the
number of coordinating solvent molecules per cation can be determined. This is
typically six for cations such as Mg2+, Zn2+, Al3+, Ga3+, Co2+, and Ni2+ [G3].
Studies have also been carried out with systems where the exchange of solvent
molecules between the solvation shells of the ions and the bulk is rapid. In this
case the chemical shift of the nucleus being probed, for example protons, depends
on the nature of the electrolyte and its concentration. A typical example is the 1H
chemical shifts observed for some 11 electrolytes in acetonitrile [20], which are
summarized in table 5.6. In all cases the shift is to a lower frequency, indicating
that the protons at the positive end of the molecular dipole are more strongly
shielded in the presence of the electrolyte than in pure acetonitrile. Distinct trends
are dicult to discern due to complications resulting from dierent degrees of ion
pairing, but the perchlorate anion has the least eect among the anions considered. Among the halide anions, the trend follows the order Cl  Br > I . The
eect of the large tetraalkylammonium ions is small because of their size and the
fact that they interact with the negative end of the molecular dipole. The inuence
of the alkali metal cations increases approximately in the order K < Na < Li ,
that is, in the order of their polarizing power.
Another method of examining ionsolvent interactions is to study the chemical
shifts of the solute ions. This type of investigation has been carried out for the
7 + 23
Li , Na+, and 205Tl+ cations and for the 35Cl, 81Br, and 127I anions.

Table 5.6 Molar Chemical Shifts


for the Proton Resonance of
Acetonitrile in Electrolyte Solutions
at 258C [20]
Electrolytea
LiI
NaI
KI
LiClO4
NaClO4
Et4 NCl
Et4 NBr
Bu4 NCl
Bu4 NBr
Bu4 NI

Chemical Shiftb d/Hz M1


6.5
7.5
6.0
4.0
3.0
7.5
7.4
6.3
6.9
5.0

Et4 N is tetraethylammonium and Bu4 N ,


tetrabutylammonium.
b
With respect to that for pure acetonitrile.
a

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

225

Variation in the 23Na+ chemical shift with solvent nature has been very helpful in
elucidating the nature of the ionsolvent interactions, especially for aprotic solvents. Popov [21] showed that there is a linear correlation between the chemical
shift observed for 23Na+ in an aprotic solvent and the Gutmann donor number
DN when an electrolyte with minimal ion pairing is used. Values of d obtained in
NaPh4B are plotted against DN for 11 aprotic solvents in g. 5.10. A very good
correlation is found with a correlation coecient of 0.976. Data points for formamide, water, and methanol are also shown in this plot. The result for formamide falls on the regression line but those for water and methanol are clearly
below it. This led to the suggestion [21] that the eective donor numbers of water
and the alcohols are much higher than the values given by Gutmann [22] when
these solvents have their bulk structure with the accompanying hydrogen bonding. However, the Gutmann values of DN for these solvents are conrmed by
independent estimates of solvent basicity (see section 4.9).
Chemical shifts for the 7Li nucleus have also been studied as a function of
solvent nature for a variety of electrolytes including lithium perchlorate and
lithium tetraphenylborate [21]. Although they change with solvent nature, there
is no correlation with solvent donicity. Popov attributed the failure of the 7Li
system to monitor basic properties of the solvent to the fact that the paramagnetic
and diamagnetic screening constants for this atom are approximately equal, so
that they cancel one another. In the case of 23Na, the paramagnetic screening
constant is much larger than the diamagnetic one, so that this system can be used
to monitor the basicity of aprotic solvents.
Solvation of the halide ions in various solvents has been studied by measuring
the chemical shifts for 35Cl, 79Br, and 127I in water and several other polar
solvents [23]. The chemical shifts are strongly solvent dependent and correlate to
the UV absorption band energy corresponding to charge transfer to the solvent.

Fig. 5.10 Chemical shift for 23Na using sodium tetraphenylborate dissolved in various
solvents [21]. The regression line was drawn considering only aprotic solvents (lled
circles). Abbreviations for solvents given in chapter 4: PYR pyridine.

226

LIQUIDS, SOLUTIONS, AND INTERFACES

Polar molecular solutes have been used to probe the donoracceptor properties
of polar solvents. 19F chemical shifts have been measured for interaction between
triuoroiodomethane and the solvent molecule as electron pair donor [24]. As
interaction between the donor molecule and the iodine atom in this molecule
increases, electron density at the uorine atoms increases with a resulting positive
chemical shift in the 19F NMR signal. An excellent correlation between these
shifts and the Gutmann donor number was reported [24].
The 31P chemical shifts in triethylphosphine oxide measured in polar solvents is
used to dene the acceptor number scale for solvent acidity [25]. In this case, the
oxygen atom in the PO bond acts as an electron pair donor to the solvent as a
Lewis acid. The resulting inductive eect lowers the electron density at the phosphorus atom and results in a chemical shift which depends on solvent acidity.
In summary, NMR techniques based on the chemical shifts of a solute atom
provide a useful way of probing solutesolvent interactions. They demonstrate
clearly that the chemical nature of these interactions is important, and must be
considered in developing an overall understanding of the structure of both electrolyte solutions and solutions of polar molecules.

5.6 Vibrational Spectroscopy in Solutions


Vibrational spectroscopy is a powerful tool for studying solvation in polar solvents. These solvent molecules have permanent dipole moments and therefore
absorb radiation in the infrared region of the electromagnetic spectrum due to
the vibrational modes of motion. In the present section, the principal experimental techniques used in vibrational spectroscopy are outlined with emphasis on
methods for analyzing solvent structure and solvation.
A non-linear polyatomic molecule with N atoms has 3N  6 degrees of vibrational freedom. Each vibrational mode is characterized by a frequency which is
determined by the force constant characterizing the vibrational motion, and the
reduced mass of the system in a harmonic oscillator representation. For example,
acetonitrile (CH3CN) has six atoms and 12 degrees of vibrational freedom. A very
important vibrational mode in this molecule is the CN stretch, which is associated with the polar cyano group. If this group interacts with an ionic or molecular solute in the solvation process, the electron density in the bond is aected,
and a change in the vibrational frequency is observed. Other vibrations in this
molecule are associated with the methyl groups and the CC bond.
EXAMPLE

Estimate the force constant for the CC bond in acetonitrile using the harmonic oscillator approximation, given that the frequency of the CC stretching
mode expressed in wave numbers is 918 cm1 .
In the harmonic oscillator approximation the vibrational frequency is given
by
n

 
1 k 1=2
2p m

5:6:1

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

227

where k is the force constant and m, the reduced mass. The reduced mass is
estimated assuming that the vibrating groups are methyl (15.04 g) and cyano
(26.02 g):
m

0:01504  0:02602
1:583  1026 kg molec1
6:022  1023 0:01504 0:02602

5:6:2

In SI units, the frequency is


n 918  2:998  1010 2:752  1013 s1

5:6:3

On the basis of equation (5.6.1), the force constant is


k 4p2  1:583  1026  2:752  1013 2 473 N m1 molec1

5:6:4

There are two kinds of vibrational spectroscopy commonly used to study


solvent structure and solvation, namely, infrared and Raman spectroscopy.
These methods dier signicantly with respect to the nature of the vibrational
features which may be observed. Therefore, some fundamental concepts and
experimental methods are introduced before specic results are presented.

A. Infrared Spectroscopy
Infrared spectroscopy is normally carried out in the mid-infrared region, that is,
from 4000 to 200 cm1 . The near infrared region is at higher frequencies (12,500
to 4000 cm1 ) and the far infrared, at lower frequencies (200 to 10 cm1 ).
Experiments in these regions require special techniques and are not considered
further here.
Infrared radiation is only absorbed by the irradiated molecule at the appropriate frequency if the corresponding vibration results in a change in molecular
dipole moment. This means that not all vibrational modes are infrared active. An
analysis of which vibrational modes in a polyatomic molecule are active is based
on group theory and the symmetry properties of the molecule. More details about
this subject may be found in monographs devoted to spectroscopy [G4].
Modern infrared spectroscopy is normally carried out in the Fourier transform
mode (FTIR). Thus, the experimental information is gathered as an interferogram
in the time domain and then Fourier transformed to obtain absorbance as a
function of wavelength. A number of interferograms may be recorded in a few
seconds. These are averaged before Fourier transformation. In this way, the
signal-to-noise ratio in the resulting spectrum is signicantly enhanced with
respect to a spectrum obtained in a traditional dispersive spectrometer
In a simple transmission experiment the liquid sample is examined in a cell
made of a suitable infrared transparent medium. These include sodium chloride,
potassium bromide, zinc selenide, cadmium telluride, and germanium. Materials
like sodium chloride should not be used to study solutions in protic solvents like
methanol and water.
In the case of strongly absorbing media, infrared experiments are more conveniently carried out using internal reectance techniques. An example of an

228

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 5.11 Schematic diagrams illustrating (A) an attenuated total reection experiment at
the interface between a hemispherical window and a test solution and (B) the evanescent
wave, which decays rapidly with distance into the test medium.

experimental setup to carry out such an experiment is shown in g. 5.11. The


infrared radiation enters a hemispherical window at an angle y to the normal
drawn from the window j solution interface. When the refractive index of the
solution is less than that of the window, the radiation is totally reected at the
interface if the angle y is greater than the critical angle yc . On the basis of the wave
nature of the radiation the beam actually penetrates the optically less dense medium a very short distance. This penetrating wave is called the evanescent wave
because it decays exponentially with distance. From the theory of physical optics
the depth of penetration is the order of the wavelength.
EXAMPLE

Estimate the depth of penetration of infrared light with a frequency of


2000 cm1 into an aqueous solution given that it is transmitted through a
ZnSe hemisphere (nop 2:93) at an angle 28 greater than the critical angle.
The critical angle is given by
 s 
nop
yc sin
nw
op
1

5:6:5

where nsop is the refractive index of the solution and nw


op , that of the window.
Assuming that nsop 1:333,


1:333
yc sin1
278
5:6:6
2:93
The depth of penetration is given by
dp

lw
2 1=2
2psin y  nsop =nw
op
2

5:6:7

where lw is the wavelength of the radiation in the window. The required


wavelength is

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

lw

2:93  101
1:465  105 m
2000

229

5:6:8

Thus, for an angle of incidence equal to 298


dp

1:465  105
1:39  105 m
2p0:235  0:2071=2

5:6:9

For this system the depth of penetration is 14 mm. This distance is comparable
to the wavelength of the infrared radiation which is 5 mm.
The internal reectance technique is usually called attenuated total reection
(ATR) spectroscopy. It is especially useful for studying strongly absorbing media,
for example, aqueous solutions. When the infrared radiation is absorbed in the
test medium, one obtains a spectrum similar to that from a transmission experiment. However, there are distortions in the ATR spectrum, especially in the
region of intense bands. One reason for distortion is the fact that the depth of
penetration varies with wavelength. The other eect is due to the change of the
refractive index of the solution in the region of the intense band. ATR spectra
should be corrected for these eects so that they may be compared to normal
transmission spectra.
The combination of ATR and FTIR spectroscopies gives a powerful tool for
studying the eects of solvation in solutions made from polar solvents. Some
recent data obtained in experiments using these methods are discussed later in
this chapter.
B. Raman Spectroscopy
In Raman spectroscopy, the vibrational modes of a molecule are activated but in
an entirely dierent way. In such an experiment the system is irradiated with a
strong source of light, usually from a laser which emits in the visible region. A
molecule whose major dimension is less than the wavelength of the light will
scatter the light if it is not absorbed. The electrons in the irradiated molecule
oscillate as a result of this interaction and thereby produce radiation of the same
frequency but scattered in all directions with respect to the incident beam. This
phenomenon is known as Rayleigh scattering. However, a small fraction of the
incident radiation can interact with the molecule via its vibrational degrees of
freedom. If the vibrational motion results in a change in molecular polarizability,
then the quantum of scattered light is slightly dierent in energy from that of the
stimulating radiation. When this occurs, the phenomenon is known as Raman
scattering.
EXAMPLE

Given that carbon dioxide is a linear molecule, which of its vibrational modes
are infrared active, and which, Raman active?
As a linear triatomic molecule, carbon dioxide has four degrees of vibrational motion. These are the symmetrical stretch (n1 ), the asymmetrical stretch
(n3 ), and the bending mode (n2 ). The later vibration is doubly degenerate and
can be described in two directions perpendicular to the interatomic axis.

230

LIQUIDS, SOLUTIONS, AND INTERFACES

Because of its symmetry with respect to the central carbon atom, carbon
dioxide has no net dipole moment. In a symmetrical stretching vibration, the
dipole moment of the molecule remains zero. Therefore the n1 mode is not
infrared active. However, the electron density along the interatomic axis is
alternately elongated and condensed. Thus, the molecular polarizability
changes with symmetrical stretching and the n1 mode is Raman active.
Exactly the opposite conclusions are reached for the asymmetric stretching
mode (n3 ). Since one CO bond contracts while the other stretches, the molecule develops a dipole moment during vibration. Thus, the n3 mode is infrared
active. At the same time the increase in polarizability due to the stretching
bond is oset by the decrease due to the contracting bond. As a result there
is no net change in polarizability and the n3 is Raman inactive. The same kind
of arguments apply to the bending modes (n2 ). Thus, n2 is infrared active and
Raman inactive.
This example demonstrates that infrared and Raman spectroscopies are
often complementary. By applying a normal mode analysis using group theory,
one may determine which vibrational modes in more complex molecules are
infrared or Raman active.
The shift in frequency of the Raman scattered radiation from the stimulating
radiation may result in quanta of lower or higher frequency. The former process is
known as Stokes scattering and the latter as anti-Stokes scattering. The quantummechanical theory of the Raman eect involves the formation of a virtual
excited quantum state at an energy level higher than the ground state by an
amount hn0 , where n0 is the frequency of the stimulating radiation. The vast
majority of molecules which reach the virtual excited state decay back to the
ground state with the emission of Rayleigh scattered light of exactly the same
frequency. However, a very few molecules in the virtual excited state decay down
to the rst excited vibrational level of the ground state, thereby giving rise to
Stokes scattered light. The energy of the quantum of scattered light will be less
than hn0 by an amount corresponding to the energy dierence between the ground
vibrational state and the rst excited vibrational state. This is hnvib . It follows that
the frequency of the Stokes line is
nst n0  nvib

5:6:10

A very few molecules in the sample are in the rst excited vibrational level when
they interact with the stimulating radiation. They reach a virtual excited state
which is correspondingly higher in energy than most excited molecules. The
majority of these fall back to the same vibrational level, thereby emitting scattered
Rayleigh light of frequency n0 . However, some also reach the ground vibrational
level and emit a quantum of anti-Stokes scattered light. Because of the total
energy change involved, the frequency of the anti-Stokes line is
naSt n0 nvib

5:6:11

Because the population of the rst excited vibrational level is much less than that
of the ground state, the intensity of the anti-Stokes lines is less than that of the

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

231

Stokes lines. In most Raman experiments, only the Stokes part of the spectrum is
examined.
The Raman spectrum of carbon tetrachloride is shown in g. 5.12. The stimulating radiation, which has a wavelength of 488.0 nm, was obtained from an
argon-ion laser. On the wave number scale this corresponds to 20,492 cm1 ,
which is blue light. Three lines are resolved on each side of the central peak,
which is itself due to Rayleigh scattering. These lines correspond to ve vibrational modes in the CCl4 molecule which are Raman active. The intensities of the
Stokes lines which occur on the low-frequency side are higher than those of the
anti-Stokes lines. In addition, the shift of each Stokes line from the central
Rayleigh line is exactly equal to that for the corresponding anti-Stokes line.
Thus, the features of the spectrum conform to the quantum-mechanical analysis
discussed earlier.
Raman spectroscopy is an important technique used in the study of solvent
structure and solvation. Because of its complementary nature it is often used in
connection with infrared spectroscopy. Although most of the examples discussed
in the following sections involve infrared experiments, many examples of Raman
experiments can be found in the literature.

Fig. 5.12 Raman spectrum of carbon tetrachloride obtained using an argon-ion laser
operating at 488.0 nm. Each line is labeled in terms of its shift from the central Rayleigh
line. (From reference G5, with permission.)

232

LIQUIDS, SOLUTIONS, AND INTERFACES

5.7 Infrared Spectroscopy of Polar Solvents


All polar solvents considered in chapter 4 are polyatomic species and therefore
have vibrational spectra. Some vibrational modes are infrared active and others
are Raman active. Especially interesting are those modes associated with the
molecular dipole because they give information about intermolecular interactions.
In this section, attention is focused on the infrared spectra of pure polar solvents.
A. Protic Solvents
The most common protic solvent is water. It is also one of the most complex from
the point of view of vibrational spectroscopy because of its highly structured
nature. Since water is a triatomic, non-linear molecule it has three vibrational
modes, which are illustrated in g. 5.13. The n1 mode is the symmetrical stretch; n2
is the bending mode; and n3 is the asymmetrical stretch. All three vibrational
modes for water are active in the infrared because they involve changes in the
dipole moment. Activity in the Raman spectrum requires that the polarizability of
the molecule changes during vibration. Analysis of this aspect of molecular properties is more dicult but it shows that all three modes are also Raman active. A
summary of the frequencies of these vibrations for H2O, and the isotopes D2O,
and HOD determined from gas phase spectra are given in table 5.7.
The infrared and Raman spectra of liquid water are broad and complicated by
several types of vibrational interactions. Three regions can be distinguished in the
infrared spectrum (see g. 5.14). The OH stretching region due to the n1 and n3
modes is observed between 2800 and 3800 cm1 . The broad character of this band
is a result of the large, uctuating distribution of hydrogen bonds. In fact, one can
distinguish two classes of OH stretching vibrations which depend on whether the
OH group is involved in a weak or strong hydrogen bond. The second region
involves the n2 bending mode observed between 1500 and 1800 cm1 . A librational or restricted rotational region is observed between 250 and 800 cm1 .
Finally, there is a translational or hydrogen bond stretching region in the far
infrared from 20 to 250 cm1 which is not shown in g. 5.14.
The diculties in interpreting the vibrational spectrum of water are obvious.
Because of the broad nature of the bands, the two stretching modes n1 and n3
overlap. In addition, overtones complicate the assignment of bands. Thus, the
rst overtone of the n2 bending mode, 2n2 , lies close in frequency to the stretching
modes n1 and n3 . For these reasons, there are advantages in studying HOD, a
molecule for which the vibrational frequencies are quite dierent. As a result,

Fig. 5.13 Normal modes of vibration of a water molecule. The arrows indicate the relative
motion of each atom.

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

233

Table 5.7 Vibrational


Frequencies for H2O, D2O,
and HOD from Gas Phase
Measurements
Frequency/cm1
Molecule Mode
H2O
HOD
D2O

n1

n2

n3

3657 1595 3756


2727 1402 3707
2671 1178 2788

overtone and combination bands are more widely separated. Thus, the vibrational
properties of water are conveniently studied using dilute solutions of HOD in
H2O or D2O [18].
Protic solvents always have more complex infrared spectra because of the
presence of hydrogen bonding in the liquid state. In methanol, this involves
interaction of the acidic proton on the OH group in one molecule with the oxygen
atom in an adjacent molecule (g. 5.15). The infrared spectrum shows a wide band
centered at 3346 cm1 which is due to the OH stretch. When methanol is dissolved as a dilute solute in carbon tetrachloride, this band is sharp and appears at
3644 cm1 . An OH bending mode appears at 1449 cm1 . Another broad band
due to OH out-of-plane deformation is centered at 663 cm1 . The other features
of the methanol spectrum are due to the vibrational modes of the CH3 group or
to skeletal vibrations [27].
Another example of a protic solvent is formamide in which hydrogen bonding
involves the proton in the NH2 group and the carbonyl oxygen in an adjacent
molecule (see g. 5.16). A broad band centered at 3320 cm1 is due to the asym-

Fig. 5.14 Infrared spectrum of puried water in the frequency range 4000400 cm1 .
(From reference 26, with permission.)

234

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 5.15 Ball-and-stick diagram of a methanol molecule together with its infrared
spectrum as a liquid. (From reference 26, with permission.)

metric and symmetric stretching vibrations of the NH2 group. Other bands due
to this group occur at 1605, 1050, and 602 cm1 . An important band for this
molecule is the  CO stretching vibration at 1685 cm1 . However, this band is
not sharp, other spectral features being very close in frequency. The band at
1392 cm1 is assigned to the symmetric OC  N stretching mode and that at
1308 cm1 , to the CH deformation [27, 28]. As one would expect, the frequencies
of the bands due to vibrational modes associated with hydrogen bonding change
when formamide is a dilute solute in an aprotic solvent. Then, the NH2 band at
3320 cm1 and the  CO band at 1683 cm1 shift to higher frequencies.
B. Aprotic Solvents
As one would expect the vibrational spectra of aprotic liquids are usually much
simpler than those for protic liquids. Acetonitrile is an example of an aprotic
solvent whose polar properties are due to the large dipole moment associated
1
with the  C
N stretch at 2254 cm is a prominent feature
N bond. The  C

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

235

Fig. 5.16 Ball-and-stick diagram of a formamide molecule together with its infrared
spectrum as a liquid. (From reference 26, with permission.)

of the IR spectrum of liquid acetonitrile (g. 5.17). Other important bands include
1
1
the C  C
N bending mode at 748 cm , the C  C stretch at 918 cm , the CH3
1
rocking mode at 1040 cm and CH3 deformation modes at 1376 and 1445 cm1 .
The CH3 stretching modes are seen at 2945 and 3003 cm1 . The spectrum contains
two Fermi resonance bands in the region shown, an important one arising at
2293 cm1 . This band is due to a combination of the bands at 918 cm1 and
1
1375 cm1 , and interacts somewhat with the C
N band at 2254 cm because it
1
is only separated by 39 cm . Because of the electron density on the nitrogen
atom, this end of the molecule interacts strongly with cations and with molecular
solutes which are good Lewis acids. For this reason, the C
N stretching band is
often used to assess interactions of acetonitrile as a solvent with ionic and molecular solutes. More information about this aspect of the IR spectroscopy of the
acetonitrile molecule is given in the following section.
Acetone is an aprotic liquid with a very dierent structure. Its infrared spec stretch.
trum possesses a strong band at 1716 cm1 due to the asymmetric
CO
Other prominent features of its spectrum include the CH3 asymmetric and sym-

236

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 5.17 Ball-and-stick diagram of an acetonitrile molecule together with its infrared
spectrum as a liquid. (From reference 26, with permission.)

metric deformation modes at 1420 and 1364 cm1 , respectively, the C  C  C


asymmetric stretch at 1222 cm1 , and the CO deformation mode at 530 cm1
(g. 5.18). The CH3 stretching vibrations appear around 3000 cm1 . The  CO
stretching band can be used to monitor solutesolvent interactions in acetone
solutions but it is not as sharp as the  C
N stretching band in acetonitrile.
This shows that several overlapping bands occur in this region of the acetone
spectrum. The two principal components are due to the CO stretch of the
acetone monomer, and to the same stretching mode in an acetone dimer which
occurs at slightly smaller wave numbers. Because of the high dipole moment
associated with the double bond in this molecule, dimers are formed in two
dierent congurations. Dimerization in acetone has been studied by both
Raman [29] and infrared spectroscopy [30].
Dimethylformamide (DMF) has a much more complex structure than either
acetonitrile or acetone, but it is interesting to compare its infrared spectrum with
that of formamide. By replacing the two acidic protons on the amino group by
methyl groups, one obtains an aprotic liquid. As can be seen by comparing gs
5.16 and 5.19, the infrared spectrum of DMF is much simpler than that of for-

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

237

Fig. 5.18 Ball-and-stick diagram of acetone together with its infrared spectrum as a liquid.
(From reference 26, with permission.)

mamide. However, the features of the spectrum due to the  CO group and the
nitrogen atom are similar. The strongest band in the spectrum occurs at
1675 cm1 and is due to the  CO stretching mode. Another prominent feature
  N stretching mode. The CH3 rocking mode
at 1389 cm1 is assigned to the OC
1

is seen at 1095 cm and the O C  N deformation at 659 cm1 .
The infrared spectra of other aprotic solvents are also characterized by a strong
band or bands associated with the polar group in the molecule. For example,
dimethylsulfoxide has a strong absorption at 1057 cm1 due to the  SO stretching mode. However, absorption in this region is complicated by several overlapping bands, one of which is due to DMSO dimers [31]. Propylene carbonate,

238

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 5.19 Ball-and-stick diagram of dimethylformamide together with its infrared spectrum in the liquid state. (From reference 26, with permission.)

which has a  CO bond attached to a ve-member heterocyclic ring, has a


strong  CO band at 1797 cm1 . In the case of nitrobenzene and nitromethane,
the polar group is triatomic. In nitromethane, the strongest band in the infrared
spectrum is at 1563 cm1 due to the asymmetric stretching mode of the NO2
group. The symmetric stretch mode at 1378 cm1 is considerably weaker. The
NO2 group has other vibrational modes at lower frequencies.

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

239

In summary, the infrared spectra of aprotic solvents are much simpler than
those of protic solvents because of the absence of complications due to hydrogen
bonding. On the other hand, the aprotic liquids are characterized by very high
molecular dipole moments. As a result, dimers can be formed in which some of
the molecules line up with their dipole vectors in an antiparallel fashion [30]. This
can lead to the spectra being complicated by additional spectral features due to
solvent aggregates. Nevertheless, the prominent band due to the polar group in
these solvents can be used to probe solutesolvent interactions in non-aqueous
media. This subject is discussed in more detail in the next section.

5.8 Infrared Spectroscopy of Non-Electrolyte Solutions


When a polar solute such as acetonitrile is dissolved in another organic solvent,
the shift in the frequency of the polar group may be used to monitor solute
solvent interactions. This type of study is especially interesting because it demonstrates clearly the importance of short-range chemical interactions in determining
the properties of the solution.
A number of studies of the IR spectra of polar molecules dissolved in a variety
of solvents both polar and non-polar have been carried out [32]. In the case of
acetonitrile, the  C
N stretching frequency (n2 band) is shifted to higher values
in solvents which are stronger Lewis acids. Many of these solvents are protic and
interact with the electronegative  C
N group via hydrogen bonding. The electron density in this bond shifts toward the Lewis acid. Since the electron density is
associated with an antibonding orbital, the net eect is to make the  C
N bond
stronger, and a blue shift, that is, a shift to higher frequencies is observed.
A plot of the shift of the n2 band for both acetonitrile and deuterated acetonitrile
(CD3CN) as a function of the solvents acceptor number AN is shown in g. 5.20
for 12 solvents which are more acidic than acetonitrile. An excellent correlation
between n2 and the acceptor number AN is found except for formamide (F) and
N-methyl formamide (NMF). In the latter cases, the solvents are both strong Lewis
acids and strong Lewis bases. Corresponding results are obtained when acetonitrile
is dissolved in solvents which are stronger Lewis bases. In this case, there is a good
correlation between n2 and the solvents donor number DN, with the solvent
shifts being negative (g. 5.21). These experiments point out the importance of
Lewis acidbase properties in determining the nature and strength of short-range
interactions in solution. The strong Lewis bases interact with the CH3 group, which
is at the positive end of the molecular dipole. This interaction aects the  C
N
group, so that more electron density is associated with this part of the molecule. As
a result, a red shift occurs, that is, negative values of n2 are observed.
Solvent-induced frequency shifts have also been studied for dimethylsulfoxide
(DMSO), which is a strong Lewis base. Most solvents behave as Lewis acids and
interact with DMSO via the electron density on the  SO group. This interaction leads to a red shift for this band which is as large as 56 cm1 in the presence of
acetic acid [34]. The magnitude of the shift correlates well with the solvents
acceptor number giving the relationship
nSO 1080  1:375AN

5:8:1

240

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 5.20 Plot of n2 for CH3CN () and CD3CN () in more acidic solvents against the
solvents acceptor number AN. The best straight lines were estimated without the data for
F and NMF. The data for CD3CN have been shifted vertically by 20 cm1 for clarity.
(From reference 33, with permission.)

Fig. 5.21 Plot of n2 for CH3CN () and CD3CN () in more basic solvents against the
solvents donor number DN. The best straight lines were estimated without the data for F
and NMF. The data for CD3CN have been shifted vertically by 10 cm1 for clarity. (From
reference 33, with permission.)

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

241

For this system, removal of electron density from the  SO bond results in its
being weakened as one would expect without knowing the detailed molecular
orbital structure.
Acetone provides another interesting system for studying intermolecular interactions. The basicity of this solvent, whose DN is 17.0, is close to that of water.
On the other hand, it is a very weak Lewis acid with an AN equal to 12.5. Thus,
one expects the CO stretching frequency n3 to shift with change in the acidity of
the solvent in which acetone is dissolved. A good correlation is found between the
frequency of this band in 22 solvents and the solvents acceptor number AN, with
the frequency shifting in the red direction as AN increases. The equation describing the correlation is
n3 1718  0:286AN
5:8:2
with a correlation coecient equal to 0.876. Interaction of the acetone molecule
with a Lewis acid results in a weakening of the CO bond due to withdrawal of
electron density. The correlation is weakened by the eects of acetoneacetone
interactions which are stronger in solvents which are weak Lewis acids [29].
The eects of intermolecular interactions are seen much more clearly for the n17
mode which is the skeletal asymmetric stretch. Values of the frequency of this
vibration are plotted against solvent AN in g. 5.22. The equation describing the
linear correlation is
5:8:3
n17 1216 0:339AN
with a correlation coecient of 0.984 [30]. This mode is relatively unaected by
acetone dimerization, and shifts in the blue direction with increase in solvent
acidity.
Other systems in which solvent-induced frequency shifts have been studied
include benzonitrile, cyclopentanone, and tetramethylurea [32]. These studies all

Fig. 5.22 Plot of the frequency of the asymmetric stretching band of the molecular skeleton (n17 ) of acetone as a dilute solute in various solvents against the acceptor number of the
solvent, AN.

242

LIQUIDS, SOLUTIONS, AND INTERFACES

demonstrate the importance of specic solvation eects in determining intermolecular interactions in these systems. Vibrational spectroscopy provides a valuable
tool for probing these interactions in liquid solutions.

5.9 Infrared Spectroscopy of Electrolyte Solutions


Ions are stabilized in electrolyte solutions by the dipolar character of the solvent
molecules. Thus, one expects the iondipole interaction to result in a shift in
electron density along the direction of the dipole vector. This, in turn, should
result in a change in frequency of the vibrational modes associated with the
molecular dipole. As has been seen earlier, there is a strong band in the spectrum
of aprotic molecules which is associated with the electronegative group. Changes
in the frequency of this group allow one to monitor interactions of the solvent
molecules with cations. Interactions with anions are more dicult to see in the
vibrational spectrum of these systems but can be assessed under some circumstances. In the case of protic solvents, hydrogen bonding is important in the
solvation of anions. Thus, features of the IR spectrum associated with this aspect
of solvent structure are aected by the anion in the system.
Another way of assessing cationsolvent interactions is to examine the vibrational characteristics of the bond formed between the cation and the negative end
of the solvent molecules dipole. This bond is mainly electrostatic in character and
therefore is much weaker than intramolecular covalent bonds. As a result the
infrared band corresponding to vibration of the metalsolvent bond is normally
observed in the far infrared at frequencies less than 500 cm1 . Some results
obtained for the alkali metal cations in four aprotic solvents are summarized in
table 5.8.
It is clear that the frequency of the metalsolvent band decreases with increase
in the size of the alkali metal, that is, with decrease in the eld due to the charge on
the ion. When ion pairing is absent, the value of the frequency is independent of the
nature of the anion. This is denitely the case in DMSO, which strongly solvates
cations because of its high donor number. In addition, the relatively high permittivity of this solvent reduces the inuence of long-range ionion interactions.
Because instrumentation capable of working in the far infrared is not commonly available, studies of interactions between polar solvent molecules and ions
have more commonly involved intramolecular vibrational modes in the solvent

Table 5.8 Frequency of CationSolvent


Band, n/cm1 [G1]
Solvent Cation

AC

DMSO

NMP

PC

Li
Na
K
Rb
Cs

425
195
140



429
199
153
124
109

398
204
140
106


397
186
144
115
112

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

243

molecule. In the case of cations, vibrations associated with the polar group at the
negative end of the molecular dipole can be studied. Thus, cationsolvent interactions can be assessed by following changes in the  C
N stretching frequency
in acetonitrile, in the  SO stretching frequency in dimethylsulfoxide, or in the
 CO stretching frequency in acetone.
The eect of dissolving LiClO4 in acetonitrile (AcN) is illustrated in g. 5.23 on
the basis of a dierence spectrum. The lower spectrum in this gure shows the
absorbance features of pure AcN in the region from 600 to 3400 cm1 . The upper
spectrum was obtained by subtracting the spectrum of pure AcN from the spectrum of an AcN solution containing 0.7 M LiClO4. As a result the dierence
spectrum has both positive-going features corresponding to new bands in the
electrolyte solution, and negative-going features corresponding to bands whose
intensity decreased in the electrolyte solution. The most important changes are
1
those associated with the  C
N stretching mode at 2253 cm . In the dierence
spectrum a negative-going band is observed at this frequency, indicating that the
concentration of free acetonitrile has decreased in the electrolyte solution. These
AcN molecules are now coordinated to Li+ ions through the negative charge
density on the N atom and have their  C
N stretching frequency shifted in
the blue direction to 2280 cm1 . Negative-going bands are also observed at
918 cm1 (C  C stretching mode) and 748 cm1 (C  C
N bending overtone).
Spectral properties associated with the CH3 deformation modes at 1375 and
1453 cm1 are also aected by the addition of electrolyte. Perchlorate ion has
its own vibrational spectral features which appear at 625 and 1100 cm1 .
By following the concentration dependence of the negative-going band at
2253 cm1 , one can determine the average number of AcN molecules which are
coordinated to the metal ion in solution. Experiments show that the integrated
intensity of this band is linear in the electrolyte concentration over reasonable
concentration ranges. Interpretation of the negative slope of these plots requires
that the extinction coecient of free acetonitrile molecules be determined in a

Fig. 5.23 Dierence spectrum for an


acetonitrile solution containing
0.7 M LiClO4 obtained by subtracting the
spectrum of pure acetonitrile from that of
the solution, together with the spectrum of
pure acetonitrile.

244

LIQUIDS, SOLUTIONS, AND INTERFACES

suitable inert medium. This was done by observing the intensity of the  C
N
stretching mode for AcN dissolved in carbon tetrachloride as solvent [35, 36]. In
this way, the average number of solvent molecules coordinated to a single cation
was determined. Results for several monovalent and divalent cations in acetonitrile are summarized in table 5.9.
It is clear from the results in table 5.9 that the average coordination number nc
of solvent molecules to a cation varies signicantly with cation nature. This
variation is attributed to a corresponding variation in the extent of ion pairing.
If the coordination number is less than the maximum value for a given cation,
then the value of nc can be used to estimate the average number of anions associated with a cation, and thus, the average charge on the cationic species. The
maximum number of solvent molecules which can coordinate to a cation is
usually considered to be six, but for small cations it can be four.
The observed spectral shift for the  C
N stretching mode n2 varies considerably with cation nature. It is always in the blue direction, indicating that the C
N
bond is stronger in the presence of the positive electron-withdrawing eld of the
cation. This observation suggests that the electron density withdrawn from the
C
N system involves antibonding orbitals. The variation in n2 with cation is
usually attributed to variation in the cations electrical eld. The latter quantity is
usually estimated from the ratio of the cationic charge zi e0 to its radius ri .
However, a reasonable correlation between n2 and zi e0 =r is not obtained without considering the eects of ion pairing. On the other hand, if the eld is estimated using the eective average cationic charge, zi0 , estimated from the average
coordination number nc an acceptable correlation is obtained (see g. 5.24).
Cations also aect other solvent bands for AcN including the combination
band at 2293 cm1 (n3 n4 ), the C  C stretching mode at 918 cm1 (n4 ), and
1
the C  C
N deformation mode at 746 cm (2n8 ). Changes in the intensity of
these bands with electrolyte concentration may also be used to assess ion pairing
in acetonitrile solutions [35, 36].
Anions aect the features of the AcN spectrum to a much smaller extent [37].
Any change in the spectrum is usually associated with CH3 symmetrical stretch-

Table 5.9 Average Coordination Number for Acetonitrile


to the Metal Cation and Frequency Shift of the n2 Band
(  C
N stretch) from IR Spectra of Metal Perchlorate
Solutions in Acetonitrile [36]
Cation

Average Coordination Number nc

Frequency Shift n2

Li+
Na+
Mg2+
Ca2+
Sr2+
Ba2+
Zn2+
Cd2+
Pb2+

3.7
3.8
3.4
4.9
5.9
4.8
5.7
5.4
5.0

23
13
42
24
42
12
41
32
11

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

245

Fig. 5.24 Plot of the shift of the C


N stretching frequency of acetonitrile, n2 observed in
solutions containing various metal perchlorates against the eective eld of the metal
cation, z0i =ri [36].

ing mode at 2944 cm1 (n1 ) and the corresponding antisymmetrical mode at
3002 cm1 (n5 ). Polyatomic anions such as ClO4 and NO3 have very little eect
on this region of the spectrum. On the other hand, monoatomic ions such as the
halides, and linear polyatomic ions such as NCS aect this region of the spectrum strongly. This suggests that the anion is interacting with the methyl group at
the positive end of the molecular dipole, and that the extent of interaction
depends on the electrical eld associated with the anion [37].
Electrolyte eects on the vibrational spectra of polar solvents have been studied in a number of other solvents including acetone, pyridine, dimethylsulfoxide,
dimethylformamide, tetramethylsulfone, and nitromethane [37]. These studies
provide valuable information on the nature of solvation of ions in these systems.
In addition, they can be used to assess ion pairing and its variation with electrolyte nature and concentration.

5.10 UltravioletVisible Spectroscopy and


Solvatochromic Effects
Ultraviolet-visible spectroscopy usually involves electronic transitions in which
valence electrons in molecules and polyatomic molecules move to higher unlled
orbitals. This type of spectroscopy is well known in organic chemistry and often
involves the p electrons in groups such as CC, CO, NN, and NO. The
electronic transitions taking place are p ! p transitions, and in molecules with
heteroatoms, n ! p transitions, that is, from nonbonding orbitals for electrons
on atoms such as oxygen to an antibonding p orbital. Electronic transitions also
occur between s bonding orbitals and s antibonding orbitals but the associated

246

LIQUIDS, SOLUTIONS, AND INTERFACES

energy is usually quite high, so that the absorption is observed in the vacuum
ultraviolet at a wavelength less than 150 nm.
The discussion in this section is mainly concerned with species containing a
transition metal ion and the involvement of its d electrons in electronic transitions.
The simplest description of electronic energy levels in a transition metal complex
is based on crystal eld theory, but a more detailed description requires the
application of molecular orbital theory. When the metal ion is surrounded by
six ligands it is in an octahedral eld, and the d orbitals are no longer energetically
degenerate. The three orbitals with electron density directed away from the axes
of the reference coordinate system, namely, dxy , dyz , and dxz have lower energy
than those with electron density directed along these axes, namely, dx2 y2 and dz2 .
The energy dierence between the three lower levels (t2g orbitals) and the two
higher ones (eg orbitals) is called the crystal eld splitting energy and is designated
as 0 (see g. 5.25). The value of 0 depends both on the nature of the metal ion,
on the number of d electrons, and on the nature of the ligands. On the basis of a
large number of spectroscopic studies the splitting energy has been determined for
a wide variety of complexes. The variation in 0 with metal ion nature is illustrated with ions formed from the elements in the rst transition series of the
periodic table in table 5.10 for the case that the ligands are six water molecules.
The energy associated with the electronic transition varies from a minimum of
9.3 meV for Mn2+ to a maximum of 26.0 meV for Mn3+. Considerable variation
in 0 is also found with the nature of the ligand. In this case 0 increases in the



series I < Br < SCN < Cl < N
3 < OH < H2 O < NCS < NH3 < NO2

< CN < CO. The sequence is known as the spectrochemical series.
Another common coordination number observed in transition metal complexes
is four. When the ligands are situated as far away from each other as possible, one
obtains a tetrahedral conguration. In this case the ligands interact repulsively
with the dxy , dyz and dxz orbitals, which have their electron density directed

Fig. 5.25 Crystal eld


splitting of the d orbitals in
a transition metal ion in an
octahedral eld and a
tetrahedral eld due to
surrounding ligands (Lewis
bases).

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

247

Table 5.10 Crystal Field Data for the Complex Ions M(H2O)n
6 from the First
Transition Series
Ion

d Electrons

Ti3+

Ground State for Free Ion

Octahedral Field Conguration

0 =cm1

t12g

20,100

3+

t22g

19,950

V2+

t32g

12,100

Cr3+

t32g

17,400

Cr2+
Mn3+

4
4

D
5
D

t32g e1g
t32g e1g

14,000
21,000

Mn2+

t32g e2g

7,500

3+

t32g e2g

14,000

Fe2+

Fe

t42g e2g

9,350

3+

Co

t62g

20,760

Co2+

9,200

t52g e2g

2+

Ni

t62g e2g

8,500

Cu2+

t62g e3g

12,000

between the axes of the x, y, z coordinate system. As a result, the d orbitals are
split into two degenerate sets with the dx2 y2 and dz2 orbitals (e orbitals) having
lower energy than the dxy , dyz , and dxz orbitals (t2 orbitals). The energy dierence
is designated as t (see g. 5.25). Another conguration with four ligands is the
square planar geometry. As the name implies, the ligands lie in a plane centered
on the transition metal ion. This system is favored by metal ions with a d 8 conguration and has a more complicated distribution of d orbital energy levels than
either the octahedral or tetrahedral systems. Other geometries observed for transition metal complexes include a linear one with two ligands, and a trigonal one
with three ligands.
One normally thinks of the electronic spectroscopy of transition metal complexes as involving d ! d transitions. In fact, many of the spectra observed for
these systems do involve the promotion of d electrons from a lower lying level to
one which is higher because of the crystal eld splitting [38]. However, there are
also charge transfer transitions from an orbital associated with a ligand to an
empty one associated with the metal (LMCT) or from a d orbital on the metal to
an empty orbital associated with the ligand (MLCT). These are more frequent
when there are p bonds in the ligands of the transition metal complex.
Solvatochromic eects occur then the color of a solute depends on the nature
of the solvent in which it is dissolved. Two such systems were discussed in section
4.9. The rst is the betaine dye, 4-(2,4,6-triphenylpyridinium)-2,6-diphenylphenoxide, which is used to dene the DimrothReichardt parameter ET . This molecule undergoes a p ! p transition in the visible region whose wavelength is very
solvent dependent. In the strongly acidic solvent water it is equal to 453 nm which
corresponds to an energy gap of 264 kJ mol1 . In the very weakly acidic solvent
diphenylether, the wavelength for the same transition is 810 nm. This corresponds

248

LIQUIDS, SOLUTIONS, AND INTERFACES

to an energy gap and value of ET equal to 148 kJ mol1 . The change in the color of
the dye with solvent nature is clearly related to the charge transfer which accompanies the p ! p transition as illustrated in g. 4.12. Since the negatively charged
O atom in the ground state is stabilized to an extent which depends on solvent
acidity, the ET parameter gives an excellent way of estimating this molecular
property of the solvent.
Solvatochromic eects related to solvent acidity have been found for several
transition metal complexes. Burgess [39] studied the visible spectra of bis-(2,2 0 bipyridyl)biscyanoiron(II), bis-(1,10-phenanthroline)biscyanoiron(II), and related
iron complexes in a wide range of solvents, both polar and non-polar. In most
cases the wavelength of maximum absorption depends on solvent acidity and is
linear in the solvents acceptor number. The structure of the phenanthroline
complex is shown in g. 5.26. It is clear that the solvent interacts with the negative
charge density on the two cyano groups so that the complex probes the ability of
the solvent to act as a Lewis acid. Iron(II) is a d 6 system and the ligand eld
splitting of the d orbitals is large for these systems. Thus, all six d electrons are in
the low-lying t2g orbitals. Burgess [38] reported the frequency for an MLCT band,
that is, for charge transfer from a t2g orbital on the metal to a p orbital on the
bipyridyl or phenanthroline ligand. As the acidity of the solvent increases and its
interaction with the cyano ligands becomes stronger, the splitting between the t2g
and p orbitals increases. At the same time the frequency observed at maximum
absorption shifts in the blue direction. For example, the phenanthroline complex
absorbs at 634 nm in hexamethylphosphoramide, an extremely weak Lewis acid,
so that the solution is blue in color. In ethanol, a moderate Lewis acid, maximum
absorption occurs at 557, and in triuoroacetic acid, a very strong Lewis acid, at
395 nm. The relationship between the frequency (cm1 ) at maximum adsorption
and the Gutmann acceptor number AN is
nmax 107:18AN 14,340

5:10:1

on the basis of data in 12 polar solvents r 0:980 [40]. A similar study with bis(2,20 bipyridyl)biscyanoruthenium(II) and related complexes has also been carried

Fig. 5.26 Chemical structure of bis-(1,10phenanthroline)biscyanoiron(II). Solvent


molecules can interact with the electron
density on the cyano groups.

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

249

out [41]. These results show the same sensitivity to solvent acidity seen in the
earlier work with iron complexes.
Another group of transition metal complexes behave as solvatochromic indicators of solvent basicity. The best known of these is Cu(II) N; N; N 0 ; N 0 -tetramethylethylene diamine acetoacetonate or Cu(II)(tmen)(acac) (see g. 5.27). In
this complex the two chelates are located in a plane so that the resulting geometry
is approximately square planar. The transition of maximum frequency corresponds to a d electron associated with the o-planar orbitals dxz and dyz being
promoted to the dx2 y2 orbital which has its electron density in the plane containing the ligands. As the strength of interaction of the solvent molecules in the axial
positions with the metal ion increases, the eective geometry of the complex
changes from square plane through tetragonal to octahedral. At the same time
the splitting between the lowest occupied and the highest empty d orbital
decreases so that the frequency associated with the d ! d transition shifts in
the red direction. Values of the wavelength associated with the transition for
the polar solvents considered in chapter 4 are given in table 4.10 where they are
designated as Bsc , the solvatochromic basicity. Considerable variation in wavelength is observed, from a minimum of 522 nm in nitrobenzene, a weakly basic
solvent to 633 nm in hexamethylphosphoramide which is a strong Lewis base. For
this system, the wavelength correlates strongly with solvent basicity as assessed by
the Gutmann donor number (see equation (4.9.2)).
Another group of complexes exhibiting solvatochromic properties are Ru(II)
and Ru(III) ammine complexes containing one or more other ligands with p
bonds [40, 41]. A simple example is the Ru(II) pentammine pyridine cation,
which has an MLCT band at 407 nm in acetonitrile. This transition corresponds
to a d electron in a t2g orbital on the metal being transferred to a p orbital on
pyridine. When the solvent is changed to a more basic one such as dimethylsulfoxide, the wavelength increases. As a result there is a correlation between the
wavelength for the MLCT band and the Gutmann donor number DN, namely,
lSC 390:9 1:698DN

5:10:2

The correlation is very strong but the experimental study was limited to aprotic
solvents.
One can argue that correlations such as equations (4.9.2) and (5.10.2) are not
physically reasonable in that they are based on the wavelength of the electronic
transition related to the solvatochromic eect, not its frequency. The frequency is

Fig. 5.27 Chemical structure of Cu(II)N,N,N0 ,N0 -tetramethylethylenediamine


acetoacetonate. Solvent molecules can
interact as Lewis bases with the axial sites
in the complex as shown.

250

LIQUIDS, SOLUTIONS, AND INTERFACES

directly proportional to the associated energy dierence, which in turn reects the
strength of the interaction of the solvent as a Lewis base with the transition metal
complex. Thus, the frequency is the more relevant parameter to consider in assessing the relation between the solvatochromic eect and the Gutmann donor
number. In fact, equally strong correlations are found between the frequency
and the DN for both of these systems. The fact that linear correlations are
found with both frequency and wavelength, which is related to the reciprocal of
the frequency, reects the fact that the net change in either parameter with respect
to its average value is small. In this case the reciprocal of one quantity is approximately linear in that quantity over a limited range on the basis of a Taylors series
expansion. Equations (4.9.2) and (5.10.2) are used here because the parameters
BSC and lSC can then be used as empirical measures of solvent basicity which
increase with increase in basicity.
The examples of electronic transitions in transition metal complexes discussed
here have emphasized solvatochromic eects and often involve intramolecular
electron transfer. The role of the solvent in electron transfer is an important
aspect of these processes and is discussed in more detail in chapter 7. Many
electronic transitions do not display the type of solvent eects considered here
but depend instead on bulk solvent properties. The systems discussed above
interact in a specic way with the solvent usually as a result of a signicant change
in the dipole moment of the molecule or the complex ion as a result of the
electronic transition. There are many other interesting aspects of this area of
spectroscopy which have been discussed in more detailed treatments [38, 43].

5.11 Concluding Remarks


The discussion in this chapter has only considered representative examples of the
application of spectroscopy to the elucidation of the structure of liquids and
solutions. Raman spectroscopy is complementary to infrared spectroscopy and
has been used just as frequently to study solutesolvent, solutesolute, and solventsolvent interactions in solution. Electron spin resonance spectroscopy
involves the spins of unpaired electrons in molecules and ions and their interaction with a magnetic eld. It has been used to study hydrogen bonding and
hydrophobic interactions in aqueous solutions. Mossbauer spectroscopy involves
the nuclear transitions that result from the absorption of g-rays by certain nuclei.
It is used to study the coordination spheres of the corresponding ions in solution.
Dielectric spectroscopy is used to determine the dielectric properties of liquids and
solutions at microwave frequencies. As shown in chapter 4, this technique gives
information about molecular reorientation in an alternating electrical eld.
Ultrasonic absorption spectrometry is a study of the density changes which
occur when sound energy is passed through a liquid or solution and provides
information about structural relaxation times. Electron diraction studies are
related to neutron and X-ray diraction. Electrons are diracted by the local
electrical potential in the sample, which depends on the spatial conguration of
the nuclei and density distribution of the associated electrons. It is complementary
to X-ray diraction because it is more sensitive to the distribution of light atoms

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

251

in the liquid sample. More information about all these techniques, including those
discussed in more detail in this chapter, are available in the reviews in reference
[G1].
The important contribution of spectroscopic studies is structural information
about liquids and solutions at the atomic and molecular level. Most of the information discussed in earlier chapters is thermodynamic in nature and does not
provide a microscopic description of the system. When the spectroscopic details of
intermolecular interactions are available, one is able to understand thermodynamic results in much greater detail. Spectroscopic experiments were developed
mainly in the latter half of the twentieth century. As a result of the detailed
information they provide, understanding of the structure of condensed phases
is now at the same level as our understanding of the much simpler gas phase.

General References
G1. Dogonadze, R. R.; Kalman, E.; Kornyshev, A. A.; Ulstrup, J. The Chemical Physics
of Solvation, Part B: Spectroscopy of Solvation; Elsevier: Amsterdam, 1986.
G2. Marcus, Y. Ion Solvation; Wiley-Interscience: New York, 1986.
G3. Burgess, J. Metal Ions in Solution; Ellis Horwood: Chichester, 1978.
G4. Drago, R. S. Physical Methods in Chemistry, 2nd ed.; Saunders, Fort Worth, TX,
1992.
G5. Nakamoto, K. Infrared and Raman Spectra of Inorganic and Coordination Compounds,
5th ed.; Wiley Interscience, New York, 1997.

References
1. Enderby, J. E.; Neilson, G. W. Rep. Prog. Phys. 1981, 44, 593.
2. Blum, L.; Narten, A. H. Adv. Chem. Phys. 1976, 34, 203.
3. Palinkas, G.; Radnai, T.; Hajdu, F. Z. Naturforsch. 1979, 35a, 107.
4. Magini, M.; Licheri, G.; Paschina, G.; Piccaluga, G.; Pinna, G. X-Ray Diraction of
Ions in Aqueous Solutions: Hydration and Complex Formation; CRC Press: Boca
Raton, FL, 1988.
5. Ohtaki, H.; Radnai, T. Chem. Rev. 1993, 93, 1157.
6. Radnai, T.; Kalman, E.; Pollmer, K. Z. Naturforsch. 1984, 39a, 464.
7. Tamura, Y.; Spohr, E.; Heinziger, K.; Palinkas, G.; Bako, I. Ber. Bunsen-Ges Phys.
Chem. 1992, 96, 147.
8. Enderby, J. E. Chem. Soc. Rev. 1995 24, 159.
9. Neilson, G. W.; Enderby, J. E. J. Phys. Chem. 1996, 100, 1317.
10. Tromp, R. H.; Neilson, G. W.; Soper, A. K. J. Chem. Phys. 1992, 96, 8460.
11. Powell, D. H.; Neilson, G. W.; Enderby, J. E. J. Phys. Condens. Mater 1993, 5, 5723.
12. Hindman, J. C. J. Chem. Phys. 1962, 36, 1000.
13. Davies, J.; Ormonroyd, S.; Symons, M. C. R. Trans. Faraday Soc. 1971, 67, 3465.
14. Deverell, C.; Richards, R. E. Mol. Phys. 1996, 10, 551.
15. Templeman, G. J.; van Geet, A. L. J. Am. Chem. Soc. 1972, 94, 5578.
16. Bloor, E. G.; Kidd, R. G. Can. J. Chem. 1972, 50, 3926.
17. Deverell, C.; Richards, R. E.; Mol. Phys. 1969, 16, 421.
18. Desnoyers, J. E.; Jolicoeur, C. In Comprehensive Treatise of Electrochemistry;
Conway, B. E., Bockris, J. OM., Yeager, E., eds.; Plenum: New York, 1983; Vol. 5.
19. Covington, A. K.; Newman, K. E. In Modern Aspects of Electrochemistry; Bockris, J.
OM., Convway, B. E., eds.; Plenum: New York, 1977; Vol. 12, Chapter 2.
20. Coetzee, J. F.; Sharpe, W. R. J. Solution Chem. 1972, 1, 77.
21. Popov, A. I. Pure Appl. Chem. 1975, 41, 275.

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23.
24.
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26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
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LIQUIDS, SOLUTIONS, AND INTERFACES

Gutmann, E.; Wychera, E. Inorg. Nucl. Chem. Lett. 1966, 2, 257.


Stengle, T. R.; Pan, Y.-C. E.; Langford, C. H. J. Am. Chem. Soc. 1972, 94, 9037.
Spaziante, P. M.; Gutmann, V. Inorg. Chim. Acta 1971, 5, 273.
Mayer, U.; Gutmann, V.; Gerger, W. Monatsh. Chem. 1975, 106, 1235.
Hansen, D. L., Ed. Sprouse Collection of Infrared Spectra, Book IV, Common Solvents:
Condensed Phase, Vapor Phase and Mass Spectra; Sprouse Scientic Systems: Paoli,
PA.
Lin-Vien, D.; Colthrup, N. B.; Fateley, W. G.; Grasselli, J. G. The Handbook of
Infrared and Raman Characterstici Frequencies of Organic Molecules; Academic
Press: New York, 1991.
Smith, C. H.; Thompson, R. H. J. Mol. Spectrosc. 1972, 42, 227.
Perelygin, I. S. Fluid Phase Equilib. 1996, 116, 395.
Cha, D. K.; Kloss, A. A.; Tikanen, A. C.; Fawcett, W. R. Phys. Chem. Chem. Phys.
1999, 1, 4785.
Fawcett, W. R.; Koss, A. A. J. Chem. Soc., Faraday Trans. 1996, 92, 3333.
Fawcett, W. R. In Quantitative Treatments of Solute/Solvent Interactions; Politzer, P.,
Murray, J. S., eds.; Elsevier: Amsterdam, 1994; Chapter 6.
Fawcett, W. R.; Liu, G.; Kessler, T. E. J. Phys. Chem. 1993, 97, 9293.
Fawcett, W. R.; Kloss, A. A. J. Phys. Chem. 1996, 100, 2019.
Fawcett, W. R.; Liu, G. J. Phys. Chem. 1992, 96, 4231.
Fawcett, W. R.; Liu, G.; Kloss, A. A. J. Chem. Soc., Faraday Trans. 1994, 90, 2697.
Perelygin, I. S. In Ionic Solvation; Krestov, G. A., Ed.; Nauka: Moscow, 1987; Chapter
3.
Lever, A. B. P. Inorganic Electronic Spectroscopy, 2nd ed.; Elsevier: Amsterdam, 1984.
Burgess, J. Spectrochim. Acta 26A, 1970, 1369, 1957.
Soukup, R. W.; Schmid, R. J. Chem. Educ. 1985, 62, 459.
Timpson, C. J.; Bignozzi, C. A.; Sulliman, B. P.; Kober, E. M.; Meyer, T. J. J. Phys.
Chem. 1996, 100, 2915.
Curtis, J. C.; Sullivan, B. P.; Meyer, T. J. Inorg. Chem. 1983, 22, 224.
Murrell, J. N. The Theory of Electronic Spectra of Organic Compounds; Wiley: New
York, 1963.

Problems
1. The overall pair correlation function for acetonitrile is obtained by X-ray and
neutron diraction experiments. List the component pair correlation functions which make up Gr in each experiment. Devise a strategy for separating
these based on isotopic substitution.
2. Write down the pair correlation functions which are involved in a neutron
diraction study of aqueous LiNO3 solutions. Devise a strategy for separating these using isotopes.
3. Estimate the fraction of 7 Li atoms in each of the four quantum states when
this atom is in a magnetic eld of 5 T at 258C.
4. The equation relating the chemical shift for

23

Na to the DN is

d23 Na 16:78  0:510DN


Estimate the chemical shift for 23 Na in nitrobenzene, benzonitrile, and butyronitrile using the DN data in table 4.10.

SPECTROSCOPIC STUDIES OF LIQUID STRUCTURE AND SOLVATION

253

5. Examine the importance of isotope eects on the IR spectrum of acetonitrile.


Estimate the frequencies of the symmetric and asymmetric CH3 stretching
modes in deuterated acetonitrile given that they are 2945 and 3003 cm1 in
13 15
normal acetonitrile. What is the frequency of the C
N stretch in CH3 C N?
6. The following frequencies have been observed for the C
N stretch in various
nitriles:
2253 cm1
2247 cm1
2228 cm1

Acetonitrile
Propionitrile
Benzonitrile

Can these results be accounted for quantitatively using the simple harmonic
oscillator model?
7. In the NMR spectroscopy of liquids, the spin lattice relaxation time falls in
the range 102 to 102 s. This inuences the width of the NMR adsorption line.
Estimate the corresponding minimum width of the line using the relationship
n

1
2pT1

What is the source of this relationship?


8. The correlation between the wavelength of the solvatochromic absorption by
the Cu complex shown in g. 5.27 is
lSC 525:2 2:89DN
where DN is the Gutmann donor number. Re-express this equation in terms
of the energy hn associated with the transition. Show that the energy is also
approximately a linear function of DN for the energy range in question.

Non-Equilibrium Phenomena in
Liquids and Solutions

Lars Onsager was born in 1903 in Oslo,


Norway, where he grew up and attended
school. In 1920 he entered the Norwegian
Institute of Technology in Trondheim to study
chemical engineering, graduating in 1925. After
spending several months with Debye in Zurich,
he became interested in the theory of
electrolytes and developed the model for
electrolyte conductivity which he later
published with Debye. In 1928 he moved to the
United States and held positions at Johns
Lars Onsager
Hopkins and Brown Universities. He moved to
Yale University in 1933, where he was
appointed Gibbs Professor of Theoretical Chemistry in 1945, and remained
there until he retired. Onsager is best known for his work in the area of
irreversible thermodynamics where he developed the reciprocal relations which
are now known after him. He submitted this work as a doctoral thesis to his
alma mater in Trondheim but it was not accepted. Clearly his work in this area
of physical chemistry was very advanced for its time. Onsager also worked in
other areas of physical chemistry including colloids, dielectrics, orderdisorder
transitions, metals and superuids, hydrodynamics, and fractionation theory.
He received the Nobel Prize in chemistry in 1968 for his discovery of the
reciprocal relations. His work was also recognized by many other awards both
in the United States and internationally. He died in 1976.

6.1 Non-Equilibrium Processes Are Usually Complex


The topics considered up to this point have involved liquids and solutions at
equilibrium. Attention is now turned to systems which are not at equilibrium,
and the processes which occur spontaneously in such systems. The physical phenomena involved can be quite complex, so that the task faced in early experiments
was to separate the various processes and understand the physical properties of
the system which govern them.
Consider what happens when a beaker of pure isothermal water is placed on a
hot plate. The water near the bottom rises in temperature and a temperature
gradient is set up. As a result heat ows from the bottom of the beaker, producing
254

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

255

a gradual increase in temperature in the water at a given height above the bottom.
In addition, the temperature varies with distance, being highest at the bottom and
lowest at the top. Eventually, the temperature of the water in the beaker is uniform and equal to that of the hot plate, assuming that the water does not boil.
However, the ow of heat is not the only process resulting from the heat source.
The density of the hot water is less than that of the cold water, so that a convection process is set up in order to achieve uniform density. Convection results in
cold water moving down into the hot region so that the ow of water molecules
assists the ow of heat. The changes which occur in this system cannot be understood without considering both processes.
A system undergoing an irreversible change involving an electrolyte is electrolysis in an electrochemical cell. When current ows between two copper electrodes
in an aqueous solution of CuSO4, the charge in solution is carried by migration of
Cu2 ions moving in one direction and SO2
4 ions moving in the opposite. At the
cathode, the incoming Cu2 ions are reduced to metallic copper, thereby lowering
the concentration of these ions in the electrodes vicinity. At the anode, Cu metal
is oxidized to produce Cu2 ions in the solution, so that the local concentration of
cations is increased. The changes in ionic concentrations near each electrode result
in the establishment of concentration proles. As a result, diusion of ions occurs
as well as migration in the electrical eld. If the density of the solution is signicantly changed near the electrode, convection is also present so that three
irreversible processes contribute to the mass transfer, and thus, to the total current observed in the electrolysis experiment.
In general, non-equilibrium processes are a function of both position in the
system and time. A convenient way of discussing these processes is in terms of
uxes, that is, the ow of matter or energy through unit area per second in a given
direction. The ux is a vector quantity which depends on the specic location in
the system, and it is also usually a function of time. When the ux is independent
of time, the non-equilibrium process is called a steady-state process. Irreversible
thermodynamics is used to relate the uxes in the non-equilibrium system to the
forces which give rise to them. As will be seen in the next section in this chapter,
this subject gives a very useful way of relating these quantities when there is more
than one of each, as illustrated in the examples discussed above.
In this chapter, attention is focused on mass transfer processes in isothermal
systems, especially in electrolyte solutions. Heat transfer is not discussed, but the
methods used to treat this problem are very similar to those used to analyze
diusion problems. Chemical reactions in solutions are another example of
non-equilibrium processes. These are discussed in detail in chapter 7.

6.2 The Thermodynamics of Irreversible Processes


Onsager [1] developed an approach to the study of non-equilibrium processes
which is based on elementary thermodynamic concepts. This provides a useful
background to the subjects discussed in this chapter and helps show the connection between various processes occurring in a system undergoing an irreversible
change.

256

LIQUIDS, SOLUTIONS, AND INTERFACES

The fundamental quantity describing the irreversible process is the ux vector


Ji for species i. In the case of mass transfer, it describes a ow in a given direction
in space in units of moles or grams crossing unit area per second. It can also be
described as the product of the local concentration ci times the velocity vi at which
molecules or ions are moving. Thus,
Ji c i v i

6:2:1

The latter denition is conceptually helpful when the concentration is changing


with position in the system. One may write a similar relationship for an energy
ux, Je , that is
J e re v e

6:2:2

where re is the energy density in joules per cubic meter and ve , its velocity in a
given direction.
The change in the ux with position in the system may be related to the time
derivative of the local concentration by applying Gauss theorem. Consider a
system with volume V and surface area A. Suppose that substance i is owing
out of this volume. Then the rate of substance i leaving in moles per second can be
found by integrating the ux Ji over the surface area A, so that

dn
 i Ji
dA
6:2:3
dt
A
where dni =dt is the rate of loss of the substance ni in moles per second. This can
be related to the divergence of the ow, which is dened in vector notation as
divJi

@Ji @Ji @Ji

@x @y @z

6:2:4

Physically, a positive divergence of the ow at a given point x; y; z in the system


means that substance i is owing out of that point, that is, the point is a source.
On the other hand, if the divergence is negative, substance i is owing into the
point and it is a sink. By integrating div Ji over the volume of the system, one can
determine the net change in mass with respect to time for the system. Thus,

divJi dV Ji
dA
6:2:5
V

This is Gauss theorem stated with respect to mass transfer.


The nal part of the analysis involves relating the change in the number of
moles of component i to the changes in its concentration within the system.
Assuming conservation of mass and no chemical reactions, this means that

dni
@ci

dV
6:2:6
dt
@t
V

Combining equations (6.2.3)(6.2.6), one obtains

dni
@ci

dV  Ji
dA  divJi dV
dt
@t
V

6:2:7

257

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

It follows that
@ci
div Ji
@t

6:2:8

This is an important result connecting the variation in concentration with time at


a given point in the system to the divergence of the ux at the same point. It is
called the equation of continuity with respect to mass.
The cause of the ux in the irreversible process is called a force. This term is not
used in the strict Newtonian sense but instead it can refer to any source of
perturbation. Forces resulting in uxes include a temperature gradient, a concentration gradient, a density gradient, and a gradient in electrical potential. These
forces are vectors and are represented by the general symbol Xi . If concentration
is varying in the x direction in a system, the gradient is @ci =@x. In order to keep the
discussion general, the gradient is written in vector notation so that variations in
ci in all possible directions can be considered. Thus,
Xc rci

@ci
@c
@c
i ij ik
@x
@y
@z

6:2:9

where Xc is the force due to the concentration gradient and i, j, and k are unit
vectors in the x; y, and z directions respectively. The force due to a temperature
gradient is
XT rT

6:2:10

that due to a gradient in electrical potential


X r

6:2:11

and so on. It is obvious that forces dened in this way have dierent units.
The general equation relating forces and uxes from Onsagers theory is
Ji

n
X

Lik Xk

6:2:12

k1

where Lik is the phenomenological coecient relating force Xk to ux Ji . This


linear relationship only holds when the departure from equilibrium is not large.
The exact limitations for equation (6.2.12) can only be determined experimentally.
It is usually found that each force leads to a dierent ux. Thus, if there are two
forces, there are two uxes and four phenomenological coecients. A system with
three forces has three uxes and nine phenomenological coecients. Fortunately,
these coecients are not all unique, as will be seen below.
The example of the beaker of water on a hot plate is now considered with
respect to equation (6.2.12). There are two forces in this system, namely, a temperature gradient XT , and a density gradient, Xr . Thus, one may write,
JT LTT XT LTr Xr

6:2:13

Jr LrT XT Lrr Xr

6:2:14

and

258

LIQUIDS, SOLUTIONS, AND INTERFACES

where LTT , LTr , LrT and Lrr are the phenomenological coecients. JT and Jr are
the uxes for the temperature and density, respectively. LTT is directly related to
the coecient of thermal conductivity for water, and Lrr , to the viscosity of
water. The coecients LrT and LTr are related to the eect one process has on
the other. According to one of Onsagers theorems, the cross-coecients are equal
to one another if the forces are dened appropriately. This is an example of an
Onsager reciprocal relation. In this case, only three phenomenological coecients
are required to describe the irreversible process in the system. The easiest way to
achieve an appropriate denition is to dene the force as the gradient of the
energy associated with the process. This conclusion is illustrated in more detail
in this chapter.
Some of the phenomenological coecients relating forces and uxes are
already familiar from less general treatments of the subject. For example, the
phenomenological coecient relating a concentration gradient and a mass transfer ux is the diusion coecient. Other phenomenological coecients are related
to the ionic mobility, the coecient of thermal conductivity, and the solvent
viscosity. These are discussed in more detail later in this chapter.
EXAMPLE

Compare the phenomenological coecient for mass transfer dened in terms


of the concentration gradient with that based on a Newtonian force dened for
the gradient of the chemical potential.
The traditional relationship between the ux of species i and its concentration gradient is
Ji Di rci

6:2:15

where Di is the diusion coecient, that is, the traditional phenomenological


coecient. The negative sign expresses the fact that the ux vector is pointed in
the opposite direction to that in which the concentration gradient increases. If
rci has units of mol m4 and Ji , units of mol m2 s1 , the units of the diusion
coecient are m2 s1 .
In order to dene a Newtonian force, one must relate the concentration
gradient to an energy gradient. The easiest way of achieving this is to use
the chemical potential of species i, which is the thermodynamic measure of
the species ability to do useful work. The chemical potential of species i may
be written as
mi mii0 RT ln ai

6:2:16

where mi0 is the standard chemical potential and ai , the activity of species i. The
gradient of the chemical potential is
rmi RT r ln ai

6:2:17

Ji Li RT r ln ai

6:2:18

Now one may write

where Li is the Newtonian phenomenological coecient for mass transfer. The


units of rmi are J m1 mol1 or N mol1 . Thus the units of Li are mol2 m2
N1 s1 .

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

259

Another important aspect of Onsagers theory is the principle of microscopic


reversibility. This is usually discussed with respect to the detailed balancing of
chemical reactions. When it is considered with respect to the phenomenological
coecients, it leads to the reciprocal relations discussed above, namely that
Lik Lki

6:2:19

In other words, the matrix giving the phenomenological coecients for the system
is symmetric. Another important part of this theory is that one can estimate the
entropy generated in an irreversible process. Onsager showed that the local rate of
entropy production per unit volume is
y

1 @S 1 X

J
X
V @t T i i i

6:2:20

This relationship can only be applied when the forces are appropriately dened.
In the case of mass transfer, if the force is measured in J m1 mol1 and the ux in
mol m2 s1 , the rate of entropy production is obtained in J K1 m3 s1 .
Onsagers theory provides an elegant background for the consideration of nonequilibrium processes. It is especially helpful when more than one mechanism of
irreversibility is present. This subject has only been briey introduced here. More
details can be found in monographs devoted to this area of physical chemistry
[G1, 2].

6.3 The Viscosity of Liquids


Viscosity is the property of a uid which characterizes its resistance to ow. It is
often measured by timing the ow of a liquid through a cylindrical tube under the
inuence of gravity. In order to understand the denition of the viscosity, consider a uid owing between two large plane parallel plates (g. 6.1). The velocity
of the uid in the direction of the ow, vx , varies with position. It is at its maximum midway between the plates and decreases to zero between each plate on the
basis of experimental observation. Now imagine that the uid is made up of
horizontal layers which are parallel to the plates. The movement of one layer
with respect to another is retarded by a frictional force which is related to the
uids viscosity. The origin of this friction is clearly intermolecular forces.
In order to dene the viscosity, one imagines a cylinder of thickness dx and
radius r located on the central axis of the tube. The retarding force is proportional
to the surface area of the cylinder involved in the ow and to the gradient of the

Fig. 6.1 Schematic diagram of a


liquid owing between two parallel
plates. The arrows indicate the
magnitude of the velocity and the
direction of the ow.

260

LIQUIDS, SOLUTIONS, AND INTERFACES

velocity in the r-direction (see g. 6.1). This leads to Newtons law of viscosity,
which is
Fx ZA

dvx
dr

6:3:1

where Fx is the force in the x-direction, dvx =dr, the velocity gradient in the
r-direction, Z, the viscosity, and A, the area of contact. The outer area of the
cylinder for the example considered is 2pr dx. In the case of laminar ow,
the velocity on the outer surface of the cylinder is constant. This means that
the retarding force due to the viscous drag is exactly counterbalanced by the
force driving the liquid forward, which usually is a pressure dierential in the
tube. In the classical experiments used to measure liquid viscosity the pressure
dierential is established by gravity. If the pressure gradient is dP=dx, then the
force in the x-direction on the cylinder is
Fx pr2

dP
dx

6:3:2

where the minus sign takes into account the fact that the pressure drops as x
increases. Equating these forces with the appropriate value for the contact area,
one obtains
dvx
r dP

dr
2Z dx

6:3:3

If the radius of the tube is r0 , integration of equation (6.3.3) gives the result that
vx

1 2
dP
r  r20
4Z
dx

6:3:4

This shows that the forward velocity is a parabolic function of position in the tube
varying from zero at the wall where r is equal to r0 , to the maximum value at the
center of the cylindrical tube, where vx is equal to r20 dP=dx=4Z. It is emphasized that equation (6.3.4) is only applicable to laminar or non-turbulent ow in a
cylindrical tube. When a liquid ows under dierent geometrical boundary conditions, the relationship between the ux and the force is not the same.
From equation (6.3.1), the SI units of viscosity are N s m2 or Pa s. In the older
literature, the viscosity is cited in cgs units, that is, in dyn s cm2 . 1 dyn s cm2 is
called a poise. Since one Newton is equal to 105 dynes, it follows that one poise is
equal to 0.1 Pa s. At room temperature, liquids typically have viscosities of 1 cP,
which corresponds to 1 mPa s.
Another important relationship used to describe the movement of a heavier
solid object through a uid was derived by Sir George Stokes. In the case that the
object is a sphere, the viscous drag or force on it in the direction opposite to its
movement is
F 6pZrv

6:3:5

where r is the radius of the moving sphere. When a heavier solid sphere, for
instance, a marble, is dropped into a viscous liquid, its velocity, which should
continuously increase under the force of gravity alone, is observed to decrease and

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

261

eventually become constant. At this point, the gravitational force corrected for
buoyancy is exactly balanced by the viscous drag. This leads to the following
relationship:
vmax

2r2 g
r  r1
9Z s

6:3:6

Here vmax is the maximum velocity, g, the acceleration due to gravity, rs , the
density of the solid, and r1 , the density of the liquid. Stokes law is important
in relating the movement of ions and molecules dissolved in liquids to other
transport properties.
In order to connect the above expressions to Onsagers theory, it is necessary to
extend equations such as (6.3.1) to three dimensions. This equation shows that a
force in one direction leads to velocity changes in the other two spatial directions.
A general treatment of uid ow requires that one identify the components of the
pressure tensor associated with the force which leads to uid ow. The force
vector F has, in general, a component in each of the three Cartesian directions.
The component in the x-direction, Fx , gives rise to three pressure components,
one in the same direction, Pxx , and two shear components, Pxy and Pxz . Six more
pressure components are obtained from the force components in the y- and zdirections, Fy and Fz . As a result, there is a second-rank pressure tensor Pij with
nine components. Analysis on the basis of classical dynamics leads to the conclusion that the o-diagonal elements, Pij and Pji , are equal. As a result, six distinct
elements of this tensor must be determined to dene it. The second important step
is to write an equation of continuity in terms of momentum. Dening the momentum density  as
 rv

6:3:7

where r is the local density and v, the local velocity, the momentum equation of
continuity is
@
r
J
@t

6:3:8

where J is the ux of momentum. J is also a second-rank tensor so that the


relationship between  and F can only be obtained by considering the tensorial
nature of the problem. As solution of the problem was obtained many years ago
and resulted in the NavierStokes equation [3]. This equation is the basis of the
subject of hydrodynamics. An excellent introduction to this topic can be found in
the monograph by McQuarrie [3].
Values of the viscosity for the polar liquids discussed in chapter 4 are collected
in table 6.1. A large variation in viscosity is seen, varying from 0.3 mPa s for
acetone to 10 mPa s for tetramethylenesulfone. The viscosity is a direct reection
of intermolecular forces, which obviously change considerably in strength in this
group of liquids. Debye [5] considered the viscosity in more detail in this regard
and pointed out that there should be a connection with the relaxation time tD
observed when a polar liquid is exposed to a high frequency alternating electrical
eld (see chapter 4). This parameter also reects the eect of intermolecular forces
when a molecule or group of molecules undergo rotational diusion. Debye

262

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 6.1 Values of the Viscosity


and the Enthalpy Associated with Its
Temperature Dependence for
Selected Polar Solvents at 258C [4]
Solvent

Viscosity
Z=mPa s

Enthalpy
HZ =kJ mol1

0.890
0.545
1.083
1.956
2.593
3.302
1.65

2.09
9.3
12.5
17.2
18.6
18.6
12.1

0.303
0.341
1.237
0.549
0.927
0.802
1.996
3.245
1.666
1.795
0.610
0.410
2.513
10.29
1.395

5.9
6.1
12.0
8.5
9.4
8.5
13.6
15.0

12.7
7.5
6.6
14.9
20.0

Protic
1.
2.
3.
4.
5.
6.
7.

W
MeOH
EtOH
PrOH
BuOH
F
NMF

Aprotic
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.

AC
AcN
BzN
BuN
DMA
DMF
DMSO
HMPA
NMP
NB
NM
PrN
PC
TMS
TMU

developed a model for tD in which it was imagined that one polar molecule which
is assumed to be a sphere undergoes rotational diusion in a liquid continuum
whose intermolecular forces are evaluated by the bulk viscosity Z. On this basis,
he derived the relationship
tD

4pZr3m
kB T

6:3:9

in which rm is the radius of the molecule. If this is applied to estimate the value of
tD for the solvents listed in table 6.1, the result obtained for aprotic solvents is of
the correct magnitude, but always too high.
EXAMPLE

Estimate the Debye relaxation time for nitromethane at 258C given that its
viscosity is 0.61 mPa s and assuming that its molecular diameter is 431 pm.

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

263

On the basis of equation (6.3.8),


tD

4p6:1  104 2:155  1010 3


1:86  1011 s
1:38  1023  298:2

6:3:10

This estimate of 19 ps is much larger than the experimental estimate of 4 ps,


which is obtained by applying the Debye model to dielectric relaxation data for
the pure solvent (see table 4.2). However, an approximate relationship between
tD and Zr3m is found when data for more solvents are considered, as shown
below.
The fact that estimates of tD are the correct order of magnitude suggests that
there is an approximate relationship between tD and Z, at least for liquids which
obey the Debye relaxation model (see section 4.5). This point is illustrated in g.
6.2 where tD is plotted against Zr3m with logarithmic scales for the aprotic solvents
listed in table 6.1. A very good correlation is found, conrming that equation
(6.3.9) is approximately correct. On the basis of a least-squares t for 14 solvents,
the relationship is
ln tD 5:4  103 0:91 lnZr3m

6:3:11

with a correlation coecient of 0.961. Addition of the data for the protic solvents
results in a much poorer t. This is not surprising because the value of tD for these
liquids reects the rotational diusion of hydrogen-bonded clusters, not that of
single molecules as assumed in the simple Debye model.
The simplest model for the temperature dependence of the viscosity is that
proposed by Arrhenius for a reaction rate constant which leads to the equation

Fig. 6.2 Plot on logarithmic scales of the Debye relaxation time tD for aprotic solvents
against the product Zr3m , where Z is the viscosity and rm , the molecular solvent radius.

264

LIQUIDS, SOLUTIONS, AND INTERFACES

HZ
Z A exp
RT


6:3:12

where HZ is the activation enthalpy associated with viscous ow and A, a preexponential factor. Values of HZ are also summarized for the polar solvents
considered here in table 6.1. Since the temperature dependence of tD is assumed to
have the same form (equation (4.7.1)) the analysis presented in g. 6.2 allows one
to relate HD and HZ for aprotic solvents. Assuming that rm is independent of
temperature, the relationship is
HD 0:91HZ

6:3:13

Comparison of the data in tables 4.2 and 6.1 shows that this is approximately
correct.
The discussion here has been directed to the viscosity of pure liquids. When an
electrolyte or other solute is added, the viscosity changes. Many data exist in the
literature for the viscosity of solutions. This subject is of special importance to
engineers interested in the ow properties of solutions. The discussion here is
meant to be only a brief introduction to the basic concepts. In the following
sections, attention is turned to the transport of solute species in solutions.

6.4 Isothermal Diffusion in Solutions


As seen in the earlier discussion of Onsagers theory (section 6.2), in the classical
approach diusion is a response to a concentration gradient. If species i is diusing then the ux of i is given by
Ji Di rci

6:4:1

where Di is the diusion coecient of i. This relationship is known as Ficks rst


law. It is most readily applied to describe a steady-state situation in which the ux
Ji is independent of time. Very often, the mass transfer problem involves conditions in which the local concentration is also a function of time. By applying the
equation of continuity with respect to mass one obtains the result
@ci
rJi Di r2 ci
@t

6:4:2

This is known as Ficks second law; it states that the time derivative of the
concentration at a given point in space is equal to the diusion coecient times
the Laplacian of the concentration. In deriving this equation it has been assumed
that the diusion coecient is independent of concentration.
In a simple situation the variation of concentration only occurs in one direction
in space. Then Ficks rst law becomes
Jxi Di

@ci
@x

6:4:3

where Jxi is the component of the ux in the x-direction. In one dimension, Ficks
second law is

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

@ci
@2 c
Di 2i
@t
@x

265

6:4:4

This is a second-order partial dierential equation whose solution gives the concentration of species i as a function of position and time, that is, of x and t.
As seen earlier, the dimensions of the diusion coecient in SI units are m2 s1.
Typical diusion coecients in aqueous solutions are the order of 1  109
m2 s1 . On the basis of Onsagers theory the quantity leading to the ux, that
is, the force should have the dimensions of Newtons. On the basis of classical
thermodynamics this is most directly achieved by writing Ficks laws in terms of
the chemical potential rather than the concentration. This means that Ficks rst
law becomes
Ji Li rmi

6:4:5

where rmi is the gradient of the chemical potential of species i, and Li , the
phenomenological coecient relating the ux to the force for the diusion process. In general, the chemical potential can be related to the activity of species i,
and thus to its concentration using the equation
mi mi0 RT ln ai mi0 RT ln yi ci

6:4:6

where ai is the activity on the concentration scale, yi , the activity coecient and
mi0 , the standard chemical potential. Combining equations (6.4.5) and (6.4.6), one
obtains
Ji Li RT r ln ai 

Li RT
rai
ai

6:4:7

If the solution is ideal (yi 1) or if the activity coecient is constant for the range
of concentrations involved in the experiment, then this equation becomes
Ji 

Li RT
rci
ci

6:4:8

It follows that the relationship between the Onsager phenomenological coecient


and the traditional diusion coecient is
Li

Di ci
RT

6:4:9

In many cases, for example, electrolyte solutions, the eects of solution nonideality must be considered. Then equation (6.4.7) can be written as
Ji Li RTr ln ci  Li RT r ln yi


Li RT
L RT r ln yi
rci  i
rc
ci
ci r ln ci i

6:4:10

It follows that the diusion coecient depends on the concentration of the diusing species according to the relationship
Di Di0 Di0

r ln yi
r ln ci

6:4:11

266

LIQUIDS, SOLUTIONS, AND INTERFACES

where Di0 is the diusion coecient in the ideal solution. In one dimension this
equation has the form
Di Di0 Di0

d ln yi
d ln ci

6:4:12

EXAMPLE

The diusion coecient of Na is 1:34  109 m2 s1 at innite dilution in


water at 258C. Estimate its value for a Na concentration of 0.1 M in a
solution of the same ionic strength. Use the extended DebyeHuckel theory
to estimate the concentration dependence of the activity coecient assuming
that the ion size parameter is 400 pm.
The activity coecient for the Na+ ion is given by
ln yi 

ADH z2i I 1=2


ADH ci1=2


1 BDH aI 1=2
1 BDH ac1=2
i

6:4:13

where I is the ionic strength, and the DebyeHuckel constants are ADH
1:174 M1=2 and BDH 3:288 M1=2 nm1 . The derivative of this quantity
with respect to ci is
d ln yi
0:5ADH ci1=2
0:5ADH BDH a


1=2
dci
1 BDH aci1=2 2
1 BDH aci

6:4:14

d ln yi
0:5ADH c1=2
0:5ADH BDH aci
i


1=2
d ln ci
1 BDH aci
1 BDH aci1=2 2

6:4:15

Thus,

Substituting into equation (6.4.15) for the case that ci is 0.1 M, the value of
d ln yi =d ln ci is 0:093.
Now, on the basis of equation (6.4.12), the diusion coecient for Na+ in
the 0.1 M solution is 1.22  109 m2 s1 .
In practice, conditions in a diusion experiment can be maintained such that
the activity coecient does not change signicantly with electrolyte concentration. For electrolyte solutions, this is done by adding an inert electrolyte whose
ions are not involved in the mass transfer process. Then, it can be assumed that
the ionic strength is constant and independent of position in the system.
Otherwise, the mass transfer problem becomes extremely dicult to solve and
requires information about the diusion coecient as a function of concentration.

6.5 Linear Diffusion from a Wall


In this section, a simple example of the solution of a mass transfer problem is
presented. When one solves dierential equations, it is very important to state the
boundary conditions clearly. In the present example, diusion takes place in the

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

267

positive x-direction into a solution, but half of the space is lled with a wall
extending in the minus x-direction for all values of y and z. The diusing material
or solute dissolves into the solution and its concentration at the wall is maintained
constant and equal to c0 . As a result the value of the concentration varies with
distance from the wall, x and with time, t. Since the system does not reach a
steady state, the partial dierential equation to be solved is
@c
@2 c
D 2
@t
@x

6:5:1

c cx; t

6:5:2

where
It is also assumed that the diusion coecient D is independent of location in the
solution (x > 0).
The boundary conditions with respect to x are
c0; t c0

6:5:3

c1; t 0

6:5:4

and
The second condition implies that diusion does not occur for a very long time, so
that the concentration far from the wall is zero. The boundary condition with
respect to time is
cx; 0 0

6:5:5

which states that the solute is not present anywhere in the solution initially. The
solution to equation (6.5.1) is obtained using the method of Laplace transforms.
Since there are two independent variables in the present problem, this means that
Laplace transformation must be performed twice, once with respect to the variable t, and then again with respect to the variable x. The Laplace transform of the
concentration with respect to time is given by (see appendix A)
1

cx; s

cx; test dt

6:5:6

The variable s now contains the information about the time dependence of the
problem. Applying Laplace transformation to the derivative on the right-hand
side of equation (6.5.1), one obtains
d 2c

dx2

@2 c st
e dt
@x2

6:5:7

Laplace transformation of the left-hand side is more dicult and requires use of
the product rule. In the present case, this gives
dc est est
Thus, one obtains

@c
 s est c
@t

6:5:8

268

LIQUIDS, SOLUTIONS, AND INTERFACES


1

1
1


@c st
st 
e dt ce  s c est dt sc
@t
0

6:5:9

Now the partial dierential equation has been transformed into an ordinary
dierential equation in c, namely
D

d2 c
sc
dx2

6:5:10

At this point, Laplace transformation is carried out with respect to x using the
relationship
1

c~u; s

cx; seux dx

6:5:11

The most dicult part of the solution involves transformation of the derivative on
the left-hand side of equation (6.5.10) which requires that the product rule be used
twice:
1

1
1

d2 c ux
dc ux 
dc ux
e
e dx
e
dx

u

dx
dx
dx2
0
0

1
1


dc0; s
uc eux  u2 c eux dx
dx
0

6:5:12

dc0; s
 uc0; s u2 c~

dx
Laplace transformation of the right-hand side gives
1

sc eux dx s c~

6:5:13

The result can be expressed as


Du2 c~  DAu  DB s c~

6:5:14

A c0; s

6:5:15

where

and
B

d c; 0; s
dx

6:5:16

Equation (6.5.14) is rearranged to obtain an expression for c~:


c~
where

DAu DB Au B
2
Du2  s
u  v2

6:5:17

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

v2

s
D

269

6:5:18

By using the method of partial fractions this result may be expressed as


c~

a
b

uv uv

6:5:19

where the constants a and b may be found by equating the numerators of equations (6.5.17) and (6.5.19) when equation (6.5.19) is in complex form. In other
words
au  v bu v Au B

6:5:20

From the coecients of u,


abA

6:5:21

vb  a B

6:5:22

and from the constant term,

At this point, the inverse Laplace transformation of equation (6.5.19) is carried


out. In order to do this, one must consult a table of Laplace transforms such as
the one given in appendix A. Operating on each term individually, one obtains


a
L1
a evx
6:5:23
uv
and
L

1


b
b evx
uv

6:5:24

As a result, the general expression for cx; s is


cx; s aevx bevx

6:5:25

Now, the boundary conditions with respect to x are applied so that the solution
specic to the problem addressed can be found. When x is innitely large, the
concentration goes to zero (equation (6.5.4)). The only way that this result is
obtained is by setting the constant b equal to zero. When x is equal to zero,
the concentration is constant and equal to c0 (equation (6.5.3)). Laplace transformation of this boundary condition with respect to time gives
1

c0 est dt 

1
c0 st 
c
e  0 c0; s
s
s
0

6:5:26

By comparing this result with equations (6.5.15) and (6.5.21), it is clear that a selfconsistent solution has been obtained. Thus, one may now write
cx; s

c0 vx
e
s

6:5:27

270

LIQUIDS, SOLUTIONS, AND INTERFACES

The nal step is to perform inverse Laplace transformation on cx; s to obtain


cx; t. Using the table of Laplace transformations, inverse transformation of
equation (6.5.27) results in


x
cx; t c0 erfc
6:5:28
4Dt1=2
where erfc is the error function complement.
The error function of the parameter z is dened as
z
2
2
erfz 1=2 ey dy
p

6:5:29

This function corresponds to the area under the normal error distribution curve
from its maximum value to a value z. The error function has a value of 0 when z is
zero, and a value of one when z is innity. The error function complement is
simply dened as
erfcz 1  erfz

6:5:30

This function goes from one to zero.


The nal result in equation (6.5.28) shows that the concentration falls from its
initial value of c0 at the wall in a manner determined by the error function and the
diusion coecient D. Typical concentration proles estimated at various values
of t are shown in g. 6.3. Obviously, the concentration increases at a given
distance from the wall as time increases.
It is also useful to calculate the ux of the diusing species using Ficks rst
law:
Jx; t D

@cx; t
@x

6:5:31

Fig. 6.3 Typical concentration proles estimated for various times for diusion from a
semi-innite wall with D 1  109 m2 s1 .

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

271

This can be done by dierentiating equation (6.5.28) with respect to x, and


requires that the rst derivative of the error function be estimated. On the basis
of equation (6.5.29),
2 dz
d erfz
2
1=2 ez
dx
dx
p

6:5:32

d erfcx=2Dt1=2  expx2 =4Dt

dx
pDt1=2

6:5:33

!
 1=2
D
x2
Jx; t c0
exp
pt
4Dt

6:5:34

 1=2
D
J0; t c0
pt

6:5:35

It follows that

Thus,

At the wall, the ux is

This is an important result used in electroanalytical chemistry.


The importance of the boundary conditions in obtaining a solution to Ficks
equation is apparent from the example presented here. This equation has been
solved for many dierent situations, including cylindrical and spherical geometries [G2, G3]. It has often been applied to mass transfer problems in electroanalysis and important examples can be found in monographs devoted to this
subject [G4].

6.6 The Electrochemical Potential


When mass transfer occurs in electrolyte solutions, the component ions can move
independently of one another. Because of the ionic charge, the Gibbs energy of an
ion depends not only on its local concentration but also on the local electrostatic
potential. It is also necessary to consider circumstances in which changes in the
local potential are brought about by application of an external eld. Thus, it is
important to be able to deal with the chemical and electrostatic contributions to
the Gibbs energy separately. The thermodynamic tool for achieving this is the
electrochemical potential.
The electrochemical potential of charged species i, m~ ai is dened as the work
done when this species is moved from charge-free innity to the interior of a
homogeneous phase a which carries no net charge [6]. The opposite process is
known as the work function and is familiar for the case of removal of an electron
from a metal. In fact, the work function for single ions in electrolyte solutions can
also be measured experimentally, as described in detail in chapter 8. This means
that the electrochemical potential is an experimentally determinable quantity.
However, separation of the electrochemical potential into chemical and electrostatic contributions is arbitrary, even though it is conceptually very useful.

272

LIQUIDS, SOLUTIONS, AND INTERFACES

A very helpful way of understanding the contributions to m~ ai has been described


by Parsons [6]. It is imagined that phase a, for example, an electrolyte solution, is
a sphere isolated in free space (g. 6.4). This sphere is divided into two regions, a
central spherical region where the distribution of ions and solvent molecules
reects the homogeneous nature of the bulk, and a thin spherical shell at the
surface which contains the interfacial double layer and any excess surface charge
associated with phase a. The double layer at the aqueous electrolyte solution|air
interface is due to any net orientation of water molecules at the surface, and to the
fact that hydrated cations and anions may have dierent distances of closest
approach due to diering degrees of hydration. Electrolyte solutions do not normally possess excess charge, but this could easily be the case if phase a were a
metal.
Now, the two parts of phase a are separated (g. 6.4) and the process of
introducing a charged species to each part repeated. The work done in the case
of the homogeneous phase a is the chemical potential mai . On the other hand, the
work done in moving the charged particle through the surface shell into the empty
interior is associated with the electrostatic characteristics of phase a and is written
as zi Ffa . fa is called the inner potential of phase a, and cannot be measured for
an isolated phase. This fact can be understood from the point of view that one is
only able to measure a potential dierence in electrostatics. One is also not able to
measure the chemical potential of a single charged species, for example, a single
ion. On the other hand, one is able to determine the chemical potential of a
neutral electrolyte in which the charges on the individual ions add to zero.
As a result of the thought experiment described above, the expression for the
electrochemical potential of species i in phase a is
m~ ai mai zi Ffa

6:6:1

For a simple 11 electrolyte MX, the electrochemical potential of the cation is


m~ aM maM Ffa

6:6:2

m~ aX maX  Ffa

6:6:3

and that of the anion

Fig. 6.4 Schematic representation of the


division of the electrochemical potential of
species i in phase a into chemical and electrical
contributions.

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

273

The electrochemical potential of the electrolyte is


m~ aMX m~ aM m~ aX maM maX maMX

6:6:4

Thus, the distinction between the electrochemical potential and the chemical
potential is lost when the properties of the electrolyte as a whole are considered.
The development of the thermodynamic properties of the electrolyte are those
discussed earlier in section 3.6.
The inner potential is an important property of individual phases. Much more
will be said about this property when the interface between two phases is discussed in chapter 8. For the moment, fa is regarded as a property of phase a
which is the same throughout the phase with a value dened with respect to
charge-free innity. On the other hand, in the case of an electrolyte solution,
the local electrostatic potential varies from point to point due to the presence
of discrete charges on the ions. Thus the electrostatic potential is more positive at
a cation and more negative at an anion. These uctuations occur about the
average value, fa . This can be seen more clearly by writing out the chemical
potential of ion i in terms of its concentration ci and activity coecient yi .
Thus, from equation (6.6.1)
m~ ai mai0 RT ln yi ci zi Ffa

6:6:5

The activity coecient is directly related to the work done to create the ionic
atmosphere around ion i, so that this equation can also be written as
m~ ai mai0 RT ln ci zi Fai

6:6:6

ai

is the micropotential or local potential experienced by this ion (see


where
section 3.8). The relationship between fa and ai is
ai fa ia

6:6:7

where ia is the discreteness-of-charge potential. On the basis of this denition, ia


is the dierence between the local potential and its average value which arises
because the charge in the solution is localized on ions. The discreteness-of-charge
potential may be expressed in terms of two contributions as follows:
a
a
zi F ia zi F self
zi F atm

6:6:8

a
self

is the self-potential of the ion which depends on its radius and the dielectric
a
, is the self atmosphere potential due to the
properties of the medium, and atm
ionic cloud formed around ion i. The latter quantity is directly related to the
activity coecient yi as follows:
a
RT ln yi zi F ;atm

6:6:9

Since the self-potential of ion is not included in the denition of yi , the standard
states in equations (6.6.5) and (6.6.6) are not the same (see section 3.8).
The concept of the electrochemical potential is also helpful in analyzing
changes in the Gibbs energy of dipoles and multipoles when the electrical environment is changed. In the case of a dipole, the electrostatic energy is determined
by the local eld Ee . The local eld can change due to a change in environment or

274

LIQUIDS, SOLUTIONS, AND INTERFACES

the imposition of the eld from an external electrical source. A well-known example of an environmental change occurs when a dipolar molecule is adsorbed at an
interface. Under these circumstances the local eld can be quite dierent, so that
the electrostatic contribution to the Gibbs energy changes signicantly.
The electrochemical potential of a dipolar molecule may be written as
m~ ai mai0 RT ln ai pi  Ee

6:6:10

where ai is the activity of molecule i, pi , its dipole moment, and Ee , the local eld.
The electrostatic energy is expressed as a vector dot product because the angle
between the vectors must be known in order to estimate it. An example of the
application of dipolar electrochemical potentials is given in chapter 10.
Discussion of non-equilibrium processes involving ions in terms of the micropotential is especially helpful because it focuses attention on the fact that major
source of non-ideality in these systems is electrical in character. The arbitrary
nature of the separation of the electrochemical potential into chemical and electrical contributions has often been pointed out in the literature. In fact, chemical
interactions are fundamentally electrical in nature. However, the formal separation discussed here is conceptually important. Its usefulness becomes clear when
one tackles problems related to the movement of ions in electrolyte solutions
under the inuence of concentration and electrostatic potential gradients. These
problems are discussed in the following section.

6.7 The Conductivity of Electrolyte Solutions


Electrolyte solutions contain ions which can move in response to a gradient in
electrical potential. The transport properties of these systems are important in
devices such as batteries and in living systems. The movement of ions in solution
is very dierent from the movement of electrons in metallic conductors, and it is
important to understand the fundamental laws which govern the conductivity of
electrolyte solutions. Ions move according to the classical laws of physics, whereas
the movement of electrons is quantal.
The force governing the movement of ions is the local gradient of the electrostatic potential, ri . If eects due to the presence of an ion at a given point in the
solution and other ions surrounding it are ignored, and only the macroscopic
potential gradient is considered, then ri can be replaced by rf. Local electrostatic eects are generally considered to be the major source of non-ideality in
electrolyte solutions at equilibrium. In the classical treatment of conductivity all
eects due to non-ideality are included in the phenomenological coecients,
namely, the mobility and the molar conductance discussed below. The ux of ion
i is normally written in terms of the current density, ii . Recalling that ux has units
of moles per square meter per second, the corresponding current density is given by
ii zi FJi

6:7:1

where zi is the valence of ion i. The total current density which is observed
experimentally is the sum of the contributions from each ion:

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

zi FJi

275

6:7:2

Since cations and anions move in opposite directions under the inuence of an
electrical eld, the vector JM for a cation is in the opposite direction to that for an
anion JX . This means that the ux Ji multiplied by the ionic valence zi has the
same sign for all ions; as a result each ion contributes to the solution conductivity
in such a way that it becomes larger.
The phenomenological coecient relating the current density and the macroscopic potential gradient is the conductivity due to the ion, ki . Thus, one has the
general relationship
ii ki rf

6:7:3

The minus sign reects the fact that a positive ion moves in the direction opposite
to the increase in electrical potential. If rf is positive, the electrical potential
increases in a specied direction, for instance the x-direction, but a cation
moves in the opposite direction. This equation is a special form of Ohms law
written in terms of the current density and the potential gradient, rather than the
current and the potential dierence. The experimentally measured quantity is the
conductivity ke , which is the sum of the contributions from each ion in solution:
X
ke
ki
6:7:4
i

In order to measure the conductivity of an electrolyte solution, a special cell is


constructed in which the two electrodes of accurately known dimensions are
placed at a known distance from one another (g. 6.5). The electrodes are usually
made of an inert material such as platinum. If a d.c. voltage is applied to such a
cell, no current ows until a certain minimum value is reached. Below this minimum, no reactions occur at the electrodes, and the electrode|solution interface
behaves as a capacitor. When d.c. current ows, reactions occur at each electrode
and ions move in the electrolyte solution. The nature of the reactions depends on
the nature of the electrolyte but certainly the component ions are involved in these
reactions. For this reason, d.c. experiments are not used in the precise determination of solution conductivity. On the other hand, if an a.c. voltage of low amplitude is applied to the cell, its conductivity may be determined in the absence of
any net change in the composition of the solution. Traditionally, this experiment
was carried out by making the conductance cell one arm of an a.c. Wheatstone
bridge designed to measure resistance.

Fig. 6.5 Schematic diagram of


a conductivity cell (a) and its
impedance representation as an
equivalent circuit (b).
Capacitances C1 and C2 are at
the electrode|solution

276

LIQUIDS, SOLUTIONS, AND INTERFACES

The relationship between the solution resistance Rs and the conductivity ke is


ke

d
Rs A

6:7:5

where d is the separation between the plates of the conductivity cell and A is the
area of the electrodes. The units of ke are 1 m1 . In order to estimate ke from
the experimental value of the resistance, the cell parameters d and A must be
carefully determined. In practice, the ratio d=A is found by calibrating the conductivity cell with a solution of known conductivity.
Another important parameter related to electrolyte solution conductivity is the
transport number ti . This is dened as the fraction of the current carried by
species i. On the basis of equation (6.7.4), it is clear that ti is given by
ti

ki
ke

6:7:6

The classical way of measuring transport numbers is in a Hittorf cell, which is


illustrated schematically in g. 6.6. The cell consists of three compartments designated L (left), M (middle), and R (right). In the present example the two electrodes are composed of pure copper, and the electrolyte is an aqueous solution of
Cu(NO3)2. Direct current ows through the cell, and the amount of charge which
passes through the system, q, is measured by the coulometer in the circuit.
For the example chosen, the reaction at electrode L, which is the cathode, is
Cu2 2e !Cu

6:7:7

This is accompanied by the transport of Cu2 ions into L and transport of NO
3
ions out of L. The net change in number of moles of Cu2 ion in compartment L
is

Fig. 6.6 Hittorf cell for determining transport


numbers with associated circuitry. Circuit element C
is a coulometer. The three compartments are labeled
L (left), M (middle), and R (right).

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

nL Cu2 

q
t q
t q
 
2F 2F
2F

277

6:7:8

Since there are only two kinds of ions, the fractions t and t must add to unity.
The number of moles of NO
3 ion moving out of L is
nL NO
3 

t q
F

6:7:9

Since each nitrate ion has a charge of 1, the number of moles is obtained by
dividing the charge moved by the Faraday constant F. Thus, the total change in
the number of moles of Cu(NO3 2 is t q=2F with the requirement of electroneutrality being maintained.
The reaction at the anode R is the opposite, namely
Cu!Cu2 2e

6:7:10

In this compartment, Cu2 ion is transported out and NO


3 ion moves in.
Analysis of the next changes leads to the result
nR Cu2

nR NO
t q
3

2
2F

6:7:11

The net change in the middle compartment is zero. By analyzing the contents
of each compartment after passing a known charge q through the system, the
transport numbers t and t can be calculated.
Two other quantities are commonly used in discussing the transport properties
of electrolytes. The rst is the molar conductivity of ion i, which is dened as
li

ki
ci

6:7:12

where ci is the concentration of the ion. In order to obtain reasonable dimensions


for li , the concentration is expressed in mol m3 so that li has units of 1 m2
mol1 . As the concentration of ion i increases one expects the conductivity of the
solution to increase as well. To a rst approximation, this increase should be
proportional to the change in concentration, so that li is a constant. In fact, li
decreases with increase in electrolyte concentration as a result of the eects of
non-ideality. This observation is discussed in detail in the following section.
Another way of presenting information about the concentration dependence of
ki is in terms of the equivalent conductance dened as
l i

ki
jzi jci

6:7:13

One equivalent of ion i is the amount which contains one mole of univalent
charge. This quantity is often found in the older literature.
Another important parameter used to discuss the transport properties of electrolytes is the ionic mobility, ui . This is the velocity of the ion in a unit electrical
eld. It can be found from the molar conductivity by dividing it by the charge on a
mole of ions:

278

LIQUIDS, SOLUTIONS, AND INTERFACES

ui

li
jzi jF

6:7:14

Dimensional analysis shows that ui has units of m2 V1 s1 in the SI system. It
is also useful to relate ui to the conductivity of the solution. Combining equations
(6.7.4), (6.7.12), and (6.7.14), one obtains
X
ke
jzi jF ui ci
6:7:15
i

EXAMPLE

The molar conductance of 0.5 M MgCl2 in water is 165.52 cm2 mol1 1 at
258C. The cationic transport number is 0.308 at this concentration. Estimate
the molar conductances of the individual ions. Also estimate the ionic mobilities.
The molar conductance for Mg2 is given by
lMg2 0:308  165:52 50:98 cm2 mol1 1
For the Cl ion,
lCl

1  0:308  165:62
57:27 cm2 mol1 1
2

Using equation (6.7.14), the mobility of Mg2 is


uMg2

50:98
2:64  104 cm2 s1 V1
2  96;485

and that of Cl is


uCl

57:27
5:94  104 cm2 s1 V1
96;485

The Mg2 ion is much more strongly solvated by water molecules than Cl .
Thus, it moves with more water molecules and its mobility is much less.
The relationship between ionic conductivity and Onsagers theory can now be
presented in terms of the electrochemical potential. By expressing the force leading to the transport of ions in terms of the gradient of m~ i , one nds important
relationships between the diusion coecients of the ions, and the molar conductivity and mobility. Furthermore, when the force has the correct Newtonian
units, one is also in a position to calculate the rate of entropy production. On the
basis of the thermodynamics of irreversible processes, the relationship between
the ux of ion i and the force rm~ i is
Ji Li rm~ i

6:7:16

where Li is the appropriate phenomenological coecient. Using equation (6.6.5),


this can be written as


L RT
r ln yi
1
6:7:17
rci  Li zi Frf
Ji  i
ci
r ln ci

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

279

The factor in front of rci is simply the diusion coecient Di (equation (6.4.10)).
Now, using equations (6.7.1) and (6.7.3), the contribution to the ux from the
potential gradient may be expressed in terms of the molar conductivity. The result
is
k
6:7:18
Ji Di rci  i rf
zi F
Since
ki jzi jF ui ci

6:7:19

the ux of ion i can also be written as


Ji Di rci 

z i ui c i
rf
jzi j

6:7:20

Comparing equations (6.7.17) and (6.7.20), one nds that


Li

Di ci
uc
i i
RT jzi jF

6:7:21

In the limit of innite dilution, where the eects of non-ideality are absent, one
obtains the Einstein relationship between these parameters for a single ion:
Di0

RT
u
jzi jF i0

6:7:22

The subscript 0 designates the values of Di and ui in the innitely dilute limit.
A typical mobility for an ion in water is 5  108 m2 s1 V1 . For a monovalent
ion, the corresponding diusion coecient at 258C is 1:3  109 m2 s1 .
The diusion coecient of an individual ion may also be related to its molar
conductance. Making use of equation (6.7.14), one may write
li0 jzi jui0 F

z2i F2 Di0
RT

6:7:23

For the whole electrolyte, the limiting molar conductivity is


i0 n l0 n l0

F2
n z2 D n z2 D0
RT 0

6:7:24

where n and n are the stiochiometric numbers of the cation and anion, respectively. This is known as the Nernst-Einstein equation.
Another important relationship relevant to the mobility of ions may be derived
from Stokes law. If it is imagined that the ion is a sphere moving through a
solvent of viscosity Z at a constant velocity vi , then the force due to the electrical
eld is exactly counterbalanced by the force due to the viscous drag. The electrical
force is the ionic charge zi e0 times the electrical eld E. Thus, using equation
(6.3.5), one may write
jzi je0 E 6pZri vi

6:7:25

280

LIQUIDS, SOLUTIONS, AND INTERFACES

The ratio of vi to E is simply the ionic mobility ui so that


jz je
ui i 0
6pZri
In terms of the diusion coecient, one obtains
kT
Di
6pZri

6:7:26

6:7:27

This relationship is known as the StokesEinstein equation. Strictly speaking it


should only be applied at innite dilution to monoatomic ions. However, in
practice it is applied to more complex ions and at nite ionic strengths. If the
diusion coecient for the ion is measured experimentally, an eective radius for
the ion can be estimated using the viscosity of the pure solvent.
EXAMPLE

Using the data given in the previous example and in table 6.1, estimate the
diusion coecients for Mg2 + and Cl in 0.5 M MgCl2 . Estimate also their
eective Stokes radii.
The mobility of Mg2 is 2:64  104 cm2 s1 V1 . The diusion coecient is
equal to
0:0257
3:39  106 cm2 s1
DMg2 2:64  104 
2
Using equation (6.7.27), the Stokes radius for this ion at 258C is
kT
4:11  1021

6pZDi 6p  8:9  104  3:39  106  104


7:24  1010 m 724 pm

ri

For Cl , the diusion coecient is


DCl 5:94  104  0:0257 1:527  105 cm2 s1
The Stokes radius is
ri

4:11  1021
1:60  1010 m 160 pm
6p  8:9  104  1:527  109

The results for the Stokes radii are reasonable but they should have been
obtained using the viscosity of the solution, not that of the pure solvent.
Unfortunately, the necessary data are usually not available.
At nite concentrations, the uxes of the ions of the electrolyte are not completely independent of one another because of ionion interactions. This can be
seen clearly when this phenomenon is examined within the context of Onsagers
treatment of ion transport. It is assumed in the following that the electrolyte MX
contains two univalent ions. The ux of the cation is
JM LMM rm~ M  LMX rm~ X

6:7:28

where rm~ M and rm~ X are the gradients of the electrochemical potentials of the
cation and anion, respectively, LMM , the phenomenological coecient describing

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

281

the ux of the cation resulting from rm~ M and LMX , that describing the ux of the
cation resulting from rm~ X . The cross-coecient LMX is expected to be much
smaller than the principal coecient LMM , but both must be considered in a
general treatment. For the anionic ux, the corresponding expression is
JX LXM rm~ M  LXX rm~ X

6:7:29

where LXX is the principal phenomenological coecient for the anion, and LXM ,
the cross-coecient. Because of the principle of microscopic reversibility, the
coecients LMX and LXM are equal. This means that three phenomenological
coecients must be determined in order to obtain the transport properties of
the system. In terms of traditional treatments, the three quantities determined
experimentally at a given electrolyte concentration are the diusion coecient
of the electrolyte and the mobilities of each ion. By examining the experiments
used to determine each of these quantities on the basis of the Onsager treatment,
the relationships among LMM , LMX , LXX , and the traditional parameters can be
obtained.
In a conductivity experiment, the conductance is determined in the absence of a
concentration gradient by using an a.c. potential gradient rfac so that the force
on ion i is zi F rfac . Thus, the ionic uxes in this experiment are
JM zM LMM F rfac  zX LMX F rfac

6:7:30

Jx zM LMX F rfac  zX LXX F rfac

6:7:31

and

Using equation (6.7.2) the a.c. current density for a 11 electrolyte is


iac FJM  FJX F2 LMM  2LMX LXX rfac

6:7:32

Thus, according to equations (6.7.3) and (6.7.4), the conductivity of the solution is
k F2 LMM  2LMX LXX

6:7:33

Expressions may also be written for the transport numbers tM and tX using the
above analysis:
tM

FJM
LMM  LMX

iac
LMM  2LMX LXX

6:7:34

and
tX 

FJX
LXX  LMX

iac
LMM  2LMX LXX

6:7:35

As required by the denition of the transport numbers, tM and tX add to unity.


When diusion occurs in an electrolyte solution in the absence of an external
electrical eld, local electrical neutrality must be maintained. When rf is zero, the
ionic uxes are
JM LMM rmM  LMX rmX
and

6:7:36

282

LIQUIDS, SOLUTIONS, AND INTERFACES

JX LMX rmM  LXX rmX

6:7:37

The net electrical current in the solution must be zero so that


FJM  FJX 0

6:7:38

LMM  LMX rmM LXX  LMX rmX

6:7:39

It follows that

The gradient of the chemical potential of the electrolyte is given by


rme rm~ M rm~ X rmM rmX

6:7:40

Combining equations (6.7.39) and (6.7.40), one nds after some straightforward algebra that
rmM

LXX  LMX
rm
LMM  2LMX LXX e

6:7:41

rmX

LMM  LMX
rm
LMM  2LMX LXX e

6:7:42

and

Now, using equations (6.7.36) and (6.7.37), one nds that


JM JX 

LMM LXX  L2MX


rm
LMM  2LMX LXX e

6:7:43

The ux of each ion is also equal to the overall ux of the electrolyte Je when
electroneutrality is maintained. The relationship between this quantity and rce is
Je De rce

6:7:44

where De is the overall diusion coecient of the electrolyte. The relationship


between rme and rce is
rme RTr ln ae

RT

rc
ce e e

6:7:45

where

e 1

r ln ye
r ln ce

6:7:46

This leads to the nal result that


De

RT
LMM LXX  L2MX

e
ce
LMM  2LMX LXX

6:7:47:

Equations (6.7.33), (6.7.45), and (6.7.34) or (6.7.35) form a system of three


equations in three unknowns which may be solved for the individual phenomenological coecients LMM , LMX , and LXX . The results are
LMM

De ce ke t2M
2
RT
e
F

6:7:48

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

LMX

283

De ce ke tM tX

RT
e
F2

6:7:49

De ce ke t2X
2
RT
e
F

6:7:50

and
LXX

The non-ideality of the electrolyte solution leads to complex relationships


between the phenomenological coecients and the transport parameters measured experimentally. These only become simple in the limit of innite dilution
where LMX goes to zero and
e to unity. For example, under these conditions
equation (6.7.47) reduces to
De0

RT LMM LXX
ce LMM LXX

6:7:51

Since the diusion coecients for the individual ions can be dened from LMM
and LXX using equation (6.7.21), one may write
De0

DM0 DX0
DM0 DX0

6:7:52

where DM0 and DX0 are the diusion coecients for M and X , respectively, at
innite dilution. This equation was rst derived by Nernst.
As can be seen from the above development, study of the transport properties
of electrolyte solutions led scientists in the late nineteenth and early twentieth
centuries to think about these systems on a microscopic scale. Important connections between the movement of ions under the inuence of thermal and electrical
eects were made by Einstein. This was all brought together in an elegant way by
Onsager. An important question faced by those involved with these studies is
whether the electrolyte is completely dissociated or not. The answer to this question can be found be examining both the equilibrium and non-equilibrium properties of electrolyte solutions. The latter aspect turns out to be more revealing and is
discussed in more detail in the following section.

6.8 Experimental Studies of Conductivity


The study of electrolyte conductivity dates from the latter half of the nineteenth
century when it was realized that simple salts dissociate into ions in aqueous
solution. Furthermore, when a current ows in such a solution, the cations
move to a large extent independently of the anions, resulting in two separate
vectorial components with positive charge moving in one direction and negative
charge in the opposite. These studies showed that the molar conductivity varies
with electrolyte concentration. In addition, it was possible to distinguish two types
of behavior, namely, that characteristic of strong electrolytes, and that characteristic of weak electrolytes.
Many of the careful early experiments were carried out in the laboratory of
Kohlrausch who showed that the conductivity of solutions of dilute strong elec-

284

LIQUIDS, SOLUTIONS, AND INTERFACES

trolytes was linear in the square root of the electrolyte concentration. The
Kohlrausch result may be expressed as
0  ke c1=2
e

6:8:1

where 0 is the molar conductance at innite dilution and ke , the slope of the
relationship between and c1=2
e . Examples of the conductivity behavior of several
electrolytes are shown in g. 6.7. In all cases, the conductivity decreases as the
concentration increases. This can be understood as an eect of the ionic environment on the motion of individual ions. Three of the electrolytes shown in g. 6.7,
namely, NaCl, KCl, and sodium acetate (NaC2 H3 O2 ) show the behavior predicted by equation (6.8.1). Thus, the conductivity is linear in the square root of
the concentration in the limit of low concentrations so that these systems can be
classied as strong electrolytes. Extrapolation to zero concentration is easily carried out, so that values of 0 can be estimated. In the case of acetic acid, a weak
electrolyte, the behavior is quite dierent and the value of 0 is impossible to
obtain on the basis of the Kohlrausch plot.
The second important parameter obtained directly from experiment is the
transport number for one of the ions of the electrolyte. On the basis of the
analysis in section 6.7, the cationic transport number for a 11 electrolyte can
be written as
t

l
u

l l u u 

6:8:2

where li is the molar conductivity of ion i, and ui , its corresponding mobility. If it


is assumed that the individual ionic molar conductivities are also given by an
equation similar to equation (6.8.1), then one may write

Fig. 6.7 Plots of the molar conductivity against the square root of the electrolyte concentration for three strong electrolytes (*) and one weak electrolyte (^). The data for the
strong electrolytes were tted to a straight line at lower concentrations in order to obtain
the limiting molar conductivity 0 .

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

li li0 1 

ki c1=2
e
li0

285

6:8:3

where ki is the constant describing the concentration dependence of li for ion i.


Substituting this expression for each molar conductivity into (6.8.2), the following
expression is obtained for the concentration dependence of t at low concentrations:
t t0 kt c1=2
e

6:8:4

t0 is the transport number in the limit of innite dilution, and kt , the constant
describing the concentration dependence of t . The sign of kt can be positive or
negative depending on the relative values of the corresponding coecients for the
constituent ions, k and k . Since the transport numbers t and t add to unity,
the corresponding equation for t is
t t0  kt c1=2
e

6:8:5

Typical transport number data for 11 electrolytes are shown as a function of c1=2
e
in g. 6.8. It is clear that these data can easily be extrapolated to obtain the value
of the transport number at innite dilution.
Having obtained the limiting conductance for an electrolyte and the limiting
transport number for one of its ions, one may calculate limiting molar conductivities for the individual ions. Examination of experimental data for strong electrolytes shows that l0 for a single cation, say Na , is independent of the nature of
the anion. Similarly, for a series of electrolytes with a common anion, say Cl , the
value of l0 is independent of the nature of the cation. Thus, by selecting contributions from the appropriate ions one can calculate the limiting ionic conductance for any electrolyte whose constituent ions are listed in table 6.2. For

Fig. 6.8 Plots of the cationic transport number 258C against the square root of the electrolyte concentration for three strong electrolytes in water.

286

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 6.2 Limiting Molar Conductivities of Single Ions


in Water at 258C [7]*
Cation

li0 =cm2 mol1 1

H
Li
Na
K
Rb
Cs
Ag
NH
4
Mg2
Ca2
Sr2
Ba2
Cd2
Zn2
Ni2
Pb2

349.8
38.68
50.10
73.50
77.81
77.26
61.90
73.55
106.1
119.0
118.9
127.3
108.0
107.0
108.0
140.0

Anions
OH
F
Cl
Br
I
NO
3
ClO
4
C2 H3 O
2

N3
CN
SCN
SO2
4
CO2
3
C2 O24
Fe(CN)3
6
Fe(CN)4
6

li0 =cm2 mol1 1


198.3
55.4
76.35
78.14
76.84
71.46
67.36
40.90
69.5
78.0
66.5
160.04
138.6
148.3
302.7
442.0

*In the older literature, the limiting conductance is usually given per
equivalent of the ion rather than per mole as cited here. The equivalent
conductance is equal to the molar conductance divided by the number
of charges on the ion. Thus, the equivalent conductance for the divalent
cations listed above is equal to the molar conductance divided by two.

example, in the case of Zn(ClO4 )2 , there is a contribution of 107.0 cm2 mol1 2
from the Zn2 ion, and a contribution of 134.7 cm2 mol1 1 from the two
perchlorate ions. These add to a value of 0 equal to 241.7 cm2 mol1 1 for the
electrolyte. The same data can be used to estimate the limiting ionic conductivity
for a weak electrolyte. In the case of acetic acid the result is 390.7 cm2 mol1 1 .
Examination of the data for this system presented in g. 6.7 shows that the value
of changes markedly at low concentrations, so that 0 clearly could not be
estimated on the basis of the Kohlrausch plot.
The limiting molar conductance is a fundamental property of ions in electrolyte
solutions. It can be used to estimate the ionic mobility (equation (6.7.14)) and the
diusion coecient of the ion (equation (6.7.22)) in the limit of innite dilution.
When data are available for ions in a given series, trends can be seen in the values
of li0 . In the case of the alkali metal cations, l0 increases with increase in cation
atomic number up to Rb , the values for Rb and Cs being approximately the
same. A similar trend is seen for the halide ions for which l0 increases in the
series F < Cl < Br , and then decreases slightly for I . These results are
usually interpreted in terms of the extent to which the ion is solvated in water.
Since Li is the smallest crystallographic radius in the alkali metal series, it is the
most strongly hydrated and carries some surrounding water molecules when it
moves. On the other hand, the large Cs ion is only weakly hydrated, and therefore, it can move more rapidly through the electrolyte solution.
The concepts that ions move independently and that the individual ionic limiting conductivities can be used to estimate the limiting conductivity of an electro-

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

287

lyte were major achievements in developing an understanding of the properties of


electrolyte solutions. However, many studies were also made with weak electrolytes which are only partially dissociated. The concentration behavior of these
systems, for example, acetic acid (see g. 6.7), is clearly dierent. When a simple
11 electrolyte is only partially dissociated one has the equilibrium
MX M X

6:8:6

whose equilibrium constant is


Ka

aM aX
y2 a2 ce

aMX
yMX 1  a

6:8:7

ai is the activity of species i, yi , the corresponding activity coecient, ce , the


concentration of the weak electrolyte and a, the fraction of the electrolyte
dissociated. Dening Kc as the equilibrium constant in terms of concentration,
one may write
Kc

yMX Ka
a 2 ce

1a
y2

6:8:8

Kc will be constant only in the limit of very low concentrations where the activity
coecients are unity. The second assumption regarding weak electrolytes is that the
fraction dissociated can be directly obtained from the ionic conductivity, that is,
a

6:8:9

Combining equations (6.8.8) and (6.8.9), and writing the result in a linear form,
one obtains
1
1
c

e
0 Kc 20

6:8:10

This is the Ostwald dilution law for weak electrolytes.


Plots of data for two weak electrolytes, namely acetic acid and ammonium
hydroxide, according to Ostwalds law are shown in g. 6.9. These plots give
reasonable straight lines with somewhat more scatter in the case of NH4OH.
The value of 0 for acetic acid from the intercept is 388.5 cm2 mol1 1 ,
which agrees quite well with the value calculated from the limiting ionic conductivities in table 6.2 (390.7 cm2 mol1 1 ). The value of Kc estimated from the
slope is 7:8  105 M, which is close to the value found in tabulations of acidity
constants. In the case of NH4OH, the estimate of 0 from the intercept is 115.9
cm2 mol1 1 , which is very dierent from the value obtained from limiting
conductances (271.4 cm2 mol1 1 ). The estimate of Kc from the slope is 7:8 
105 M compares with 1:8  105 M from basicity constant tabulations. These
calculations show the weakness of the Ostwald analysis. Since 0 is much larger
than the measured conductances, the error associated with estimating it from its
reciprocal in the plots shown is very large. Any error in 0 is then reected in the
estimate of the Kc which comes from the reciprocal of the slope, equal to Kc 20 .
An additional problem comes from the neglect of the activity coecients involved

288

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 6.9 Plot of 1/ at 258C against ce for two weak electrolytes, namely, acetic acid (^)
and NH4 OH (*).

in the thermodynamic association constant Ka . Robinson and Stokes [7] have


described an iterative technique for extracting values of 0 and Ka , which includes
consideration of activity coecients for the constituent ions on the basis of the
DebyeHuckel law. This technique is useful when highly precise conductivity data
are available.
Many studies of electrolyte conductivity have been carried out [7]. This work
certainly helped to conrm modern ideas about electrolyte solutions. One aspect
of the behavior of strong electrolytes which was initially not well understood is the
fact that their molar conductance decreases with increase in concentration.
Although this is now attributed to ionion interactions, early work by
Arrhenius [8] ascribed the decrease in all electrolytes to partial dissociation.
However, it is clear from the vast body of experimental data that one can distinguish two types of behavior for these systems, namely, that for strong electrolytes
and that for weak electrolytes, as has been illustrated here. The theory of the
concentration dependence of the molar conductance of strong electrolytes was
developed earlier this century and is discussed in detail in the following section.

6.9 The DebyeOnsager Model for Conductivity


In chapter 3, it was shown that the DebyeHuckel theory for ionion interactions
is able to account for solution non-ideality in very dilute systems. The same model
forms the basis for understanding the concentration dependence of the conductance observed for strong electrolytes. Thus, Onsager [9] showed in 1927 that the
limiting conductance law for 11 electrolytes has the form
0  B1 0 B2 c1=2
e

6:9:1

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

289

where B1 and B2 are constants whose signicance is discussed below. The success
of the DebyeOnsager theory is that it is able to account quantitatively for the
behavior observed empirically by Kohlrausch at low concentrations (equation
(6.8.1)).
The inuence of the interionic forces is due to two phenomena, namely, the
electrophoretic eect and the time-of-relaxation eect. The net ionic atmosphere
around a given ion carries the opposite charge and therefore moves in a direction
opposite to the central ion. The nal result is an increase in the local viscosity, and
retardation of the central ion. This is called the electrophoretic eect. The time-ofrelaxation eect is also related to the fact that the ionic atmosphere around a
given ion is moving and therefore disrupted from its equilibrium conguration. It
follows that the ionic atmosphere must constantly be re-formed from new counter
ions as the ion under observation moves through the solution. The net eect is
that the electrical force on each ion is reduced so that the net forward velocity is
smaller.
The derivation of an expression for the electrophoretic eect is based on the
DebyeHuckel theory described earlier in section 3.8. On the basis of the
Boltzmann distribution law, the local concentration of ion i at a distance r
from a central reference ion j is
cri c i expzi f

6:9:2

c i

where
is the average concentration of ion i, zi , its valence, and , the local
potential. Expanding the exponential as an innite series in zi f, the following
expression is obtained for the deviation of the local concentration from its average
value:
cri  c i c i

1
X
1n
n1

n!

zi fn

6:9:3

In keeping with the DebyeHuckel theory, it is assumed that the electrostatic


energy of an individual ion is small with respect to kB T so that only the rst
term in the expansion need be considered; as a result
cri  c i zi c i f

6:9:4

If fi is the force acting per mole on ion i in a spherical shell which is at a distance r
from the reference ion, and the shell has a thickness dr , then the incremental force
on the ions of type i in the shell is
dFi 4pzi c i fr2 fi dr

6:9:5

For a binary electrolyte with one type of cation and anion, the incremental force is
dF 4pfr2 z c f z c  f dr

6:9:6

Using Stokes law (equation (6.3.5)) this can be related to an incremental change
in the velocity of ion j. Thus,
dvj 

2
f rz c f z c  f dr
3Z j

6:9:7

290

LIQUIDS, SOLUTIONS, AND INTERFACES

where j is the local potential due to ion j and Z is the viscosity of the solution.
The net change in velocity is found by integrating this expression from the boundary of ion j at r a to innity. Thus,
1

vj 

2fj
z c f z c  f r dr
3Z

6:9:8

The expression obtained for j in DebyeHuckel theory (equation (3.8.26)) is


 ka 
zj e0 ekr
e
j
6:9:9
4p"0 "s r 1 ka
where k is the DebyeHuckel reciprocal distance (equation (3.8.13)).
For simplicity the derivation is restricted here to symmetrical zz electrolytes.
Substituting equation (6.9.9) into equation (6.9.8) for the case that the central ion
is a cation,
1
 ka 

z2 fe0 c e
e
f  f ekr dr
v 
6pe0 es Z 1 ka

6:9:10

or, after integration,


v 

z2 fe0 c e f  f
6pe0 es Z k1 ka

6:9:11

For a symmetrical zz electrolyte the ionic strength is equal to z2 c e . Recalling that
the DebyeHuckel reciprocal distance k is given by


2NL e0 f I 1=2
k
6:9:12
e0 es
the equation for the electrophoretic eect on the velocity of a cation may be
further simplied to obtain
v 

kf  f
12pNL Z1 ka

6:9:13

The corresponding equation for the case that the central ion is an anion is
v 

kf  f
12pNL Z1 ka

6:9:14

The forces f and f are given by the product of the charge per mole of ions and
the local eld. The latter is equal to the external applied eld E plus the relaxation
eld E. The relaxation eld arises because of the asymmetry in the ionic atmosphere caused by the motion of the ion with respect to its atmosphere. Thus, for
the cation
f NL z e0 E E z FE E

6:9:15

f z FE E

6:9:16

and for the anion

291

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

Combining these results with equations (6.9.13) and (6.9.14), one obtains
v v 

ze0 kE E
6pZ1 ka

6:9:17

This result may be interpreted as showing that the ionic atmosphere has a charge
z, opposite to that of the ion on which attention is focused. Furthermore, the
atmosphere has an eective radius equal to a 1=k. The motion of the atmosphere is in the opposite direction to that of the ion whose velocity is given by
Stokes law.
The theory of the relaxation eect makes use of the equations of hydrodynamics applied with consideration of the eects of interionic forces. It is the most
dicult part of the description of non-equilibrium processes in electrolytes, and
the details of the derivation are not given here. The result obtained for the relative
value of the relaxation eld is
E
jz z je20
q
k

E
12pe0 es kB T 1 q1=2 1 k0

6:9:18

where
q

jz z j
l0 l0
z jz j z l0 jz jl0

6:9:19

In the case of symmetrical electrolytes for which z jz j, the parameter q is


equal to 1/2.
The limiting ionic mobility for ion i, ui 0 is reduced by an amount ui (relx) as a
result of the eld relaxation eect. Thus, ignoring the electrophoretic eect one
may write


E
ui ui0 1
6:9:20
E
where the term in E=E gives the decrement in ui due to the eld relaxation eect.
From equation (6.9.17), the decrement in ui due to the electrophoretic eect is


vi
zi e0 k
E
1

ui elph
6:9:21
6pZ1 ka
E
E
Combining equations (6.9.20) and (6.9.21), one obtains



zi e0 k
E
1
ui ui0 
6pZ1 ka
E

6:9:22

The expression for E=E (equation (6.9.18)) is now substituted into equation
(6.9.22) with the result that
!
zi e0
jz z je20 ui0
q
k
6:9:23

ui ui0 
6pZ 12p"0 "s kB T 1 q1=2 1 ka
where the second-order term in E=E has been neglected.

292

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 6.3. Values of the Debye-Onsager Constants B1


and B2 for 11 Electrolytes Together with the Viscosity
of Water in the Temperature Range 0508C
T/8C

Z=mPa s

B1 =L1=2 mol1=2

B2 =cm2 L1=2 1 mol3=2

0
10
20
25
30
40
50

1.792
1.307
1.002
0.890
0.798
0.653
0.547

0.2208
0.2236
0.2272
0.2292
0.2315
0.2362
0.2416

29.71
40.91
53.65
60.57
67.78
83.39
100.3

The nal result is obtained by multiplying each mobility ui by the Faraday to


obtain the individual ionic equivalent conductances li . The values of li for the
ions in the binary electrolyte are added so that
I1=2
Fu u 0  B1 0 B2
6:9:24
1 BDH aI1=2
where
!1=2
jz z je20
q
2NL e20
B1
6:9:25
12p"0 "s kB T 1 q1=2 "0 "s kB T
and
!1=2
NL z jz je20 2NL e20
B2
6pZ
"0 "s k B T

6:9:26

The DebyeOnsager constants B1 and B2 depend explicitly on temperature, and


also on the solvent parameters es and Z, which themselves are temperature dependent. If a factor of 1000 is included in the terms under the square root sign so that
the ionic strength may be expressed in moles per liter, then B1 and B2 may be
written as
B1

jz z je20
q
B
12p"0 "s kB T 1 q1=2 DH

6:9:27

NL z jz je20
BDH
6pZ

6:9:28

and
B2

where BDH is the DebyeHuckel constant dened in equation (3.8.34). Values of


B1 and B2 for water together with its viscosity in the temperature range from 0 to
508C are given in table 6.3.
EXAMPLE

Estimate the molar conductivity of 0.1 M HCl at 258C given that its limiting
molar conductivity is 426.2 cm2 1 mol1 and assuming an ionic size parameter a of 0.45 nm.

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

293

The calculation is based on equation (6.9.24) and requires estimation of the


DebyeHuckel factor I 1=2 =1 BDH a I 1=2 ), where the value of BDH is given in
table 3.8; the ionic strength for this system is equal to its concentration so that
I1=2
0:316
0:2153 mol 1=2 L1=2

1 BDH aI1=2 1 3:288  0:45  0:316

6:9:29

The estimate of is
426:2  0:2292  426:2 60:57  0:2153 392:1

6:9:30

Thus, the molar conductance is 392.1 cm2 1 mol1 .


Application of the DebyeOnsager model to conductivity data for NaCl in water
is illustrated in g. 6.10. When the size parameter a is set equal to 0.4 nm, an
excellent t of theory to the experimental data is obtained for concentrations up
to 0.5 M (I1=2 0:7 M1=2 ). At higher concentrations the experimental data fall
below the theoretical curve indicating that the model does not describe the
decrease in with concentration properly in this range. A variety of reasons
can be cited for this failure and many of them have been discussed with respect
to the DebyeHuckel theory for the equilibrium properties of electrolyte solutions. They include the failure to describe properly the thickness of the ionic
atmosphere and the strength of ionion interactions at high ionic strength.
Attempts have been made to extend the concentration range over which equation
(6.9.24) is valid by adding extra terms in the concentration. The interested reader
is referred to more extensive discussions of this subject [7, 10] for further details.
In the limit of very dilute solutions where ion size eects may be neglected,
equation (6.9.24) becomes

Fig. 6.10 Plot of the equivalent conductance of NaCl in water according to equation
(6.9.1) against the square root of the ionic strength at 258C. The solid curve shows the
prediction of the DebyeOnsager equation with a 0:4 nm, and the straight line, the
prediction of this model in the limit that ion size eects may be neglected.

294

LIQUIDS, SOLUTIONS, AND INTERFACES

0  B1 0 B2 I1=2

6:9:31

This is identical with equation (6.9.1) in the case of 11 electrolytes. The predictions of the limiting law for the NaCl system are also shown in g. 6.10. It is valid
for concentrations up to 0.01 M. The success of the theory is clear from this result.
First of all, it conrms that plots of against the square root of ionic strength
provide a valid route for determining 0 , the equivalent conductance in the limit
of innite dilution. In addition, it explains why the slope of the plot in the dilute
solutions regime depends on the nature of the electrolyte.
The above theory can also be applied to account for the concentration dependence of transport numbers, especially in dilute solutions. Since the transport
number can be dened as a ratio of the equivalent conductance of the given
ion to the total ionic conductance (equation (6.7.6)), it is clear that a non-linear
relationship can be derived describing the concentration dependence using equations (6.9.23) and (6.9.24).
In summary, Onsagers extension of the DebyeHuckel theory to the nonequilibrium properties of electrolyte solutions provides a valuable tool for deriving single ion properties in electrolyte solutions. Examination of the large body of
experimental data for aqueous electrolyte solutions helped conrm the model for
a strong electrolyte. In more recent years, these studies have been extended to
non-aqueous solutions. Results in these systems are discussed in the following
section.

6.10 Transport Phenomena in Non-Aqueous Solutions


In the development of the theory of ionic conductance it has been shown that the
viscosity of the solvent is an important parameter determining ionic mobility.
Initially, conductivity data were only available in water so that attention was
focused on the eects of ionic size, structure, and charge in determining mobility
and its concentration dependence. More recently, data have become available in a
wide variety of non-aqueous solvents [11, 12], that is, in media with a wide range
of permittivities and viscosities. On the basis of these data one may examine in
more detail the role of solvent viscosity in determining the transport properties
of single ions. Values of the limiting ionic molar conductance for selected monovalent cations and anions are summarized in tables 6.4 and 6.5, respectively.
By combining the StokesEinstein equation (equation (6.7.27)) with equation
(6.7.23), the following expression for the limiting ionic molar conductance is
obtained:
li0

z2i F2
6pNL ZrST

6:10:1

where Z is the viscosity of the pure solvent and rST , the eective Stokes radius of
the ion. Rearranging, one obtains the following result for the Stokes radius:
rST

z2i F2
6pNL Zli0

6:10:2

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

295

Table 6.4 Limiting Ionic Conductances for


Monovalent Cations in Various Solvents at
258C
li0 =cm2 1 mol1
Solvent

Li Na K

Cs TEA TBA

38.7
39.6
17.1
8.8
8.3
14.7

50.1
45.2
20.5
10.5
9.9
18.3

73.5
52.4
23.3
12.1
12.4
19.0

77.3
69.0
26.4
13.8
13.5
21.2

32.7
60.5
29.2
15.1
10.4
21.2

19.5
38.9
19.6
10.9
6.6

72.1
69.5

20.3
26.1
11.5
5.3
13.9
14.5
53.9
8.3
4.3
14.5

74.8
76.8
19.6
25.8
30.0
14.1
5.5
14.6
15.9
56.7
9.3
3.6
16.1

78.9
85.1
23.5
25.2
31.6
14.7
5.7
15.2
17.4
59.7
11.2
4.0
15.7

84.4
87.3

27.9
35.4
15.6
6.2

12.3
4.3
16.9

91.4
85.9
24.7
32.9
36.2
17.3
9.1
18.3
16.1
48.1
13.2
3.9
22.1

67.3
62.4
17.2
22.8
26.6
11.4
6.1

11.5
34.7
9.0
2.8
15.0

Protic
1.
2.
3.
4.
6.
7.

W
MeOH
EtOH
PrOH
F
NMF

Aprotic
8.
9.
10.
12.
13.
14.
15.
16.
17.
18.
20.
21.
22.

AC
AcN
BzN
DMA
DMF
DMSO
HMPA
NMP
NB
NM
PC
TMS
TMU

The product li0 Z is known as the Walden product and is the focus of the discussion in the present section. To a rst approximation, li0 Z should be independent
of solvent nature if the ion moves in the solution without any accompanying
solvent molecules. However, some variation in li0 Z is seen on the basis of an
analysis of the data in tables 6.4 and 6.5 using the viscosities reported in table
6.1[13].
Plots of the Stokes radius for the Na and TEA cations estimated using
equation (6.10.2) in 18 dierent solvents are shown as a function of the eective
radius of the solvent molecule, rs , in g. 6.11. Quite a large change in solvent size
is involved for the solvents considered, from the very small water molecule with a
radius of 137 pm to the very large hexamethylphosphoramide molecule with a
radius of 394 pm. The results are quite striking: the Stokes radius of the TEA
cation is approximately constant and equal to 270 pm, whereas the Stokes radius
of the Na cation clearly increases with solvent size. The line shown for the Na
data in this gure was drawn with unit slope and with an intercept on the y-axis of
102 pm, that is, the crystallographic radius of the Na ion. Although there is
considerable scatter about the line, it is clear that the most important factor
determining the size of the moving ion is the size of the solvent molecules

Table 6.5 Limiting Ionic Conductances


for Monovalent Anions in Various
Solvents at 258C
li0 =cm2 1 mol1
Solvent

Cl

Br

I

76.4
52.1
22.0
10.4
17.3
53.8

78.1
56.4
24.1
12.2
17.5
53.4

76.8
62.6
27.2
13.4
16.8
51.1


ClO
4 BPh4

Protic
1.
2.
3.
4.
6.
7.

W
MeOH
EtOH
PrOH
F
NMF

67.4
70.6
31.8
16.3
16.7
51.6

36.5
20.0
10.7
6.3

AC
105.1 115.9 113.0 115.5
AcN
99.2 100.7 102.5 103.7
DMA
45.9 43.2 41.8 42.8
DMF
53.8 53.4 51.1 51.6
DMSO 24.2 23.8 23.6 24.0
HMPA 19.7 18.9 17.2 16.0
NMP
26.5 28.2 27.0 27.2
NB
22.4 22.0 21.3 21.5
NM
61.9 62.3 63.1 65.3
PC
20.2 18.9 18.5 18.6
TMS
9.3
8.9
7.2
6.7
TMU

30.1 28.8 28.4

66.0
58.0

10.7
6.1
12.2
10.8
32.5
8.4

Aprotic
8.
9.
12.
13.
14.
15.
16.
17.
18.
20.
21.
22.

Fig. 6.11 Plots of the Stokes radii rST for Na and TEA estimated using equation (6.10.2)
against the eective solvent radius rs . The data for TEA have been shifted vertically by
300 pm for the sake of clarity.

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

297

which accompany it. The scatter can be attributed to several factors, one of them
being the obvious fact that not all solvent molecules are perfectly spherical.
However, other factors also play a role. For example, the three solvents EtOH,
AcN, and NM have radii which are close to 216 pm. The Stokes radius for Na in
NM is smallest (237 pm), that in AcN intermediate (313 pm), and that in EtOH
largest (371 pm). This follows the increase in solvent donicity. Since NM is a very
weak Lewis base, the Na ion holds fewer solvent molecules on the average when
it moves, and therefore has a smaller radius. On the other hand, EtOH is a
stronger Lewis base so that the moving ion has a larger radius reecting the
fact that more solvent molecules move with it. TEA is a much larger ion than
Na with a tetrahedral structure and an approximate radius of 337 pm. For this
cation, the Stokes radius is independent of solvent nature with an average value
equal to 270 pm. This result indicates the eective size of the ion when it moves as
an unsolvated species.
The results for the Stokes radii of anions are more complex and are considered
separately for protic and aprotic solvents. In the case of aprotic solvents, the value
of rST decreases in the aprotic solvents with increase in solvent radius (g. 6.12).
Since the interaction between the anion and solvent is weak, the number of
solvent molecules which move with the ion decreases with increase in solvent

size. This trend is weaker for the larger ClO
4 ion than for the smaller Cl ion,

demonstrating that the Cl anion is more strongly solvated in solvents of the
smallest molecular size. In the case of protic solvents, hydrogen bonding is
involved in anion solvation. Data are available in only a few solvents so that a
detailed analysis is not possible at present.
The results presented here demonstrate clearly that the solvent radius is the
important parameter to be considered in discussing the solvent dependence of the

Fig. 6.12 Plots of the Stokes radii for Cl and ClO
4 ions in aprotic solvents estimated
using equation (6.10.2) against the eective solvent radius rs . The data for ClO
4 have
shifted vertically by 300 pm for the sake of clarity.

298

LIQUIDS, SOLUTIONS, AND INTERFACES

Stokes radius or of the Walden product. Ion size and structure both determine the
extent to which the ion moves with associated solvent molecules.

6.11 Proton Transport Phenomena


The proton is formed from the lightest element in the periodic table and has the
smallest ionic size. It also has a special relationship to the most common polar
solvent, namely, water. These two facts combine to give this ion the highest
mobility in water, approximately 10 times that of the Li ion, which is the next
larger monoatomic cation. In order to understand these observations one must
develop a picture of how the proton is incorporated in the structure of protic
solvents.
Using the analysis of the thermodynamic properties of monoatomic ions in
water presented earlier (section 3.5), the Gibbs energy of solvation of the proton
at innite dilution and 258C is 1104 kJ mol1 . On the basis of the MSA, using
the parameters for monoatomic cations given in table 3.5, the corresponding
radius of the H ion is 13 pm. Thus, the proton radius is close to one-sixth of
the radius of the Li ion (74 pm). This in turn means that the electrical eld due to
the H ion is approximately six times larger than that due to the Li ion. As a
result, the interaction between the proton and surrounding solvent dipoles is
extremely large compared to ions of more usual dimensions, that is, with radii
greater than 100 pm. In the case of water, a covalent bond is formed by interaction of the proton with the lone pair electron density on an adjacent water molecule. The existence of the hydronium ion, H3 O , was demonstrated using infrared
spectroscopy by Falk and Gigue`re [14]. It has also been observed in the solid state
in compounds such as HClO4
H2 O using X-ray crystallography. In dilute aqueous
solutions at equilibrium, the hydronium ion is solvated by other water molecules.
Considering the structure of water, the most probable local species corresponds to
H9 O
4.
The mechanism by which the hydronium ion moves in water is very dierent
than that by which most other ions move. As shown in g. 6.13, the conductance
process involves the transfer of a proton between two adjacent water molecules
with the proton in a hydrogen bond between these molecules. Because of the
relative orientation of the water molecules with respect to one another, the net
motion of the proton is not exactly in the direction of the electrical eld but rather
in zig-zag motion about this direction. This feature of the net forward motion can
also be described in terms of rotation of the water molecule to which the proton is
transferred so that the orbitals on this molecule are favorably oriented with
respect to the direction of the eld. The net eect is that the value of l0 at
258C is 349.8 cm2 1 mol1 , that is, much higher than any other monovalent ion.
The hydroxyl ion moves by a similar mechanism, which involves proton transfer in the opposite direction of the electrical eld. The molar conductance of the
OH ion is smaller (197.6 cm2 1 mol1 ) simply because this ion occupies more
space in the water structure. In addition, the eld due to OH is much less than
that due to H because of the much larger size of the former ion. Anomalous
proton transfer also occurs in the lower alcohols and their mixtures with water.

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

299

Fig. 6.13 Schematic diagram illustrating


the mechanism for proton and hydroxyl
ion conductance in water.

This also reects the fact that proton transfer in a solvent such as methanol
involves the species CH3 OH
2 . However, in the alcohols there is only one site
for hydrogen bond formation, whereas the water molecule has two. Thus orientational eects are more important in acidied alcohol systems, so that the enhancement of proton mobility with respect to other monovalent cations is not as great
as it is in water.
An important question regarding proton transfer in water is whether it occurs
by a classical mechanism or by quantum-mechanical tunneling. This problem can
be elucidated by comparing the rates of proton and deuteron transfer. In this way
it was concluded that transfer occurs by both mechanisms [15].
Another way of examining the mechanism of proton transfer is by comparing
its temperature dependence with that of other monoatomic cations. Plots of the
molar conductance of three cations, namely, H , Li , and K , on a logarithmic
scale are shown as a function of reciprocal temperature in the range 5558C in g.
6.14. Excellent linear plots are found from which an energy barrier associated
with the process may be calculated. Using a simple Arrhenius expression, the
temperature dependence of li for a small temperature interval is given by
li Al exp



Ul
RT

6:10:3

where Al is the pre-exponential factor, and Ul , the activation energy associated


with the conductance process. From the data presented in g. 6.14, the value of
Ul is 10.0 kJ mol1 for the proton; on the other hand, it is 16.3 kJ mol1 for Li ,
and 14.2 kJ mol1 for K . This type of analysis certainly oversimplies the
physical picture of proton transport because several mechanisms are involved.
However, it clearly shows that the net eect for the proton is that the average
activation barrier is much less than that for other cations.

300

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 6.14 Plot of the molar conductance for H , Li , and K ions against the reciprocal
temperature in the range 5558C.

The study of proton transfer in solutions is a rich area of research [16] which
has only been briey introduced by the present discussion. It is obviously important not only in conduction processes but also in acidbase processes in solution.
More information about these reactions is given in chapter 7.

6.12 Concluding Remarks


The discussion in this chapter has emphasized the Onsager approach to non-equilibrium phenomena. This provides an excellent background for understanding the
way in which the uxes observed experimentally often depend on several forces in
the system. Early experimental work dealt mainly with electrolyte solutions.
Conductivity and diusion measurements in these systems were very important
in developing a microscopic picture of the structure of electrolyte solutions.
Electrolyte solutions are non-ideal, and the non-ideality is reected in non-equilibrium processes by the concentration dependence of the phenomenological coecients. The work by Debye and Onsager has shown that the concepts developed to
understand non-ideality in electrolyte solutions at equilibrium are applicable to the
same systems, when they are not at equilibrium. The DebyeOnsager theory
described here is currently being extended to include a more careful description
of ionic atmosphere eects on the basis of the MSA which was introduced in
chapter 3.
Mass transfer and heat transfer are important subjects in engineering. Whole
monographs have been devoted to solutions of the pertinent dierential equations
for a variety of boundary conditions [G2, G3]. Only one example is worked out in
this chapter to give an idea of what is involved mathematically. Mass transfer
problems make up an important part of electroanalytical chemistry. In a typical
experiment the current which ows in the electrochemical cell which is not at

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

301

equilibrium is used to determine the amount of analyte. This species reacts at the
working electrode and the observed current depends not only on the concentration of the analyte but also on the mass transfer conditions by which it reaches the
reaction site at the electrode. Much more can be found about this subject and the
associated mass transfer problems in monographs devoted to electroanalysis [G4].
General References
G1. Katchalsky, A.; Curran, P. F. Non-Equilibrium Thermodynamics in Biophysics;
Harvard University Press: Cambridge, MA, 1967.
G2. Jost, W. Diusion in Solids, Liquids, Gases; Academic Press: New York, 1960.
G3. Bird, R. B.; Stewart, W. E.; Lightfoot, E. N. Transport Phenomena; Wiley: New York,
1960.
G4. Galus, Z. Fundamentals of Electrochemical Analysis; Ellis Horwood: New York, 1994.

References
1. Onsager, L. Phys. Rev. 1931, 37, 405; 1931, 38, 2265.
2. de Groot, S. R. Thermodynamics of Irreversible Processes; North-Holland:
Amsterdam, 1952.
3. McQuarrie, D. A. Statistical Mechanics; Harper and Row; New York, 1976.
4. Riddick, J. A.; Bunger, W. B.; Sakano, T. K. Organic Solvents, 4th ed.; Wiley: New
York, 1986.
5. Debye, P. Polar Molecules; Chemical Catalogue Co.: New York, 1929.
6. Parsons, R. Modern Aspects of Electrochemistry; Bockris, J. OM., Conway, B. E.,
Eds.; Butterworths: London, 1954; Chapter 3.
7. Robinson, R. A.; Stokes, R. H. Electrolyte Solutions, 2nd ed; Butterworths: London,
1959.
8. Arrhenius, S. Z. Phys. Chem. 1887, 1, 631.
9. Onsager, L. Phys. Z. 1927, 28, 277.
10. Justice, J. C. In Comprehensive Treatise of Electrochemistry; Conway, B. E., Bockris,
J. OM., Yeager, E., eds.; Plenum Press: New York, 1983; Vol. 5, Chapter 3.
11. Karapetyan, Yu. A.; Eychis, V. N. Physico-chemical Properties of Non-Aqueous
Electrolyte Solutions (in Russian); Khimia: Moscow, 1989.
12. Barthel, J.; Neueder, R.; Schroder, P. Electrolyte Data Collection; Dechema:
Frankfurt, 1992; Vol. XII, Part 1; 1993; Vol. XII, Part 1a; 1994; Vol. XII, Part 1b;
1996; Vol. XII, Part 1c.
13. Fawcett, W. R. Mol. Phys. 1998, 95, 507.
14. Falk, M.; Gigue`re, P. Can. J. Chem. 1957, 35, 1195.
15. Conway, B. E.; Bockris, J. OM., Linton, H. J. Chem. Phys. 1956, 24, 834.
16. Lengyel, S.; Conway, B. E. In Comprehensive Treatise of Electrochemistry; Conway, B.
E., Bockris, J. OM., Yeager, E., Eds.; Plenum Press: New York, 1983; Vol. 5,
Chapter 5.

Problems
1. The viscosity of DMSO is 1.996 mPa s at 258C. Estimate its Debye relaxation
time assuming a molecular diameter equal to 491 pm. Compare your answer
with the experimental value, which is 18.9 ps.
2. Ficks law for diusion to a sphere of radius r0 is written

302

LIQUIDS, SOLUTIONS, AND INTERFACES

"
#
@cr; t
@2 cr; t 2 @cr; t
D

@t
r @r
@r2

Solve this expression for cr; t with the conditions


cr; 0 c ; cr0 ; t 0t > 0; lim cr; t c r ! 1
Show that the ux J at r r0 follows the expression


1
1
J Dc

r0 pDt1=2
(Hint: By making the substitution vr; t r cr; t in Ficks equation and in
the boundary conditions, the problem becomes essentially the same as that
for linear diusion.)
3. Using the limiting ionic conductances recorded in table 6.4 for the alkali
metal ions in acetonitrile, estimate their diusion coecients and Stokes
radii.
4. The following parameters apply to mass transfer in 0.01 M NaCl:
D 1:545  105 cm2 s1
118:53 cm2 1 mol1
t 0:3918
Assume that the coecient
e given in equation (6.7.46) can be estimated
using the DebyeHuckel theory with an ion size parameter equal to 0.42 nm.
Calculate values for the phenomenological coecients LMM , LXX , and LMX
using equations (6.7.48)(6.7.50).
5. The following data are reported for the conductivity of solutions of chloroacetic acid in water at 258C.
Conc./M

/cm2 1 mol1

1.101104
3.027104
5.899104
1.323103
2.821103
3.812103
7.462103
1.4043102

362.10
328.92
295.58
246.15
197.14
177.98
139.85
109.00

Determine the acidity constant for this acid and its limiting ionic conductivity.
6. Determine the best value of the ion size parameter for LiNO3 given the
following data obtained at 188C. At this temperature the DebyeHuckel

NON-EQUILIBRIUM PHENOMENA IN LIQUIDS AND SOLUTIONS

303

BDH is 3.274 M1=2 nm1 , and the DebyeOnsager constants are B1


0:2264 M1=2 and B2 50:99 cm2 M1=2 1 mol1 .
ce /M

=cm2 1 mol1

0.001
0.005
0.01
0.05
0.1
0.5
1.0

92.9
90.3
88.6
82.7
79.2
68.0
60.8

7. Estimate the missing data points for Cs in table 6.4 using a linear correlation
between the Stokes radius and the solvent radius as illustrated in g. 6.11.
8. The following data were obtained for ZnSO4 in water at 258C.
ce /M

=cm2 1 mol1

2104
5104
1103
2103
5103
0.01
0.02
0.05
0.1

242.0
234.0
225.0
212.0
190.0
169.0
146.4
121.4
105.0

(a) Determine the limiting ionic conductance assuming that ZnSO4 is a


strong electrolyte
(b) Determine this parameter assuming that ZnSO4 can be considered a
weak electrolyte due to strong ion pairing.
(c) Comment on these results using the parameters given in table 6.2.

Chemical Reaction Kinetics


in Solution

Rudolph (Rudy) Marcus was born in 1923 at


Montreal, Quebec, Canada, where he also grew
up and went to school. He entered McGill
University to study chemistry, obtaining a BSc in
1943 and a Ph.D. in 1946. His doctoral research
under Professor Carl Winkler was in the area of
chemical kinetics. He then spent two years as a
post-doctoral fellow at the National Research
Council in Ottawa, Canada where he worked in
the photochemistry laboratory of E.W.R.
Steacie. As a young student, Marcus had strong
Rudolph Arthur Marcus
interests in both mathematics and chemistry. In
order to develop these interests further he joined
the research group of Professor Oscar Rice at the University of North Carolina
in 1949. There he worked on the theory of unimolecular reactions becoming
one of the contributors to what is now known as RRKM (RiceRamsperger
KasselMarcus) theory. In 1951, Marcus joined the faculty of the Polytechnic
Institute of Brooklyn as Assistant Professor. It was during his years in
Brooklyn that he developed the now famous theory of electron transfer. He has
subsequently held faculty positions at the University of Illinois and, at
California Institute of Technology where he presently holds the Arthur Amos
Noyes Chair of Chemistry. His work on the theory of chemical kinetics has
also involved proton and atom transfer reactions as well as reactions at
interfaces. In 1992, Marcus was awarded the Nobel Prize in Chemistry for his
contributions to the theory of electron transfer reactions in chemical systems.
He has received numerous other honors including the Peter Debye award of
the American Chemical Society and foreign membership in the Royal Society
(London).

7.1 What Time Scales Are Involved for Chemical


Reactions in Solution?
The kinetics of chemical reactions were rst studied in liquid solutions. These
experiments involved mixing two liquids and following the change in the concentration of a reactant or product with time. The concentration was monitored by
removing a small sample of the solution and stopping the reaction, for example,
304

CHEMICAL REACTION KINETICS IN SOLUTION

305

by rapidly lowering the temperature, or by following a physical property of the


system in situ, for example, its color. Although the experiments were initially
limited to slow reactions, they established the basic laws governing the rate at
which chemical changes occur. The variables considered included the concentrations of the reactants and of the products, the temperature, and the pressure.
Thus, the reacting system was examined using the variables normally considered
for a system at equilibrium. Most reactions were found to be complex, that is, to
be made up of several elementary steps which involved one or two reactants.
As the fundamental concepts of chemical kinetics developed, there was a strong
interest in studying chemical reactions in the gas phase. At low pressures the
reacting molecules in a gaseous solution are far from one another, and the theoretical description of equilibrium thermodynamic properties was well developed.
Thus, the kinetic theory of gases and collision processes was applied rst to
construct a model for chemical reaction kinetics. This was followed by transition
state theory and a more detailed understanding of elementary reactions on the
basis of quantum mechanics. Eventually, these concepts were applied to reactions
in liquid solutions with consideration of the role of the non-reacting medium, that
is, the solvent.
An important turning point in reaction kinetics was the development of experimental techniques for studying fast reactions in solution. The rst of these was
based on ow techniques and extended the time range over which chemical
changes could be observed from a few seconds down to a few milliseconds.
This was followed by the development of a variety of relaxation techniques,
including the temperature jump, pressure jump, and electrical eld jump methods.
In this way, the time for experimental observation was extended below the nanosecond range. Thus, relaxation techniques can be used to study processes whose
half lives fall between the range available to classical experiments and that characteristic of spectroscopic techniques.
The experimental techniques for studying fast reactions provided a means of
studying fundamental processes in solution that were previously considered to be
instantaneous. These include electron and proton transfer reactions. Proton
transfer is the elementary step involved in acidbase reactions, which are so
important in classical analytical chemistry. On the other hand, electron transfer
is the elementary step involved in redox reactions. The theory of electron transfer
is especially well developed and is discussed in detail below.
This chapter is mainly concerned with fast reactions and the experimental
methods used to study them. Other than the relaxation techniques already mentioned, spectroscopic methods applied to the study of elementary reactions are
outlined. Especially important in this regard are laser methods which are able to
probe fundamental processes in solution in the femtosecond time range.

7.2 Fundamental Concepts


The experimental study of chemical kinetics traditionally involves the measurement of the concentration of a reactant or a product of the reaction as a function
of time in a homogeneous system. When the experimental data are plotted, one

306

LIQUIDS, SOLUTIONS, AND INTERFACES

usually nds that the slope of the plot, that is, the rate of reaction, decreases as
time increases. On the basis of a number of dierent experiments, the conclusion
was reached that the rate of reaction could be related to the concentration of one
reactant in a fairly simple way. Thus, for the irreversible reaction
A ! products

7:2:1

the rate of reaction is often given by the general expression




dcA
kr cnA
dt

7:2:2

where dcA =dt is the rate of reaction with respect to the reactant A, cA, its
concentration, n, the order of the reaction, and kr, the rate constant. Typical
values of n are 1 corresponding to a rst-order reaction and 2, corresponding
to a second-order reaction. However, other values are found experimentally
including fractional values such as 1/2 and 3/2. In these cases, a complex mechanism is involved.
Experimental determination of the reaction order can be made in several ways
[G1, G2]. Given values of cA as a function of time, one can estimate dcA/dt by
numerical dierentiation. Then, the reaction order can be estimated on the basis
of a plot of the logarithm of the reaction rate against the logarithm of the reactant
concentration. Thus, from equation (7.2.2)


dcA
ln
ln kr n ln cA
7:2:3
dt
The order of the reaction is estimated from the slope of the plot and the rate
constant from the intercept.
Since estimation of the rate of reaction from the experimental data involves
amplication of experimental error, an improved estimate of the rate constant is
usually sought using an integrated version of the general expression for the rate of
reaction once it is known. For a rst-order reaction (n 1), integration of equation (7.2.2) gives the result
ln cA ln cA0  kr t

7:2:4

where cA0 is the initial concentration of reactant A. It follows that a plot of ln cA


against time t should be linear, and that the rate constant kr can be determined
from the slope of the plot. If the reaction is second order (n 2), the relationship
resulting from integration of equation (7.2.2) is
1
1

kr t
cA cA0

7:2:5

Thus, a plot of 1/cA should be linear in time t with a slope equal to the rate
constant kr. Once the order of reaction is known, equation (7.2.2) can be integrated to obtain a relationship between cA and t. Using this relationship the data
may be analyzed further to obtain the rate constant kr .
Most chemical reactions involve more than one reactant. For example, for an
irreversible reaction involving two reactants such as
aA bB ! products

7:2:6

CHEMICAL REACTION KINETICS IN SOLUTION

307

the rate of reaction can be written as




1 dcA
1 dcB
n

kr cm
A cB
a dt
b dt

7:2:7

where a and b are the stoichiometric coecients for reactants A and B, respectively, and m and n, the corresponding orders with respect to each of these
reactants. The overall order is m n. The simplest case for this general system
occurs when the reaction is rst order in A, and rst order in B with an overall
order of two. When the stoichiometric coecients are also unity one can write


dcA
dc
 B k r cA cB
dt
dt

7:2:8

Integration of this equation to give an expression for cA or cB as a function of time


is very simple in two limiting cases. If the initial concentration of A is equal to that
of B, then cA is equal to cB for all values of time and equation (7.2.8) reduces to
equation (7.2.2) for the case that n 2. The integrated result is then given by
equation (7.2.5). The other limiting case obtains when the initial concentration of
one reactant is much greater than that of the other, so that the change in concentration of the dominant reactant is negligible. If reactant B is in excess, then
integration of equation (7.2.8) gives the result
ln cA ln cA0  kr cB t

7:2:9

By performing experiments with the concentration of one reactant much smaller


than the others, the order with respect to the minority component is easily found.
This is called the method of isolation.
Integration of equation (7.2.8) for the general case of non-equal concentrations
of A and B is best carried out using a variable x which is equal to the amount of A
or B which has been consumed. Thus, the dierential equation is rewritten as


dcA
dc
dx
kr cA0  xcB0  x
 B
dt
dt
dt

7:2:10

where cA0 and cB0 are the initial concentrations of A and B, respectively. Using
the method of partial fractions this becomes


dx
1
dx
dx


kr dt
7:2:11
cA0  xcB0  x cB0  cA0 cA0  x cB0  x
After integration, one obtains
 


c x
c
ln B0
ln B0 cB0  cA0 kr t
cA0  x
cA0
or


ln


 
cB
c
ln B0 cB0  cA0 kr t
cA
cA0

7:2:12

7:2:13

This equation describes the time dependence of the two concentrations cA and
cB for all cases except the case that cA0 is equal to cB0.

308

LIQUIDS, SOLUTIONS, AND INTERFACES

Many elementary reactions are reversible so that an analysis of the kinetics


must consider both the forward and reverse processes. A simple example is a
reversible reaction consisting of two rst-order reactions, which is described as
(B
A+
7:2:14
If the rate constant for the forward step is k1 and that for the backward step, k1,
then the rate of consumption of A is


dcA
k1 cA  k1 cB
dt

7:2:15

On the basis of mass balance,


cA cB cA0

7:2:16

where cA0 is the initial concentration of A. Thus, equation (7.2.15) can be rewritten as


dcA
k1 cA  k1 cA0 k1 cA
dt

7:2:17

This can be rearranged to give the dierential equation


k1 k1 dcA
k1 k1 dt
k1 k1 cA  k1 cA0

7:2:18

After integration and further rearrangement, the relationship giving cA as a


function of time is
cA

k1 cA0 k1 cA0 expk1 k1 t


k1 k1

7:2:19

When the system is at equilibrium (t 1), the concentration of A is


cAe

k1 cA0
k1 k1

7:2:20

cBe

k1 cA0
k1 k1

7:2:21

and that of B,

The equilibrium constant in terms of concentration is


Ke

cBe
k
1
cAe k1

7:2:22

This is an important result linking chemical kinetics and thermodynamics.


The concentration change occurring for a rst-order reaction with a rate constant of 1 s1 is illustrated in g. 7.1. At 7 s, the concentration of the reactant falls
below one-thousandth of its original value. It continues to fall, reaching concentrations which are presumably too small to be detected experimentally. When the
reaction is reversible with a reverse rate constant one hundred times slower than
the forward reaction (k1 0:01 s1), the concentration of the reactant reaches its
equilibrium value in approximately 10 s. In this case, the behavior of the concentration against time is noticeably dierent.

CHEMICAL REACTION KINETICS IN SOLUTION

309

Fig. 7.1 Plots of the logarithm of the concentration of reactant A against time for a rstorder reaction with a rate constant equal to 1 s1 and a reversible rst-order reaction with
the same forward rate constant and a reverse rate constant equal to 0.01 s1. The initial
concentration of A is 1 M.

Another important feature of many mechanisms is sequential steps. This is


illustrated here with the simple example of two rst-order reactions, one following
another, that is
k1

k2

A ! B ! C

7:2:23

If the rate constant for the rst reaction is k1, then the concentration of A is given
by
cA cA0 ek1 t

7:2:24

where cA0 is its initial concentration. The dierential equation giving the concentration of B is
dcB
k1 cA  k2 cB
dt

7:2:25

where k2 is the rate constant for the second step. Substituting equation (7.2.24)
into equation (7.2.25) and multiplying through by the factor ek2t, one obtains
ek2 t

dcB
k1 cA0 ek2 k1 t  k2 cB ek2 t
dt

7:2:26

d
c ek2 t k1 cA0 ek2 k1 t
dt B

7:2:27

or

This is now easily integrated with the result


cB

k1 cA0 k1 t
e
 ek2 t
k2  k1

7:2:28

310

LIQUIDS, SOLUTIONS, AND INTERFACES

where the initial concentration of B is assumed to be zero. The concentration of C


is now found by subtraction:
cC cA0  cA  cB cA0  cA0 ek1 t 

k1 cA0 k1 t
e
 ek2 t
k2  k1

7:2:29

A plot of the concentrations of A, B, and C against time is shown in g. 7.2 for


the case that the rate constant for the second step is much greater than that of the
rst (k1  k2 ). Under these conditions the concentration of B does not reach very
high values during the course of the reaction. For smaller values of k2, the intermediate B reaches higher concentrations which represent a signicant fraction of
the number of moles of the reactant A at the beginning of the experiment (cA0).
When the concentration of B is much smaller than that of A and C, so that any
change in its concentration may be neglected, it can be assumed to be in a steady
state. The steady-state assumption is an important approximation used in the
analysis of the kinetics of complex reactions which results in much more simple
rate expressions. In the present case, the steady-state approximation for the
reactive intermediate B is
dcB
0
dt

7:2:30

It follows from equation (7.2.25) that


cBss

k 1 cA k 1
cA0 ek1 t
k2
k2

7:2:31

For the product C

Fig. 7.2 Plots of the concentration of A, B, and C against time for a consecutive reaction
scheme with irreversible rst-order processes. The solid lines show the results based on the
exact solution assuming k1 1 s1 and k2 100 s1; the points were calculated on the basis
of the steady-state approximation (equations (7.2.31) and (7.2.32)).

CHEMICAL REACTION KINETICS IN SOLUTION

cCss cA0  cA0 ek1 t 

k1
c ek1 t
k2 A0

311

7:2:32

When the steady-state estimates of cB and cC (equations (7.2.31) and (7.2.32)) are
compared with the exact values (equations (7.2.28) and (7.2.29)) it is apparent that
two conditions are involved, namely, k2  k1 and k2 t  1. Values of cB and cC
obtained on the basis of the steady-state approximation are also shown in g. 7.2.
It is clear that the steady-state values provide excellent estimates of the concentrations of these species at longer times. However, when k2 t < 1, the steady-state
estimates of cB and cC are incorrect.
The examples of reversible and consecutive reactions presented here give a very
modest introduction to the subject of reaction mechanisms. Most reactions are
complex, consisting of more than one elementary step. An elementary step is a
unimolecular or bimolecular process which is assumed to describe what happens
in the reaction on a molecular level. In the gas phase there are some examples of
termolecular processes in which three particles meet simultaneously to undergo a
reaction but the probability of such an event in a liquid solution is virtually zero.
A detailed list of the elementary steps involved in a reaction is called the reaction
mechanism.
In concluding this section, the reaction mechanism involved in a very important solution reaction, namely, enzyme catalysis, is considered. In this reaction,
the enzyme E coordinates with a substrate species S to form a reactive intermediate ES. A very small fraction of the intermediate reacts to form product P releasing the enzyme for further catalysis. The majority of the reactive intermediate
reverts to the substrate and enzyme. Thus, the mechanism can be described as
k1

E S ! ES

7:2:33

k1

7:2:34

k2

7:2:35

ES ! E S
and
ES ! P E

Assuming that the concentration of the reactive intermediate is given the steadystate approximation, one has
dcES
0 k1 cE cs  k1 cES  k2 cES
dt

7:2:36

Solving for the concentration of ES at steady state, one obtains


cESss

k 1 cE cS
k1 k2

7:3:37

Since the enzyme is a catalyst its total concentration does not change so that
dcE cES dcE

0
dt
dt

7:2:38

The rate of the overall reaction can be expressed in terms of the disappearance of
substrate S,

312

LIQUIDS, SOLUTIONS, AND INTERFACES

dcS
k1 cE cS  k1 cES
dt

7:2:39

or in terms of the formation of product P,


dcP
k2 cES
dt

7:2:40

Combining equations (7.2.37) and (7.2.40), one obtains for the steady state
dcP k1 k2 cE cS

dt
k1 k2

7:2:41

The steady-state concentration of enzyme may be related to its initial concentration as follows:
cEss cE0  cESss cE0 

k1 cE cS
k1 k2

7:2:42

where cE0 is the initial enzyme concentration. Simplifying, one nds that
cEss

k1 k2 cE0
k1 k2 k1 cS

7:2:43

Thus, the expression for the rate of reaction becomes


dcP
k1 k2 cS cE0

dt
k1 k2 k1 cS

7:2:44

Since the steady-state approximation requires that k2  k1 , this expression


simplies to


dcS
dc
k k c c
 P 1 2 S E0
dt
dt
k1 k1 cS

7:2:45

This result was rst derived by Michaelis and Menten [1].


This section has provided only a brief introduction to the principal concepts in
chemical kinetics. Most of the discussion which follows in this chapter relates to
fast reactions in solution. Before describing the experimental techniques used to
study fast reactions, the important types of solution reactions are outlined and
their properties discussed.

7.3 General Types of Solution Reactions


Important solution reactions are well known from the study of quantitative analysis in analytical chemistry. These include acidbase reactions, redox reactions,
and complex formation reactions. Often the reaction is so fast that the system is
considered to come instantaneously to equilibrium, for example, in the acid
base reaction involved in a titration. In fact, any of these reactions has a nite rate
whose kinetics can be determined using modern experimental techniques.
The above reactions may be described in a more fundamental way in terms of
the elementary act involved in the reaction. For example, the reaction between an
acid and a base involves proton transfer so that it is better described as a proton

CHEMICAL REACTION KINETICS IN SOLUTION

313

transfer reaction. Redox reactions involve electron transfer between at least two
components in the system and are better described as electron transfer processes.
Complex formation reactions are really ligand exchange reactions. Fundamental
processes such as electron and proton transfer are of great interest to theoreticians, and have been studied in great detail experimentally. Some of the important
properties of fundamental solution reactions are now outlined.
Bimolecular reactions in the gas phase and in liquid solutions dier in important ways. In the gas phase the progress of the reaction is described in terms of the
collisions which occur between the two reactants A and B. In the liquid solution
the same reactants are surrounded by solvent molecules, and the approach of
these species to each other is controlled by the laws of diusion. If A and B collide
in solution, it is highly probable that they undergo numerous successive collisions
before reaction occurs. Such a set of successive collisions is referred to as an
encounter. The fact that the surrounding solvent molecules can transfer energy
to or from A and B during the course of a solution reaction is important in
developing the theory of reactions in condensed phases. A consequence is that
the couse of the reaction is described in terms of the Gibbs energy of the system
rather than by the potential energy, as is the case for gas phase reactions. More is
said about this aspect of solution reactions in the presentation of transition state
theory in section 7.4
In a bimolecular solution reaction, the reactants A and B diuse to a point
close to one another at which reaction is possible. This process is called formation
of the precursor complex. At this point, rearrangement of bond lengths and bond
angles in the two reactants, and of the surrounding solvent molecules, can occur
to form an activated complex or transition state between the reactants and products. As one would expect, the nature of this process depends on the specic
reaction involved. It is the focus of the development of the theory of the elementary step in the reaction and the associated energy requirements. In some cases it
has been studied experimentally using very fast laser spectroscopic techniques
which provide time-resolved information about the elementary step in the femtosecond range.
In the case of very fast bimolecular reactions, the contributions of both the
diusion process and the rate of decomposition of the precursor complex must be
considered in analyzing the experimental observations. The overall reaction
mechanism can be described as
A B ! AB
AB ! C D

kdiff

7:3:1

kr

7:3:2

where A and B are the reactants, AB, the precursor complex, and C D, the
products. The rate constant for formation of the precursor complex, kdi, depends
on the diusion coecients of A and B. Noyes [2] showed that the overall rate
constant, taking into account the diusion process, is
knet

kdiff kr
kdiff kr

7:3:3

314

LIQUIDS, SOLUTIONS, AND INTERFACES

In the case of slow reactions for which kr  kdiff , the overall rate constant knet is
equal to the rate constant for transformation of the precursor complex, kr.
However, for very fast reactions, kr is greater than kdi, so that the overall rate
constant is close to kdi. Therefore, it is important to understand that there is an
upper limit on reaction rates that can be measured experimentally for diusion
controlled processes. In section 7.5 it is shown that kdi for molecular reactants is
given by
kdiff 4pNL DA DB a

7:3:4

where DA and DB are the diusion coecients for A and B in the given medium,
and a, the distance between their centers in the precursor complex. Assuming that
DA and DB are each equal to 109 m2 s1 and a, 500 pm, the estimate of kdi is
8106 m3 mol1 s1 or 8109 M1 s1. For reactions involving ions, the estimate
is larger or smaller depending on whether the ions attract one another, or repel
one another, respectively. The rate of the diusion process is often comparable to
the rate of electron and proton transfer reactions in solution. Therefore, it must be
considered in analyzing the experimental data.
The distinctive features of the elementary step involved in the important classes
of solution reactions are now considered in more detail.
A. Electron Transfer Reactions
Electron transfer reactions are classied as simple or complex on the basis of the
number of electrons transferred and whether or not chemical bonds are broken or
formed in the overall reaction. An example of a complex electron transfer reaction
is
2
2
3
S2 O2
8 2FeH2 O6 ! 2SO4 2FeH2 O6

7:3:5

In this reaction two electrons are transferred and the peroxide bond in the peroxydisulfate anion is broken. It is possible that this reaction actually involves
three elementary steps. In the rst step an electron is transferred from
Fe(H2O)62 to S2O82 to form a radical anion S2O83  . The radical then breaks

. The nal step involves the
up into the anion SO2
4 and the radical anion SO4
transfer of the second electron to the radical anion SO4  .
An example of a simple electron transfer reaction is
2
3
2
CrH2 O3
6 FeH2 O6 !FeH2 O6 CrH2 O6

7:3:6

In this case, one electron is transferred from Fe(II) to Cr(III), and no bonds are
broken or formed. The reaction is also classied as heteronuclear, since the reactants belong to dierent redox couples. This means that the overall reaction
involves a net change in the standard Gibbs energy, rG . There is considerable
interest also in homonuclear reactions such as

3
3
2
FeH2 O2
6 FeH2 O6 ! FeH2 O6 FeH2 O6

7:3:7

These systems are studied using radioactive isotopes designated by the asterisk (*)
and provide an example of an electron transfer reaction for which rGo is zero.

CHEMICAL REACTION KINETICS IN SOLUTION

315

Much of the early work on electron transfer reactions focused on systems


involving transition metal ions. Many redox couples based on the Fe(III)/
Fe(II), Co(III)/Co(II), and Cr(III)/Cr(II) can be prepared in the laboratory by
changing the ligands coordinated to the central metal ion. From these studies it is
possible to distinguish between two types of reactions which would otherwise be
classied as simple. A classic example from the work of Taube [3] is the reaction
2
CoNH3 5 Cl2 CrH2 O2
6 ! CoNH3 5 H2 O CrH2 O5 Cl


7:3:8

In this reaction the Cl ligand is transferred from the substitution-inert coordination sphere of the Co(III) complex to the substitution-inert coordination sphere of
the Cr(III) product. On the other hand, the hexaquo Cr(II) complex is substitution-labile. Thus, it was postulated that the Cl ligand is shared between Cr(II) and
Co(III) in the transition state for the reaction in which one water ligand is displaced from the substitution-labile Cr(II) reactant. Accordingly, the activated
complex is [(NH3)5Co . . . Cl . . . Cr(H2O)5]4+. After electron transfer, the Co(II)
product is substitution-labile so that the Cl ligand remains with the substitutioninert Cr(III) product. This type of electron transfer reaction follows the inner
sphere mechanism. The bridging Cl ion reduces the repulsion between the cations
involved in electron transfer and thus lowers the energy required to reach the
transition state. It may also provide orbitals of the appropriate symmetry to delocalize metalion electrons and thereby provide a continuous path of good orbital
overlap between the two metal ions. Much more about the inner sphere mechanism
of electron transfer can be found in the work of Henry Taube [3].
In the outer sphere mechanism of electron transfer the ligands around each
reactant remain intact in the passage through the transition state. This mechanism
is expected when both reactants are substitution-inert. Formation of the activated
complex may involve a change in bond lengths and bond angles within the reactants but it does not involve the sharing of ligands. The theory of electron transfer
by the outer sphere mechanism has been developed in some detail and is discussed
later in section 7.8. An important aspect of this theory concerns the relative
velocities of the electron being transferred and the nuclei in the reactants. The
transfer of the electron from an orbital on one reactant to an orbital on the other
takes place in a time which is the order of femtoseconds ( 1015 s). Nuclear
motion is much slower and is characterized by the time associated with intramolecular vibration, that is, 100 fs ( 1013 s). As a result, the nuclei in the reactants
are virtually motionless during the electron jump. This results in the Franck
Condon restriction for electron transfer which was originally formulated in the
study photochemically induced electronic transitions in molecules. It follows that
the Gibbs energy of the system remains constant during electron transfer. In
addition, the spatial conguration of the nuclei is the same in the product system
as it was in the reactant system. This conguration is not the same as the low
energy equilibrium conguration of the nuclei in either system and is usually
achieved as a result of random thermal motion. This description of the formation
of the transition state for electron transfer is the basis for the Marcus model of
electron transfer [4].
The Gibbs energy barrier involved in an electron transfer reaction is shown in
g. 7.3. As a result of random thermal processes the reactants achieve the neces-

316

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 7.3 Gibbs energy prole for the formation of an activated complex 6 in a bimolecular
heteronuclear reaction (A) and a bimolecular homonuclear reaction (B).

sary nuclear conguration for electron transfer. This is the transition state for the
reaction, designated as 6. As stated above, the electron is transferred very rapidly
with respect to the time taken to achieve the required nuclear conguration. After
electron transfer the system relaxes to the product state. For a heteronuclear
reaction the Gibbs energy of the nal state P is lower than that of the initial
state R (g. 7.3A). If the reaction is homonuclear (see equation 7.3.7) then the
Gibbs energy of the nal state P is equal to that of the initial state R (g. 7.3B).
Rate constant data for several homonuclear electron transfer reactions involving transition metal complex ions in water are summarized in table 7.1. The
striking feature of the results is that the rate constants vary over a very wide
range from a low 2  107 M1 s1 to a high of 4  108 M1 s1 . Since these
reactions are all assumed to occur by an outer sphere mechanism, the observations show that the potential energy barrier shown in g. 7.3 varies signicantly
with the nature of the reactants. According to the theory of electron transfer
(section 7.8), the magnitude of the barrier depends on the energy required to

Table 7.1 Kinetic Data for Homonuclear Electron


Transfer Reactions Involving Transition Metal Complex
Ions in Water at 258C [5]*
Reaction
[Cr(H2O)6]3=2
[V(H2O)6]3=2
[Fe(H2O)6]3=2
[Co(H2O)6]3=2
[Ru(H2O)6]3=2
[Ru(NH3)6]3=2
[Ru(en)3]3=2
[Ru(bpy)3]3=2
[Co(en)3]3=2
[Co(bpy)3]3=2

Rate Constant ket =M1 s1

Ionic Strength M

2  107
1:5  102
4.2
3.3
60
3:2  103
2:8  104
4:2  108
7:7  105
18

1.0
2.0
0.55
0.5
1.0
0.1
0.1
0.1
1.0
0.1

*The chelates involved in the last four reactions are ethylenediamine (en)
and bipyridine (bpy).

CHEMICAL REACTION KINETICS IN SOLUTION

317

rearrange the ligands and solvation atmosphere around the reactants that must
occur prior to the actual transfer of the electron. However, there is another
important feature of these reactions which leads to variation in the rate constants.
Since the reactions involve highly charged ions the observed rate constants are
very dependent on ionic strength. Thus, a comparison of kinetic data for dierent
reactions should be made at the same ionic strength. An even better way of
examining these data is to use estimates of the rate constants obtained in the
limit of zero ionic strength. More details of all of the important features of
electron transfer reactions are given in section 7.8.
The other bimolecular processes which are considered here involve the movement of atoms and ions. The lightest ion is the proton, and its reactions are
discussed in the next section.
B. Proton Transfer Reactions
According to the Brnsted denition an acid is a proton donor, and a base is a
proton acceptor. It follows that acidbase reactions can also be called proton
transfer reactions. Thus, the reaction between acid HA and base B is written as
HA B(
+A HB


7:3:9

where A is the conjugate base formed from the acid HA and HB , the conjugate
acid formed from the base B. A well-known example is the reaction between HCl
and NH3:
HCl NH3 (
+Cl NH
4

7:3:10

Usually these reactions have been studied in water or in other protic solvents such
as the alcohols. Thus, the acidbase properties of the solvent are important in
determining the relative strength of acids and bases which are solutes in water.
This leads to the denition of two other types of proton transfer reaction, namely,
the protolysis reaction,
HA H2 O(
+H3 O A

7:3:11

B H2 O(
+BH OH

7:3:12

and the hydrolysis reaction,

Finally, there is the neutralization reaction,


H3 O OH (
+2H2 O

7:3:13

The thermodynamics of these reactions is well understood and is documented in


terms of the acidity and basicity constants of the corresponding acids and bases.
On the other hand, their kinetics were only determined after relaxation techniques
for studying very fast reactions became available. The neutralization reaction is
one of fastest reactions known and its rate may be estimated, assuming that its
kinetics are only controlled by diusion of the two reactants to the reaction site
(see section 7.5).
When proton transfer reactions are studied in protic solvents such as water the
role of the solvent can be very important. For example, in a neutral solution at

318

LIQUIDS, SOLUTIONS, AND INTERFACES

pH 7, the reaction between HCl and NH3 is described by equation (7.3.10). If the
pH is low, the predominant reactant is H3O+ which can be formed by protolysis,
so that the corresponding reaction is
H3 O NH3 (
+NH
4 H2 O
On the other hand, if the pH is high, OH
dominant reaction is

7:3:14

is formed by hydrolysis and the

OH HCl(
+Cl H2 O

7:3:15

This means that a complete analysis of this system involves determination of ten
rate constants: two for direct proton transfer, two for the protolysis reaction, two
for the hydrolysis reaction, and four for proton transfer reactions such as (7.3.14)
and (7.3.15). The relationship among these reactions is shown in g. 7.4 for a
general reaction involving the acid HA and the base B in water.
The theory for the elementary act of proton transfer is well developed [6]. It
involves three steps, the rst of which is formation of the precursor complex
[AH


B]:
HA B ! AH


B

7:3:16

This step involves work which can have an electrostatic component if the reactants are charged, and includes an orientational component resulting from the
requirement that HA have a specic orientation with respect to B. The second
step is the actual proton transfer which involves intramolecular and solvent
reorganization to form the transition state for proton transfer:
AH


B ! A


H


B

7:3:17

Finally, there is the disorientation step in which the complex formed after proton
transfer resolvates as the products:
A


HB ! A HB

7:3:18

The energetics of each of these steps have been described in the Marcus model for
proton transfer [6]. Proton transfer is a bimolecular process so that formation of
the transition state involves an energy barrier of the type shown in g. 7.3.
Kinetic data [7] for some acidbase reactions involving the solvated proton
H3O+ are summarized in table 7.2. The forward reaction is always very fast and
close to the diusion-controlled limit. On the other hand, the reverse reaction is
much slower as required by the relationship between the acidity constant for the

Fig. 7.4 Reaction scheme for proton


transfer between the acid HA and base
B in water illustrating the role of
protolysis (P) and hydrolysis (H)
reactions.

319

CHEMICAL REACTION KINETICS IN SOLUTION

Table 7.2 Kinetic Data for Some Simple AcidBase Reactions in Water
at 258C [7]
Rate Constants
Forward kf =M1 s1 Backward kb =s1

Reaction
H3 O OH 2H2 O
H3 O F HF H2 O
H3 O HS H2 S H2 O
H3 O HCO
3 H2 CO3 H2 O
H3 O HCOO HCOOH H2 O
H3 O CH3 COO CH3 COOH H2 O
H3 O NH3 NH
4 H2 O

1:4  1011
1:0  1011
7:5  1010
4:7  1010
5  1010
4:5  1010
4:3  1010

2:5  105
7  107
4:3  103
8  106
8:6  106
7:8  106
25

equilibrium Ka and the two rate constants kf and kb . Similar results are found
when data for a collection of reactions between OH1 and a weak acid are
considered [8]. The forward rate constant is very fast, whereas the backward
reaction reects the basicity constant for the weak base in the equilibrium.
Since ions are involved in these reactions, medium eects are important and
must be considered in a complete analysis of the experimental data.
Many more details can be found about the kinetics of proton transfer reactions
[8]. These often involve specic chemical features of the reactants. Since much of
the focus in this chapter is on experimental methods, these reactions are not
discussed further. However, the use of NMR spectroscopy to study proton transfer kinetics is considered in section 7.9.
C. Ligand Exchange Reactions
The kinetics of formation of complex ions is the subject of considerable interest in
inorganic chemistry [9]. If the discussion is limited to octahedral complexes, then
the type of reaction being considered is
z (
nz
MH2 On
H2 O
6 L +MH2 O5 L

7:3:19

The ligand exchanging with the water molecule can be a neutral molecule such as
NH3 (z 0) or monovalent anions such as the halides (z 1). The interesting
observation is that the rate of the reaction is practically independent of the nature
of the ligand but very much dependent on the nature of the metal ion. This has led
to the hypothesis that the mechanism of ligand exchange involves a reactive
intermediate with less than six ligands:
n
(
MH2 On
6 +MH2 O5 H2 O

7:3:20

The reactive intermediate then recombines with a water molecule or with the
or to give the product
ligand Lz to reform the reactant MH2 On
6
MH2 O5Lnz . This type of mechanism in which a reactant intermediate involving fewer than the normal number of ligands or bonds is formed is called the SN1

320

LIQUIDS, SOLUTIONS, AND INTERFACES

mechanism in organic chemistry. The rate of the reaction is a reection of the


strength of the MOH2 bond.
In order to characterize the ligand exchange process more quantitatively,
studies have been made of the kinetics of water exchange for a wide variety of
metal ions
17
n
(
H2 O
MH2 O6 n H17
2 O+MH2 O5 H2 O

7:3:21

By using water molecules labelled with 17O in the solvent one is able to follow the
kinetics of the reaction. One popular technique for measuring the kinetics of
reaction (7.3.21) is 17O NMR line-broadening experiments. The exchange reaction
is usually quite fast but has a wide range of rate constants. In terms of the rstorder reaction (7.3.20), the rate constant is small and close to 1 s1 when the metal
ion is Al3 , but very fast and greater than 109 s1 when the metal ion is Cs . In the
case of ions from the main group elements, the interaction between the metal ion
and the water ligands is mainly electrostatic in character. In this case, plots of the
logarithm of the rate constant against z2i r1
i , where zi is the cationic valence and ri
its radius, are linear [10]. For the alkali metal ions, the exchange rate is very fast,
with the rate constant falling in the range 108109 s1 . For the divalent alkaline
earth metal ions, the range of observed rate constants is much wider, varying from
 103 s1 for Be2 to  109 s1 for Ba2 . For the transition metal ions other
factors play an important role in determining the rate of ligand exchange, especially the ligand eld stabilization energy. Thus, a cation such as Cr3 which has a
high charge and three unpaired d electrons in the t2g orbitals (see g. 5.25) has a
very low ligand exchange rate ( 106 s1 ). For this reason Cr3 is substituently
inert. When ligand eld stabilization energy is lost by adding an electron to the eg
orbitals in chromium to form Cr2 , the rate of ligand exchange increases dramatically to 109 s1 . Thus, Cr2 is a substitutionally labile cation. Values of the rate
constants for water exchange for the common metal ions of the rst transition
series are given in table 7.3. The radii of these ions do not vary greatly so that the

Table 7.3 Rate Constants for Water


Exchange for Common Ions of the First
Row of the Transition Metals [9]
Ion
V2
Cr3
Cr2
Mn2
Fe3
Fe2
Co2
Ni2
Cu2
Zn2

Number of d Electrons

Rate Constant
kex =s1

3
3
4
5
5
6
7
8
9
10

90
3  106
8  109
3:1  107
3  103
3:2  106
2:4  106
3:5  104
8:0  109
3  107

CHEMICAL REACTION KINETICS IN SOLUTION

321

water exchange rate depends mainly on the number of d electrons and the associated ligand eld stabilization energy.
According to the above mechanism (equation (7.3.20)) the reactive intermediate in the ligand exchange process is formed in a unimolecular step. The height of
the Gibbs energy barrier in this step decreases as the rate of reaction (7.3.20)
increases in the forward direction. On the other hand, there is no barrier for
the reverse reaction in which the octahedral complex is reformed. The Gibbs
energy prole associated with a unimolecular reaction is illustrated in g. 7.5.
The stable complex has an average energy equal to that at the minimum on the
curve. As a result of thermal uctuations the energy can reach a value suciently
high to form the activated complex designated by the 6 sign. The diagram also
shows that there is no energy barrier associated with the products in the activated
state returning to form the reactant.
The water exchange process described here gives the essential details about the
ligand exchange process for octahedral complexes. There are many other interesting details which become apparent when one considers a wider variety of
ligands and complexes with dierent coordination numbers. Details can be
found in monographs devoted to this subject [9, 11].
D. Atom Transfer Reactions
The atom transfer reaction can be written in general as
A BC ! AB C

7:3:22

A is a base or nucleophile which attacks the species BC, forming a new molecule
AB and the species C. A well-known example from organic chemistry is the
reaction
Cl CH3 I ! CH3 Cl I

7:3:23

This reaction is also called a displacement reaction and it follows the SN2 mechanism. The attacking nucleophile can be an ion or a neutral molecule. Obviously the
solvent plays an important role in the kinetics of the reaction when ions are
involved.
The formation of the transition state for reaction (7.3.23) is shown in g. 7.6.
The electrophilic reactant is the simple molecule methyl iodide, which has tetrahedral geometry with respect to the carbon atom. As the attacking chloride ion

Fig. 7.5 Gibbs energy diagram for the formation of


an activated complex in a unimolecular reaction step.

322

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 7.6 Formation of the transition state in an atom transfer reaction between Cl and
CH3I.

approaches the methyl group, the CH bonds are distorted. The transition state
consists of a ve-atom species with the CH bonds all perpendicular to the linear
ClCI portion of the molecule. As the reaction proceeds to completion the
distance between the carbon and iodine atoms increases until the product state
is reached.
Extensive studies have been made of solvent eects on atom transfer reactions
involving ions [12]. In the case of reaction (7.3.23), the rate constant decreases
from 250 M1 s1 in N-methylpyrrolidinone to 3  106 M1 s1 in methanol.
This eect can be attributed to solvation of the anionic reactant Cl and the
anionic transition state [12]. Since the reactant is monoatomic, its solvation is
much more important. It increases signicantly with solvent acidity leading to
considerable stabilization of the reactants. As a result the potential energy barrier
increases and the rate decreases with increase in solvent acidity. As shown in g.
7.7, this leads to an approximate linear relationship between the logarithm of the
rate constant and the solvents acceptor number AN, an empirical measure of
solvent acidity (see section 4.9). Most of the results were obtained in aprotic
solvents which have lower values of AN. The three data points at higher values
of AN are for protic solvents.

Fig. 7.7 Plot of the logarithm of the rate constant for reaction (7.3.23) in various solvents
against the solvents acceptor number AN (table 4.10).

CHEMICAL REACTION KINETICS IN SOLUTION

323

The distinction between atom transfer reactions involving neutral and ionic
nucleophiles is important in developing the theory of these processes [G3].
Actually, proton transfer is also an ionic atom transfer reaction. However, it is
treated separately because of the special relationship that the proton has to the
most common solvent, namely, water. In addition, because of its very low mass,
proton tunnelling must be considered in proton transfer processes.
The Gibbs energy prole involved in formation of the transition state for atom
transfer is that shown in g. 7.3. When the attacking nucleophile is the same as the
leaving group, then the prole is that for a homonuclear bimolecular reaction.
This type of system can be studied using radioactive isotopes.
The above examples illustrate the important types of solution reactions, especially from the point of view of analytical chemistry. But it is not an exhaustive
list. For example, another type of solution reaction which is of interest to theorists
is the isomerization reaction [G3]. In this chapter, the theory of the electron
transfer process is considered in detail. Some of the results from this treatment
can also be applied to other bimolecular processes. More details follow in the later
sections of this chapter.

7.4 Temperature Effects and Transition State Theory


The eect of temperature on reaction kinetics was an important aspect of experimental studies dating from the earliest work. The common observation is that the
rate constant for the reaction increases with increase in temperature. This was
considered on a quantitative basis by Arrhenius, who derived the following
empirical expression:

kr Ar exp

Ea
RT


7:4:1

In this equation, Ar is the pre-exponential factor, which was assumed to be


temperature independent, and Ea , the activation energy. Further development
of the theory of the temperature dependence of the rate constant was based on
reactions in the gas phase. The simple picture is that two molecules which can
react, collide with a relative kinetic energy given by their individual velocities. If
this relative kinetic energy is greater than a certain minimum value called the
activation energy, then reaction can occur. If it is less than the minimum
value, then reaction does not occur and the two molecules behave as if they
had undergone an elastic collision. In the Arrhenius model, the number of successful collisions is estimated using the Boltzmann factor, expEa =RT), which
gives the fraction of collisions with relative kinetic energy greater than Ea . On the
basis of this discussion, the preexponential factor Ar should really be identied
with a collision frequency. Methods of calculating this quantity are well known on
the basis of the kinetic theory of gases. Using this theory it is clear that the
preexponential factor does depend on temperature. However, the temperature
dependence is much less than that expressed explicitly in the Boltzmann factor.
For this reason, it is more dicult to determine experimentally.

324

LIQUIDS, SOLUTIONS, AND INTERFACES

Transition state theory was also developed as a means of rationalizing rate


constants for gas phase reactions and their temperature dependence. It is most
directly applied to bimolecular reactions and is based on three fundamental
postulates for reactions in solution:
1. One can conceive of a Gibbs energy surface which gives the Gibbs energy of
the reacting system as a function of the distances between the atoms in both
the reactants and products. There exists a most probable path describing the
conguration of the atoms and surrounding solvent molecules in the system
and its Gibbs energy as it changes from reactants to products. This path is
called the reaction coordinate. The point where the Gibbs energy on this path
is a maximum is called the transition state (see g. 7.3).
2. The chemical species which exists at the transition state X6 is in equilibrium
with the reactant state.
3. The rate of reaction is equal to the product of the concentration of X6 and
frequency n6 with which it decomposes to the product state.

On the basis of these postulates, a bimolecular reaction may be described as


+X6
A B(

7:4:2

X ! products

7:4:3

dcA
dc
 B k6 cX6
dt
dt

7:4:4

The rate of reaction is




where k6 is the rate constant for reaction (7.4.3). Since this reaction is unimolecular, the rate constant has the units of s1 and is equivalent to the frequency of
passage through the transition state n6 . On the basis of the equilibrium process in
which X6 is formed, its concentration may be determined from the equilibrium
constant for reaction (7.4.2). For solution processes, the equilibrium constant is
a 6
y 6 cX6
K6 X X
7:4:5
aA aB yA yB c A c B
where ai is the activity of species i, and yi , its activity coecient on the concentration scale. Combining equations (7.4.4) and (7.4.5), the rate of reaction
becomes


dcA
dc
y y
y y
 B k6 A B K6 cA cB n6 A B K6 cA cB
dt
dt
yX6
yX6

It follows that the rate constant is given by


y y
k6 n6 A B
yX6

7:4:6

7:4:7

The parameters n6 , K6 , and yX6 are dened within the context of the transition
state model, whereas yA and yB are quantities which can be obtained from equilibrium thermodynamics.
In order to estimate the rate constant, the equilibrium constant is written down
in terms of the partition functions of the components of equilibrium (7.4.2):

CHEMICAL REACTION KINETICS IN SOLUTION

K6

q6
qA qB

325

7:4:8

where qi is the partition function of component i. Now, one component of q6 , the


partition function for the activated complex or transition state, corresponding to
a weak or loose vibration state, is factored out. This vibration occurs at a
frequency n6 and is the process which leads to decomposition of the transition
state to form the products of the reaction. The expression for the corresponding
vibrational partition function is



h 6 1
7:4:9
q6v 1  exp
kB T
Since the vibration is weak, n6 is small and the ratio hn6 =kB T is much less than
unity. As a result the exponential term in equation (7.4.9) can be replaced by the
rst two terms in its series expansion, so that



h 6 1 kB T
q6v 1  1

7:4:10
hn6
kB T
Thus the partition function for the activated complex becomes
q6

kB T
q
hn6 6r

7:4:11

where q6r is the remainder of the partition function for the activated complex
accounting for all other degrees of freedom. The equilibrium constant can now be
written as
K6

kB T q6r
k T
B Ke6
hn6 qA qB hn6

7:4:12

where Ke6 is the eective equilibrium constant obtained after factoring out the
contribution from one degree of vibrational motion. The expression for the rate
constant in the solution is
k T yA yB e
K
7:4:13
kr B
h yX6 6
The frequency associated with decomposition of the activated complex is kB T=h.
At room temperature this corresponds to 6:2  1012 s1 .
In the thermodynamic approach to the transition state model the equilibrium
constant Ke6 is related to the standard Gibbs energy change for process (7.4.2).
Thus, one writes
RT ln Ke6 6 G 6 H T6 S

7:4:14

where 6 G is the standard Gibbs energy change, 6 H , the corresponding


enthalpy change, and 6 S , the standard entropy change associated with reaction
(7.4.2). One should remember that these quantities are obtained for an equilibrium constant dened in terms of concentration with the standard state being
1 mol L1 .

326

LIQUIDS, SOLUTIONS, AND INTERFACES

By combining equations (7.4.7), (7.4.13), and (7.4.14), the expression for the
rate constant for a reaction in solution is obtained:


kB T yA yB
6 G
exp
kr
7:4:15
h yX6
RT
Alternatively, one may write
 6  


kB T yA yB
 S
6 H
exp
kr
exp
h yX6
R
RT

7:4:16

Comparing this result with the Arrhenius equation (equation (7.4.1)) it is clear
that the major part of the temperature dependence of the rate constant is associated with the exponential term containing the standard enthalpy of activation,
6 H .
An approximate relationship between the Arrhenius activation energy Ea and
the standard enthalpy of activation 6 H can be found by taking the derivative
of ln kr with respect to 1=T at constant pressure using equation (7.4.15).
Neglecting the temperature derivatives of the activity coecients, one obtains


@ ln kr
h kB T2 6 S 6 G
6 H RT
7:4:17




kB T h
R
@1=T p
RT
R
Comparing this result with the corresponding derivative obtained from equation
(7.4.1) it follows that
Ea 6 H RT

7:4:18

for reactions in solution.


When the rate of reaction is studied as a function of pressure, the standard
volume of activation can be found. Neglecting the pressure dependence of the
activity coecients, on the basis of equation (7.4.15),




@ ln kr
@ ln6 G =RT
6 V
7:4:19

@P
@P T
RT
T
EXAMPLE

The following rate constants are reported for the reaction between p-bromodimethylaniline and methyliodide in nitrobenzene:
Temperature/8C

Rate Constant/M1 s1

15.0
24.8
40.1
60.0

8:24  106
1:80  105
5:55  105
2:13  104

Estimate the Arrhenius activation energy, the pre-exponential factor, and


the enthalpy and entropy of activation at 258C. Ignore any eects due to
solution non-ideality.
The data are tted using least squares to the Arrhenius equation in the form

CHEMICAL REACTION KINETICS IN SOLUTION

327

Ea
RT

7:4:20

6:969  103
T

7:4:21

ln kr ln Ar 
The result is
ln kr 12:46 

The value of the activation energy is given by


Ea 6:97  103  8:314 58:0 kJ mol1

7:4:22

The pre-exponential factor is


Ar exp12:456 2:57  105 M1 s1

7:4:23

From equation (7.4.18), the enthalpy of activation is


6 H Ea  RT 57:9  2:5 55:4 kJ mol1

7:4:24

The Gibbs activation energy is calculated from equation (7.4.15) ignoring the
activity coecients. From equation (7.4.20) the rate constant at 258C is
1:82  105 M1 s1 . Thus,
!
5
1:82

10
7:4:25
6 G RT ln
100:1 kJ mol1
6:2  1012
Now,
6 S

6 H  6 G 55:4  100:1  1000


150 J K1 mol1

298:2
T

7:4:26

The entropy of activation is negative because formation of the activated


complex involves the combination of two molecules.
Estimation of the activation parameters on the basis of fundamental theoretical considerations is a formidable task for solution reactions. Because of the
surrounding solvent molecules which solvate the reactants A and B in a bimolecular process, there are many degrees of freedom which must be considered in
evaluating the partition functions qA , qB , and q6r . Moreover, the number of
degrees of freedom often changes when the transition state is formed. For example, consider the case that A and B are two highly charged cations (reaction
(7.3.6)). Each cation is strongly solvated so that the internal degrees of freedom
associated with both the cation and surrounding solvent molecules must be considered in evaluating qA and qB . The charge on the transition state, zA zB , is
much higher. As a result, more solvent molecules are probably solvating the
activated complex than the total number solvating A and B separately. Thus,
formation of the transition state is accompanied not only by a change in the
energy of the system, but also by a change in entropy. This example illustrates
the importance of considering the Gibbs energy in discussing the course of the
reaction through the transition state.
There is considerable interest in comparing the reaction rate for a given reaction in solution with that in the gas phase [G3]. Assuming that the rate of decomposition of X6 is the same in both phases, the ratio of the rate constants is

328

LIQUIDS, SOLUTIONS, AND INTERFACES

"
#
s
6 Gs  6 Gg
ksr yA yB K6 yA yB

exp 
yX6 Kg6
yX6
RT
kgr

7:4:27

where kir is the rate constant in phase i, Ki6 , the equilibrium constant to form the
activated complex in phase i and 6 Gi , the corresponding standard Gibbs activation energy. If consideration is limited to reactions not involving ions in nonpolar solvents, the activity coecients can be neglected. Furthermore the Gibbs
activation energy in solution can be expressed as follows:
6 Gs 6 Gg 6 Gsolv
6

Gsolv

Gs .

7:4:28
6

Gsolv

where 
is the solvent contribution to 
In other words, 
is the
contribution to the work done due to the presence of the solvent in bringing the
reactants A and B from sites in the solution which are very far apart up to the
transition state site where they are in the same solvent cage. The expression for the
rate constant in solution is then


6 Gsolv
ksr kgr exp
7:4:29
RT
An eective way of estimating 6 Gs and 6 Gg is to carry out molecular
dynamics calculations for the system being studied. In this way, cumbersome
quantum-mechanical calculations involving the reacting system in the solvent
are avoided. From a qualitative point of view, an atom exchange reaction involving neutral reactants in a non-polar solvent is expected to be faster in the solvent
than in the gas phase. This is due to the fact that two neutral species form one
species in the transition state. Very few experimental studies have been carried
out; one example of a reaction which has been studied is
H D2 ! HD D

7:4:30

This reaction is faster in solution than in the gas phase by approximately a factor
of 40. Theoretical calculations agree with the experimental result [G3].
Transition state theory has also been applied in quite another way to reactions
in solution. Reaction (7.4.2) can be described as a reaction precursor equilibrium
which is characterized by the diusion of A and B to a position close enough so
that reaction can take place. This pre-equilibrium has an equilibrium constant
which can also be thought of as a collision frequency. The expression for the rate
constant is then


 G
7:4:31
kr ZB exp
RT
where ZB is the collision frequency for the bimolecular process in solution and
 G is the standard Gibbs activation energy for reaction (7.4.3).  G diers
from 6 G in that it is calculated using the total partition functions for A, B, and
X6 ; on the other hand, 6 G has the contribution from one degree of vibrational
motion in the activated complex factored out. Electron transfer kinetics in solution are usually analyzed on the basis of equation (7.4.31). A more complete
description of this subject as well as methods of estimating ZB are given later
in sections 7.8 and 7.10.

CHEMICAL REACTION KINETICS IN SOLUTION

329

Medium eects are very important for solution reactions. They are dealt with
quantitatively through the activity coecient ratio which appears in equation
(7.4.15). Thus, if the nature of the non-reacting components in the solution is
changed, one can expect to observe a change in the rate constant. The easiest way
of dealing with these eects is to keep the nature of the medium constant when
other aspects of the system being studied are changed. On the other hand, there is
an interest in studying the eects of the medium on solution reactions. This
subject is considered in more detail in section 7.10.

7.5 Diffusion-Controlled Rapid Reactions


The fastest reactions in solution are limited in their reaction rates by mass transfer. For most bimolecular reactions this limitation arises because the two reactants must diuse together in order to form a reactant pair. Therefore it is
interesting to estimate the magnitude of the rate constant for a diusion-controlled reaction and to compare it with experimentally determined rate constants
for very fast reactions. The treatment presented here applies to bimolecular reactions involving either molecules or ions.
Consider a bimolecular reaction
A B ! products

7:5:1

which takes place every time these species come into contact. In order to solve the
mass transfer problem, it is imagined that only A moves and B is stationary. On
the basis of the analysis in section 6.7, the ux of species A is
z u c
JA DA ;cA  A A A ;(
7:5:2
jzA j
where ;cA is the gradient of the concentration of A, ;( the gradient of the
electrostatic potential, DA , the diusion coecient of A, uA , its mobility, and
zA , its charge. The second term obviously accounts for electrostatic eects
which are only important in the case of reactions involving ions. In the case of
reactions involving molecules, the second term disappears. Using the relationship
between the diusion coecient and mobility of an ion (equation (6.7.21)), the
above equation may be written as


z Fc
7:5:3
JA DA ;cA A A ;(
RT
It is convenient to re-express the electrostatic term in terms of the electrostatic
energy UeA , where
UeA zA F
Thus, the equation for the ux of A may be written as
c
JA DA ;cA A ;UeA
RT

7:5:4

7:5:5

The problem is now solved, assuming that diusion is a spherically symmetrical process and that it occurs at a steady state. Furthermore, the reactants

330

LIQUIDS, SOLUTIONS, AND INTERFACES

are assumed to be spherical with radii rA and rB . The ux which is a constant


independent of angular direction becomes


dcA cA dUeA

JA DA
7:5:6
dr
RT dr
Introducing the function

U
Cr cA exp eA
RT
one may write


7:5:7



UeA dCr
JA DA exp
dr
RT

7:5:8

The fact that both A and B move in reality is now dealt with by using DA DB
as the mutual diusion coecient; this eectively accounts for the motion of the
coordinate system which is now dened with respect to B. Thus,


UeA dCr
7:5:9
JA DA DB exp
RT
dr
The number of molecules moving through the surface of a sphere of radius r can
now be calculated:


dnA
UeA dCr
2
2
4pr JA 4pr DA DB exp
7:5:10
dt
RT
dr
At a steady state, dnA =dt is a constant so that solution of the dierential equation
is relatively easy.
The rate of reaction is found by integrating equation (7.5.10) in the form
dnA
dt

expUeA =RT
dr
r2

cA

4pDA DB dCr

7:5:11

In the limit that r equals a the molecules A and B are in contact, that is,
a rA rB

7:5:12

In this case, species A reacts with species B, and the concentration of A is zero. At
very large distances, the concentration of A is its bulk value, cA . After integration,
one obtains
dnA
4pDA DB a y cA
7:5:13
dt
where
1

expUeA =RT
dr
7:5:14
y1 a
r2
a

The factor a is introduced into the fraction y, so that it is dened as a dimensionless quantity. Equation (7.5.13) applies to one molecule of B. By multiplying by
the concentration of B, cB , one obtains an expression for the reaction rate:

CHEMICAL REACTION KINETICS IN SOLUTION

dnA
4pDA DB a y cA cB
dt

331

7:5:15

The second-order rate constant is


kr 4pNL DA DB a y

7:5:16

where Avogadros constant NL is introduced so that this quantity has units of


m3 mol1 s1 when DA and DB have units of m2 s1 and a, units of meters.
When the two reactants are molecules, the electrostatic energy UeA is zero and
the fraction y is equal to one. Then, the expression for kr is
kr 4pNL DA DB a

7:5:17

When the two reactants are ions, the value of y is most easily estimated for the
case that the solution is very dilute and the electrostatic energy is given by
UeA

zA zB e20 NL a

r
4pe0 es r

7:5:18

where e0 is the electronic charge, es , the relative permittivity of the solvent, and e0 ,
the permittivity of free space. Integration of equation (7.5.14) gives the nal result
1
a
y ea=a  1
7:5:19
a
Finally, if the bimolecular reaction involves the same species, namely,
A A ! products

7:5:20

the rate of reaction is given by




dcA
2kr c2A
dt

7:5:21

In this case the expression for the diusion-limited bimolecular rate constant is
kr 4pNL DA a y

7:5:22

EXAMPLE

Estimate the diusion-limited rate constant for the recombination of I


radicals
in carbon tetrachloride at 258C given that the radius of the radical is 200 pm,
and its diusion coecient, 4:12  109 m2 s1 .
The reaction is
7:5:23
I
I
! I2
Since the reactants are neutral, electrostatic eects are negligible and y is equal
to one. The collision distance a is equal to 400 pm. Thus,
kr 4p  6:022  1023  4:12  109  4:0  1010
1:27  107 m3 mol1 s1

7:5:24

The experimentally observed value for kr is 8:2  106 m3 mol1 s1 . The fact
that the experimental value is smaller than that predicted theoretically suggests
that there may be a small activation energy associated with this process.

332

LIQUIDS, SOLUTIONS, AND INTERFACES

EXAMPLE

Estimate the diusion-limited rate constant for recombination of H3O+ and


OH to form water at 258C given that the diusion coecients for these species
are 9:34  109 m2 s1 and 5:23  109 m2 s1 , respectively, and assuming that
the eective radius for each species is 250 pm.
The reaction is
H3 O OH ! 2H2 O

7:5:25

This reaction is accelerated by the attractive Coulombic force between the ions.
The electrostatic parameter is
zA zB e20 NL
1  1:602  1019 2  6:022  1023

4pe0 es RTa 4p  8:854  1012  78:5  8:3145  298:2  5  1010


7:5:26
1:429
The electrostatic factor y is
y

1:429
1:879
exp1:429  1

7:5:27

The estimate of the rate constant is


kr 4p  6:022  1023  14:57  109  5  1010  1:879
1:04  108 m3 mol1 s1

7:5:28

The experimental value of kr is 1:4  108 m3 mol1 s1 . The theoretical estimate is low probably because the model of the reactants as hard spheres is
inappropriate for this system. This follows from the fact that the reacting ions
have a special relationship to the solvent, water.
Although the treatment described here is approximate it certainly gives the
correct order of magnitude for the rate constants of very fast reactions in solution.
Methods of improving these estimates have been considered by Noyes [2]. In the
following section experimental methods of studying very fast reactions based on
relaxation techniques are considered.

7.6 Relaxation Techniques for Rapid Reactions


Relaxation techniques were developed by Eigen and coworkers [13, 14] as a means
of studying very fast reactions in solution. The experiment involves applying a
stress rapidly to a system at equilibrium and following the time lag required to
establish new equilibrium concentrations. For example, in the temperature jump
method, the temperature of the system can be changed by several degrees in a time
as short as 106 s by dissipating the energy stored in a high-voltage capacitor in a
solution which contains a conducting electrolyte. Spectrophotometric or conductometric methods are then used to follow the relaxation of the components of the
equilibrium to new concentrations which reect the value of the equilibrium
constant at the higher temperature. Then, the prole of concentration against

CHEMICAL REACTION KINETICS IN SOLUTION

333

time is analyzed to nd the rate constants characterizing the reactions taking


place. In the following section some simple examples are considered to illustrate
how the relaxation data are analyzed. Some important experimental techniques
used are also outlined.
A. Analysis of the Experimental Data
As a simple example, consider the equilibrium in a homogeneous reaction
kf

AB C
kb

7:6:1

which is characterized by a forward rate constant kf and a backward rate constant


kb . At equilibrium
cCe
k
Ke f
cAe cBe
kb

7:6:2

The initial concentrations of these components which are present before the stress
is applied to the system are cA0, cB0, and cC0. Then at any moment during the
relaxation one may write
x cA  cAe cB  cBe cCe  cC

7:6:3

where x is the extent that the instantaneous concentrations dier from their new
equilibrium values. The rate of reaction is


dcA dx

kf cA cB  kb cC
dt
dt

7:6:4

This equation is now written in terms of the variable x:


dx
kf cAe xcBe x  kb cCe  x
dt
kf cAe cBe kf xcAe cBe kf x2  kb cCe kb x

7:6:5

From equation (7.6.2)


kf cAe cBe  kb cCe 0

7:6:6

Furthermore, the term in x may be neglected because the departure from equilibrium is not large. The nal expression for the rate of reaction is
dx
kf cAe cBe kb x
dt

7:6:7

This has the same form as the expression derived for a simple rst-order reaction
with the quantity in the square brackets as the rst-order rate constant. The usual
practice in relaxation kinetics is to dene the reciprocal of this quantity as the
relaxation time t for the reaction. Thus,
t kf cAe cBe kb 1

7:6:8

By varying the equilibrium concentration of one reactant while holding the concentration of the other high and approximately constant, the two rate constants

334

LIQUIDS, SOLUTIONS, AND INTERFACES

Table 7.4 Relaxation Times for Equilibrium


Reactions Involving One Step
Reaction

Relaxation Time/t

kf

kf kb 1

A B
kb

kf

4kf cAe kb 1

2A B
kb

kf

kf cAe cBe kb 1

AB C
kb
kf

AB CD
kb

kf cAe cBe kb cCe cDe 1

which contribute to t can be separated. Relaxation times for several other


mechanisms involving one step are summarized in table 7.4. If these reactions
do not correspond to equilibria but actually are irreversible, then the relaxation
time is found by setting kb equal to zero.
Most chemical reactions involve more than one elementary step. As a result
there is more than one relaxation time associated with the reacting system. In the
case of fast reactions it is necessary to extract information about each step.
Although the mathematical analysis of complex systems can be quite involved,
it is important to understand how such an analysis is made. The following example involves a two-step mechanism in which both steps are reversible.
Consider a bimolecular process
k1f

A B AB
k1b

7:6:9

in which the reactive intermediate AB is formed. The forward rate constant for
this reaction is k1f and the backward rate constant, k1b. The species AB can
undergo an intramolecular rearrangement
k2f

AB C
k2b

7:6:10

to form the nal product C. The second step is characterized by a forward rate
constant k2f and a backward rate constant k2b.
Now one denes variables which relate to the departure of each concentration
from its equilibrium value. They are
xA cA  cAe cB  cBe
xAB cAB  cABe
xC cC  cCe

7:6:11
7:6:12
7:6:13

Mass conservation requires that


xA xAB xC 0
The rate of reaction of A is

7:6:14

CHEMICAL REACTION KINETICS IN SOLUTION

dcA
k1f cA cB  k1b cAB
dt

335

7:6:15

In terms of the variables xA and xAB this becomes




dxA
k1f xA cAe xA cBe  k1b xAB cABe
dt

7:6:16

When this expression is simplied by neglecting terms in x2 and using the equilibrium condition
k1f cAe cBe k1b cABe

7:6:17

one obtains


dxA
k1f cAe cBe xA  k1b xAB
dt

7:6:18

The expression for the rate of formation of the intermediate AB is


dcAB
k1f cA cB  k1b cAB  k2f cAB k2b cC
dt

7:6:19

On the basis of equilibrium (7.6.10)


k2f cABe k2b cCe

7:6:20

Making use of equations (7.6.11)(7.6.14), the expression for the rate of formation
xAB is
dxAB
k1f cAe cBe  k2b xA  k1b k2f k2b xAB
dt

7:6:21

Equations (7.6.18) and (7.6.21) comprise linear rst-order dierential equations in the variables xA and xAB. For simplicity they may be rewritten as
dxA
a11 xA a12 xAB
dt

7:6:22

dxAB
a21 xA a22 xAB
dt

7:6:23



where

a11 k1f cAe cBe

7:6:24

a12 k1b

7:6:25

a21 k1f cAe cBe k2b


a22 k1b k2f k2b

7:6:26
7:6:27

This system of equations may be solved by several methods including Laplace


transformation and matrix algebra. The mathematical details have been given by
Connors [G2].
The solutions to these equations may be expressed in terms of the relaxation
times t1 and t2 for step 1 and step 2, respectively. The sum of their reciprocals is
given by
1
t1
7:6:28
1 t2 a11 a22
and the product by

336

LIQUIDS, SOLUTIONS, AND INTERFACES

11 t1
2 a11 a22  a12 a21

7:6:29

Using the denitions of the coecients given above these become


1
t1
1 t2 k1f cAe cBe k1b k2f k2b
1
t1
1 t2 k1f cAe cBe k2f k2b k1b k2b

7:6:30
7:6:31

Thus, each relaxation time depends on all four rate constants.


The analysis of the experimental data to obtain the two relaxation times is
equivalent to the analysis of two consecutive rst-order reactions. If the values of
t1 and t2 are quite dierent, this is not a problem and can be accomplished using
standard methods of data analysis [G2]. If t1 and t2 are close to one another,
separate determination of these quantities is very dicult. Typically, the ratio of
the relaxation times must be greater than three to estimate them separately. In this
regard, some variation in the relative values of t1 and t2 can be achieved by
changing the values of cAe and cBe.
Further analysis of the data involves determining t1 and t2 for a range of values
of the sum cAe cBe. On the basis of equations (7.6.30) and (7.6.31), the individual rate constants can then be found using linear plots of t11 t21 against
cAe cBe and (t1t2)1 against the same quantity.
One limiting case of interest occurs when t1t2. This corresponds to reaction
(7.6.9) coming rapidly to equilibrium with the second step (7.6.10) being much
slower. Under these circumstances, the terms in k2f and k2b in the expressions for
a21 and a22 disappear. The reaction is then termed decoupled because the kinetic
processes determining the rst relaxation can be completely separated from those
determining the second.
The above system provides one example of the treatment of a relaxation process for a complex reaction involving a two-step process. Other systems involving
two or more steps can be treated by this method, and details can be found elsewhere [G2, 14].
B. Some Experimental Methods
The temperature jump (T-jump) method is the most widely used relaxation technique. It is based on the temperature dependence of the equilibrium constant for
the reaction. For a one-step process such as reaction (7.6.1), this is given by the
vant Ho equation, that is,
@ ln Ke
H

@1=T
R

7:6:32

where H is the standard enthalpy change for the reaction. The experiment
usually involves a specially designed cell with a small volume of solution. The
temperature jump is accomplished via the joule heating which occurs when a
capacitor is discharged through the solution, which must be electrically conducting. Typical temperature changes are between 1 and 10 C, and these can be
achieved in times as short as 10 ns. Although this technique was originally used
with aqueous electrolyte solutions, it can also be applied to systems with much
lower conductivity using microwave and laser heating techniques. A typical T-

CHEMICAL REACTION KINETICS IN SOLUTION

337

jump cell designed for use with an electrical discharge is shown in g. 7.8.
Monochromatic light passes through the cell and out to a detector in which the
absorption transient is recorded. The relaxation time is determined by analyzing
the absorption data as a function of time.
EXAMPLE

A system with an equilibrium constant of 5  105 L mol1 at 25 C is subjected


to a temperature jump of 5 C. Calculate the new equilibrium constant given
that the standard enthalpy change for the reaction is 10 kJ mol1 .
On the basis of equation (7.6.32)


H 1
1
ln Ke T2  ln Ke T1 

R T2 T1
7:6:33


10,000
1
1
2

6:65  10

8:314 303:2 298:2


The equilibrium constant at 30 C is 5:3  105 L mol1 corresponding to a 7%
percent change.
The pressure jump (P-jump) relaxation technique employs a sudden change in
pressure for a reversible reaction which has associated with it a signicant volume
change. In this case the change in the equilibrium constant with pressure is given
by
@ ln Ke
V

@P
RT

7:6:34

The sample is mounted in a exible cell which is placed in a pressurized vessel at a


high pressure, say, 60 atm. The pressure is suddenly reduced by rupturing a diaphragm so that it drops to the atmospheric value. Unfortunately, the value of
V associated with most reactions is rather small, so that the equilibrium is only
slightly perturbed by the pressure change.

Fig. 7.8 Experimental setup with a temperature-jump cell designed for Joule heating by
means of an electrical discharge.

338

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 7.9 Illustration of the time


dependence of the forcing function,
for example, pressure, and the
concentration of one reactant in (A) a
step relaxation experiment and (B) an
experiment with a periodic
perturbation.

The electrical eld-jump method is applied to reactions involving ions and


dipoles. The eld induces a shift in the solution equilibrium in the direction of
producing more ions, or in the orientation of dipoles. Thus, when a high electrical
eld is applied to a solution containing a weak electrolyte, the extent of dissociation increases. The method has been used to study metal ion complex formation
reactions and acidbase reactions.
Ultrasound experiments rely on the periodic oscillations which result in a solution when a high-frequency sound wave is passed through it. Sound waves produce periodic oscillations in pressure and temperature which result in a periodical
perturbation in a chemical equilibrium (see g. 7.9). In aqueous solutions, the
pressure change is more important, whereas in non-aqueous solutions the temperature change is predominant. When the frequency of the sound wave is high
enough, the chemical equilibrium cannot respond quickly enough and a phase
shift is observed between the oscillations in the concentration of one component
and the oscillations in pressure and/or temperature. Using transducers, these
oscillations can be converted to electrical signals and precisely followed using
lock-in ampliers or similar electronic instrumentation.

7.7 Laser Spectroscopy and Femtochemistry in


Solutions
The use of short light pulses to study rapid chemical reactions in solution dates
from the work of Norrish and Porter [15]. In a ash photolysis experiment a light

CHEMICAL REACTION KINETICS IN SOLUTION

339

pulse of short duration is used to irradiate the solution, where it is absorbed by


molecules or ions. The resulting excited species loses its excess energy either by
returning to the ground state via uorescence or some other process, or by a
chemical reaction which produces radicals and other intermediates of high energy.
In the latter case, further reactions of these species are monitored using a less
energetic spectroash red a short time after the initial photolysis ash. This
procedure is repeated several times with dierent delay times between the photolyzing ash and the spectroash. In this way the kinetics of the reactive intermediate can be elucidated.
In the original ash photolysis experiment a high-voltage capacitor was discharged through a ash photolysis lamp. The typical energy involved about 1000 J
which was dissipated within a few microseconds. This kind of experiment is
carried out at present using lasers. Using these devices one is able to resolve
chemical events at times less than one picosecond. This allows the experimenter
to monitor changes which occur during times for which the vibrational motion in
molecules is essentially frozen. These exciting developments have led to the coining of the new word femtochemistry, which refers to chemistry occurring in the
femtosecond time scale. In this section the important features of an experiment
involving ultrafast pulsed lasers are briey outlined. Then applications of these
experiments to reactions in solution are described.
A. Experimental Aspects
In order to discuss this topic a brief introduction to the properties of common
lasers is given. The word laser is an acronym for light amplication by stimulated
emission of radiation. A molecule can absorb a quantum of light when the associated energy corresponds exactly to a transition from the ground state in the
molecule to an available excited state. Under normal circumstances the excited
molecule decays back to the ground state by some process which may be radiative,
involving the emission of light, or non-radiative, involving the generation of heat.
Photon emission occurring this way is called spontaneous emission. On the other
hand, if the system with molecules in the excited state is irradiated with an
external light source corresponding in energy to that which would be emitted,
each molecule can relax by emitting another photon of the same frequency. Under
these circumstances the probability of emission is enhanced by the presence of
similar photons and the emission occurs preferentially in the same direction as the
external source. This leads to a population inversion with more molecules in the
excited state than in the ground state. This type of emission is called stimulated
emission and is the principal feature of laser operation. Moreover, since the emission occurs preferentially in the direction of the applied beam, this beam is
thereby amplied in intensity. The stimulated photons, have the same phase
and polarization as the incident photons, so that the laser radiation is termed
coherent.
The above discussion implies that a laser may be designed with a absorbing
system involving two quantum states, namely, the ground state and the excited
state. However, an analysis of the rate at which molecules reach the excited state
from the ground state with respect to the rate at which molecules in the excited

340

LIQUIDS, SOLUTIONS, AND INTERFACES

state return to the ground state by emission shows that a population inversion is
not possible with a two-state system. In order to realize a population inversion a
multilevel system is required. An example of a three-level system which is capable
of lasing action is shown in g. 7.10. The ground state system at energy E1 is
pumped to the excited state E2 . It rapidly undergoes a non-radiative transition to
a lower energy level E3 The lasing action involves the emission of a quantum of
light corresponding to the energy dierence E3  E1 . Other multiple level lasing
schemes have been used to design functioning lasers [15].
The three essential elements of a laser are the resonator containing the gain
medium, a pumping source that excites the gain medium, and mirrors which direct
the light beam back and forth through the gain medium (see g. 7.11). One of
these mirrors is not completely reective, so that part of the laser beam escapes
giving the output light from the laser system.
The gain medium can be a solid, a liquid solution, or a gaseous mixture. One
the rst lasers made use of a solid ruby rod which consists of Al2O3 doped with a
minor Cr3 impurity. This system outputs light at a wavelength of 694.3 nm.
Other solid-state systems make use of Nd3 or Ti3 as the gain medium.
Popular lasers with a gas as the gain medium include the HeNe laser, and the
CO2 laser. Of course, the output frequency depends on the characteristics of the
gain medium and its associated spectroscopic properties.
The energy source used to initiate lasing action is often a high-intensity light
source which is used to excite the gain medium. In the case of gas phase lasers, an
electrical discharge can be used to provide the energy to pump the gas molecules
into the excited state involved in laser action. The properties of the laser cavity are
important in achieving the necessary population inversion with more molecules in

Fig. 7.10 Transitions and energy levels in a three-level laser.

CHEMICAL REACTION KINETICS IN SOLUTION

341

Fig. 7.11 Schematic diagram of the essential components of a laser.

the excited state than in the ground state. Thus, the design of the resonating
system by which most of the light travels back and forth between the two mirrors
shown in g. 7.11 is an important feature of the system.
Lasers are operated in two modes, on a continuous-wave basis, or in a pulsed
mode. In the continuous mode the laser is pumped steadily at a rate sucient to
supply the emergent laser energy and the heat losses due to the non-radiative
processes. The pulsed laser is of interest for kinetic studies because it allows a
pulse of optical energy to be applied to the experimental system over a known
period of time. In this mode, the laser is pumped with a pulsed energy source, and
a shutter is used to control the release of energy in the laser. The shutters may be
mechanical or electrooptical, and a variety of pulsing techniques have been developed. A self-mode-locked Ti:sapphire laser is a popular system for ultrafast spectroscopy. It can be tuned to operate over a wide range of frequencies in the visible,
it has high average power output, and it can deliver ultrashort pulses down to 10
fs in duration. More details about the generation of ultrashort light pulses can be
found elsewhere [1618].
Having delivered optical energy to the experimental system using an ultrafast
pulse, the next part of the experiment involves following the changes which occur
over a very short period of time. This is called ultrafast time-resolved spectroscopy. One of these is pump-probe spectroscopy. After the system has been
pumped to an excited optical state it is probed by a series of light pulses which
are used to follow the response of the system as a function of time. For example,
the pump-pulse system may be used to excite a simple molecule from its ground
electronic level to an excited electronic level where a bond in the molecule is
ruptured. The probe pulses can follow the absorption of light by one of the
fragments of the molecule. On the other hand, the probe pulses can be used to
induce uorescence in one of the fragments, and the uorescence is followed as a
function of time. The probing pulse may be the same frequency as the pumping
pulse, or it may have a dierent frequency depending on the design of the experiment. The time delay between probe and pulse is obtained by altering the path
length for the two light signals in the optical system.
When the experimental system emits light after the initial pumping pulse, quite
dierent techniques can be used to obtain a time-resolved spectrum of the sample
emission. The simplest of these is time-correlated single photon counting. The
time resolution of this technique is limited by the design of the photon detectors.
Two other methods used in emission spectroscopy are the streak camera and

342

LIQUIDS, SOLUTIONS, AND INTERFACES

uorescence up-conversion. Details of these experiments which are beyond the


scope of this monograph can be found elsewhere [1618].
Experimental studies of solution reactions using pulse lasers have blossomed
since the 1980s. Important examples are considered in the following discussion.
B. Time-Resolved Studies of Solvation
Very interesting studies have been made of the eects of solvation on the timeresolved uorescence of certain dye molecules dissolved in polar solvents. The
solute molecules are often characterized by a non-polar ground state and a dipolar excited electronic state. As a result, when the excited state is formed by the
absorption of a quantum of light, the molecule nds itself in a solvation environment with which it is not at equilibrium. With increasing time, the solvent restructures responding to the new charge distribution in the excited state. This results in
a lowering of the energy of the excited state with respect to the ground state. As a
result the uorescence spectrum changes with time with its peak frequency shifting
to lower values. This shift in the emission spectrum in the red direction is called a
Stokes shift (SS). Analysis of the spectral features as a function of time is used to
obtain molecular details of the solvent restructuring process.
The uorescence spectra are analyzed to obtain the correlation function C(t)
dened as
Ct

nm t  nm 1
nm 0  nm 1

7:7:1

where nm(t), nm(0), and nm(1) are the frequency of the maximum on the uorescence spectra observed at time t, zero, and innity, respectively. The time
dependence of C(t) is related to the relaxation process of the solvent environment
around the dipolar excited state. A theoretical model for this process has been
derived in which the dye molecule in its excited state is considered to be a point
dipole embedded in a dielectric continuum [19]. In this case the correlation function C(t) is an exponentially decaying function of the form
 
t
7:7:2
Ct exp
tL
where tL is the longitudinal relaxation time of the solvent (see section 4.7). Studies
carried out in a wide variety of solvents show that this simple model is approximately correct. Results obtained in a variety of solvents with the coumarin dye
C152 (g. 7.12) are summarized in table 7.5.
It is clear from these results that there is an approximate correlation between
the value of the average relaxation time tS and the longitudinal relaxation time tL
(see section 4.7). However, careful examination of the time-dependent Stokes shift
(TDSS) data reveals that Ct is described by more than one relaxation process.
This is not dicult to understand, considering that many aprotic solvents are
found to have more than one relaxation process. This can be attributed to the
formation of dimers and other aggregates in these liquids. This is especially the
case in aprotic solvents such as DMSO and PC, which have very high dipole
moments. Alcohols also have multiple relaxation processes due to the presence

CHEMICAL REACTION KINETICS IN SOLUTION

343

Fig. 7.12 Structure of the coumarin dye C152.

of hydrogen bonding (see section 4.7). The most important point is that the Debye
model which is applied to the analysis of the dielectric relaxation data is a macroscopic model. What is really needed to interpret the spectroscopic data is a molecular model for the dielectric properties of the solvents.
The example given is only one of several which have been reported for solvation phenomena studied at very short times after a molecule absorbs a quantum of
light [17, 18]. These studies have only become possible with the advent of highspeed laser technology.
C. Ultrafast Photoisomerization Reactions
Stilbene is a molecule which exists in two isomeric states because of the large
energy barrier associated with rotation around the central double bond (see g.
7.13). It has been known for some time [22] that when stilbene is excited to its rst
singlet state by absorption of UV light, it rapidly uoresces to the ground state
but with some molecules in the other isomeric form. Thus, if cis-stilbene is irradiated with ultraviolet light, one obtains approximately 50% trans-stilbene and

Table 7.5 Average Relaxation Times from Time-Dependent Stokes Shifts


(TDSS) for Coumarin C152 in Various Solvents Together with the
Longitudinal Relaxation Time Determined by Dielectric Relaxation
Spectroscopy [20]
Solvent
MeOH
AC
AcN
BzN
DMF
DMSO
PC
PrN

Longitudinal Relaxation Time*


tL /ps

Average Relaxation Time from TDSS


ts =ps

1.0
4.0
0.3
0.2
5.7
0.7
1.5
2.4
0.4

6.2

0.68
0.52
5.0
1.0
1.2
2.4
0.85

*The values of tL for aprotic solvents with more than one relaxation process are averages; two
values are given for methanol, which has three relaxation processes. (See section 4.7 and [21].)

344

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 7.13 Isomerization of stilbene.

50% cis-stilbene. The kinetics of the photoisomerization reaction is so rapid that


it can only be resolved using a pump-pulse laser technique. These experiments
allow one to study the role that the solvent plays in the kinetics of the isomerization process.
Detailed studies of this photo-initiated reaction have led to a picture of the
energetics associated with the isomerization reaction (g. 7.14). When cis-stilbene
reaches the excited singlet state, it rapidly loses energy by twisting about the
central double bond. It then returns to the ground state from the energy minimum
by uorescence and gives either the trans or cis isomer, depending on how the
molecule leaves the twisted form to return to a low-energy conguration in the
ground state. For example, when cis-stilbene is irradiated at 316 nm emitted light
can be observed at 475 nm when the experiment is carried out at 20 C in decane.
The uorescence decay occurs over a few picoseconds and in this case is characterized by relaxation time t of 1.27 ps [23]. Studies have been made of the

Fig. 7.14 Energy proles for


twisting of the stilbene molecule in
the ground state S0 and rst excited
singlet state S1 .

CHEMICAL REACTION KINETICS IN SOLUTION

345

dependence of t on solvent nature, temperature, and the nature of substituents on


the stilbene molecule [22].
Fluorescence decay times measured in several polar solvents are summarized in
table 7.6. It is apparent there is a correlation between the viscosity and t, longer
decay times being observed in more viscous solvents. This eect is related to the
friction of the solvent molecules surrounding stilbene when it undergoes rotation
in the excited state. Solvent friction in solution kinetics is of considerable theoretical interest (see section 7.10). In order to determine the activation parameters
associated with photoisomerization, decay times have been measured in a series of
solvents with the same structure. The temperature of the experiment is varied so
that the solvents all have the same viscosity. A plot of the logarithm of t against
the reciprocal of the absolute temperature using data obtained in this way is
known as an isoviscosity plot. Some data for the isomerism of cis-stilbene in the
alkanes are given in table 7.6. The decay times observed in these solvents are
longer than those obtained in polar solvents indicating that a larger energy barrier
is involved. The isoviscosity plot of these data gives an activation energy of 4.6 kJ
mol1. The corresponding result for trans-stilbene is 14.6 kJ mol1 [22]. These
results are consistent with the energy prole for the excited state shown in g.
7.14. When the same reaction is studied in polar solvents, namely, a series of nalkanenitriles, the barrier is signicantly lower (10.8 kJ mol1). This suggests that
the excited state has some polar character. Much more has been learnt about this
simple unimolecular reaction on the basis of the ultrafast laser studies. It is clear
from the data presented in table 7.6 that the study could not be carried out
without the ability to resolve the spectral data on a time scale less than 1 ps.
This kind of experiment has been applied to several important solution reactions
and represents the forefront of modern research in this area.

Table 7.6 Cis-stilbene Fluorescence Decay Times in


Organic Solvents for Emission at 475 nm [23]
Solvent

Temperature
T/8C

Viscosity
Z/mPA s

Decay Time
t/ps

20
20
20
20
20

0.38
2.20
0.59
2.38
4.18

0.38
0.63
0.50
0.80
0.94

7
31
64
87

0.78
0.78
0.78
0.78

1.58
1.23
1.02
0.92

Polar
Acetonitrile
Dimethyl sulfoxide
Methanol*
2-Propanol
n-Pentanol
Non-polar
Octane
Decane**
Dodecane
Tetradecane
*Measured at 465 nm.
**Measured at 450 nm.

346

LIQUIDS, SOLUTIONS, AND INTERFACES

7.8 The Theory of Homogeneous Electron Transfer


The theory of electron transfer is the most developed of that for any reaction in
solution. In addition this type of reaction has been studied extensively by experiment. As a result many of the predictions made by theory have been addressed in
the laboratory. As was seen from earlier discussion, simple electron transfer may
proceed by two mechanisms, inner sphere and outer sphere. The inner sphere
mechanism involves both electron and atom transfer. The discussion here is limited to the outer sphere mechanism, which involves the transfer of a single electron without the formation or breaking of any chemical bonds.
Within the context of transition state theory there are two problems to be
addressed in developing a model to estimate the rate constant for electron transfer. One is the estimation of the Gibbs energy of activation for the process; the
second is estimation of the pre-exponential factor. The model used to describe the
activation barrier is considered rst.
Consider the simple electron transfer process
A B ! A B

7:8:1

+A
A e(

B e(
+B

7:8:2

involving the redox couples


7:8:3

When the reactants are at the site where electron transfer occurs, rearrangement
of the bond lengths and angles within the reactants must take place to achieve a
conguration intermediate between that of the reactants and that of the products.
In addition, there must be some rearrangement of the solvation atmosphere
2
around charged reactants. For example, if CrH2 O3
6 and FeH2 O6 are the
reactants, the length of the metal ionligand bonds must change. In the case of
CrH2 O3
6 this means that the bonds are lengthened to achieve a structure inter2
2
mediate between that of CrH2 O3
6 and CrH2 O6 . In the case of FeH2 O6 , the
length of the metal ionligand bonds decreases to achieve a conguration closer to
that of FeH2 O3
6 . This process is called inner sphere reorganization. At the same
time there must be a readjustment of the solvation atmosphere around these
highly charged ions. According to the Born model (section 3.4), the Gibbs energy
of ion solvation depends on the square of the ionic charge. The solvation atmosphere must readjust to achieve a solvation conguration intermediate between
that of reactants and product. This process is called outer sphere reorganization.
Both inner sphere and outer sphere reorganization contribute to the energy barrier associated with electron transfer. These processes occur randomly due to the
thermal uctuations in the system. According to the FrankCondon restriction,
electron transfer is only possible when this, yet unspecied, intermediate conguration is achieved.
In order to visualize the energy barrier between reactants and products, it is
assumed that each system can be represented as a classical harmonic oscillator
along the reaction coordinate. This is illustrated in g. 7.15. The left-hand parabola gives the Gibbs energy of the reactants and the right-hand parabola, that of

CHEMICAL REACTION KINETICS IN SOLUTION

347

Fig. 7.15 Gibbs energy barrier for an


outer sphere electron transfer process with
a standard Gibbs energy change of
G(A). Interaction of the surfaces for
reactants and products leads to electronic
coupling and creates an energy gap 2Jr at
the point where they intersect (B).

the products. There are three important characteristics of this diagram. The rst is
that the curvature of the two parabolas is assumed to be the same. This is equivalent to assuming that the work done to achieve a given non-equilibrium conguration of the reactant system is the same as that in the product system when
measured from the parabolas minimum. This is clearly an approximation which
may not be valid for some systems. A second important feature of the diagram is
the distance between the minima of the two parabolas. This is related to the
relative positions of the two reactants before reaction and determines the height
of the energy barrier along the reaction coordinate. As the distance between the
minima increases the value of the Gibbs energy at the point where they intersect
increases. This corresponds to an increase in the Gibbs energy of activation for
the reaction.
The third feature of the energy barrier diagram shown in g. 7.15 is related to
the point where the Gibbs energy surfaces meet. Electron transfer is not possible if
the individual parabolas remain intact. Electronic coupling of the energy surfaces
is necessary if the system is to pass from the reactant state to the product state.
This is illustrated as a fusing of the lower portions of the two parabolas at the
intersection point to create a gap of height 2Jr between the lower and upper
portions of the curve. The magnitude of Jr determines whether the reaction is
adiabatic or diabatic (non-adiabatic). An adiabatic reaction is one for which the
electronic coupling is strong. This means that every reactant system which reaches
the activated state, that is, the intersection point of the two parabolas, passes
through to the product state if solvent friction is absent. If the electronic coupling
is weak for some reason, so that Jr  kT, then the reaction is diabatic and the
passage from the reactant state to products is less probable. An important factor
involved in determining the degree of reaction adiabacity is the distance to which
the species A and B, which exchange an electron, can approach one another. If
this distance is large, then the degree of electronic coupling is small and the
reaction is diabatic. An important example of this type of electron transfer occurs
in biochemistry when one of the redox centers is embedded in a large biomolecule,

348

LIQUIDS, SOLUTIONS, AND INTERFACES

for example, in a protein. On the other hand, electron transfer reactions involving
2
simple transition metal systems such as CrH2 O3
6 =CrH2 O6 are expected to be
adiabatic because the reactants can approach one another to distances the order
of 500 pm.
The estimation of a rate constant involves determination of the Gibbs activation energy and the pre-exponential factor. An important contribution to the
latter is the Coulombic work which is involved in bringing charged reactants to
the reaction site where the precursor complex is formed. The Gibbs activation
energy and pre-exponential factor are the central components of the transition
state model. Methods of estimating the Gibbs activation energy are discussed rst
of all.
A. Estimation of the Gibbs Activation Energy
Using the properties of the parabolas shown in g. 7.15, one can determine a
relationship between the Gibbs energy of activation and the shape and position of
the parabolas on the reaction coordinate. The equation giving the Gibbs energy of
the reactant system is
GR

kf q  qR 2
2

7:8:4

where kf is the force constant describing the curvature of the parabola, q, the
position on the reaction coordinate, and qR, the position of the minimum for the
reactant system. The corresponding equation for the product system is
GP

kf q  qP 2
G
2

7:8:5

where qP is the position of the minimum for the parabola corresponding to the
products and G , the standard Gibbs energy change for the reaction. In the case
of homonuclear reactions, G is zero. At the intersection point where q is equal
to qC, the values of GR and GP are equal so that
kf qC  qR 2 kf qC  qP 2

G
2
2

7:8:6

Solving this equation for qC, one obtains


qC

qP qR
G

2
kf qP  qR

The Gibbs energy at the intersection point can now be calculated:



2
k q  qR 2 kf qP  qR
G
GR qC f C

2
2
2
kf qP  qR

7:8:7

7:8:8

In order to simplify the last equation the reorganization energy, El, is introduced,
where
El

kf qP  qR 2
2

7:8:9

CHEMICAL REACTION KINETICS IN SOLUTION

349

El is the energy that the reacting system must be given to reach the position qP
where there is a minimum on the Gibbs energy surface for the products.
Substituting equation (7.8.9) into equation (7.8.8) and simplifying, one obtains
 G GR qC  GR qR

El G 2
4El

7:8:10

This is the fundamental relationship in electron transfer theory relating the Gibbs
activation energy to the reorganization energy El and the standard Gibbs energy
change for the reaction G .
There are several points which should be noted about equation (7.8.10). First,
although the theory is developed here within the context of the transition state
model, the estimate of the Gibbs energy of activation is made without factoring
out the degree of freedom associated with passage through the transition state.
Thus,  G is similar to the quantity dened in equation (7.4.31). Second, the
rounding o of the barrier due to electronic coupling was neglected in deriving
equation (7.8.10). If this is not a negligible eect, it is easily accounted for by
subtracting JR from the right-hand side of equation (7.8.10). Finally, when the
reaction is homonuclear, so that G is zero,
 G

El
4

7:8:11

As was discussed above, the reorganization of the reacting system required to


reach the transition state is made up of two components, namely, an inner sphere
contribution and an outer sphere contribution. It follows that
 G  Gis  Gos

7:8:12

where  Gis is the inner sphere reorganization energy, and  Gos , the corresponding quantity for outer sphere reorganization. Details regarding estimation
of these quantities are given later in this section.
According to equation (7.8.10) the Gibbs activation energy is a quadratic
function of the driving force for the reaction, namely, G . This has important
consequences when the driving force is large in magnitude. As G increases,
one eventually reaches a value at which it is equal to El. Under these circumstances the reaction proceeds without a Gibbs energy barrier. Such a reaction is
called activationless. Thus, if one moves the right-hand parabola down with
respect to the one on the left, one eventually reaches a position where the righthand parabola crosses the left-hand parabola at its minimum (g. 7.16). If the
value of G is even greater then the right-hand parabola intersects the lefthand one on its left side. Clearly the Gibbs activation energy is again positive in
spite of the large driving force for the reaction. The region in which the rate of
reaction decreases with further increase in G is called the Marcus inverted
region. The variation in  G with the standard Gibbs energy change G is
shown in g. 7.17 for typical values of the parameters involved.
An interesting demonstration of the inverted Marcus region has been made
with a reaction involving photo-induced back electron transfer within a radical
ion pair. Thiophene (diaminophenothiazin-5-ium chloride) is a dye molecule
which may be excited to the triplet state using UV light. In the triplet state the

350

LIQUIDS, SOLUTIONS, AND INTERFACES

Fig. 7.16 Conguration of the Gibbs energy surfaces for reactants and products for (A) an
activation less process and (B) a process in the Marcus inverted region.

thiophene cation is strongly electrophilic and forms an ion pair with an donor
molecule in solution as follows:
3

TH D ! 3 TH



D


7:8:13

where 3TH is the triplet state of the thiophene cation and D, the donor molecule.
When this reaction is carried out in buered methanolic solution, the ion pair
disappears in two reactions [24]. One is a dissociation step which breaks up the ion
pair and gives thiophene in the ground state:

Fig. 7.17 Plot of the Gibbs activation energy  G against the Gibbs energy barrier G
for an electron transfer reaction with El equal to 100 kJ mol1.

351

CHEMICAL REACTION KINETICS IN SOLUTION


3

TH



D
 ! TH
D

7:8:14

The other reaction involves electron transfer within the ion pair with subsequent
dissociation:
3

TH



D
 ! TH D

7:8:15

The rate constant for the electron transfer step has been measured in the presence
of at least eight dierent donors with increasingly positive redox potentials. These
data are summarized in table 7.7.
As the driving force for the reaction increases the rate constant increases,
reaches a maximum, and then decreases again. When the rate of reaction is a
maximum, there is no barrier to electron transfer and the process is activationless.
This condition is reached for a rate constant of 1  109 s1 . For higher driving
forces, the electron transfer reaction occurs in the Marcus inverted region. Other
examples of this behavior have been described in the literature. They give strong
conrmation of the model for electron transfer presented here.
An important task in the theory of electron transfer is estimation of the
reorganization energy El. As discussed earlier, this consists of inner sphere and
outer sphere contributions. These are now considered in more detail.
B. The Inner Sphere Reorganization Energy
The model for the inner sphere reorganization was originally based on simple
electron transfer reactions involving octahedral inorganic complexes. For a
homonuclear electron exchange reaction such as
MH2 Oz1
MH2 Ozn (
+MH2 Ozn MH2 Oz1
n
n

7:8:16

the work required to achieve a common value l* of the MOH2 distance in each
reactant is given by [5]
nk
nk
7:8:17
w A l  lA 2 B l  lB 2
2
2
Table 7.7 Kinetic Data for Reaction (7.8.15) with Various Donor
Molecules Together with the Standard Potentials for Oxidation of the
Donor Molecule to its Cation Radical [24]

Donor Molecule
N; N; N0 ; N0 -Tetramethyl-P-phenyldiamine
p-Phenylenediamine
p-Aminodiphenylamine
1-Naphthylamine
Diphenylamine
9,10-Dimethylanthracene
1,2,4-Trimethoxybenzene
9-Methylanthracene

Electron Transfer
Rate Constant
107 ket =s1

Standard Redox
Potential
E /V

3.3
3.3
15.0
100
95
42
28
17

0.16
0.18
0.27
0.54
0.83
1.05
1.12
1.16

352

LIQUIDS, SOLUTIONS, AND INTERFACES

where ki and li are the force constant and equilibrium bond length, respectively, in
reactant i, and n, the number of ligands. When this work is minimized with respect
to l*, one nds that
l

kA lA kB lB
kA kB

7:8:18

Substitution of this expression for l * into equation (7.8.17) leads to the result
w

nkA kB lB  lA 2
2kA kB

7:8:19

For this type of system, the entropy associated with inner sphere reorganization is negligible [5]. Therefore, the work can be equated to the corresponding
change in Gibbs energy, so that
 Gis NL

nkA kB lB  lA 2
2kA kB

7:8:20

where NL is the Avogadro constant.


For a more general reaction, the following formulae have been given by
Marcus [4]:
 Gis NL m2 E li

7:8:21

1 G c GP  c GR
m 
2
2El

7:8:22

where

and
E li

X kjR kjP
lj 2
k

k
jR
jP
j

7:8:23

c GP and c GR are the Coulombic work terms for the reactants and products,
respectively. They are discussed in more detail below in the section dealing with
formation of the precursor complex. kjR and kjP are the force constants of the jth
vibrational coordinate in a species when it participates as a reactant and product,
respectively, and lj is the associated change in bond length. The latter quantities
allow one to calculate the work associated with inner sphere reorganization.
EXAMPLE

Calculate the inner sphere reorganization energy for the homonuclear electron
3
transfer between Fe(H2O)2
6 and Fe(H2O)6 given that the force constant for
1
the Fe(II)OH2 bond is 149 N m and its equilibrium length 221 pm, and that
the corresponding quantities for the Fe(III) complex are 416 N m1 and
205 pm, respectively.
The bond length required in these species to achieve electron transfer is
l

149  221 416  205


209 pm
149 416

7:8:24

CHEMICAL REACTION KINETICS IN SOLUTION

353

This result shows that the required bond length is closer to that in the Fe(III)
complex than in the Fe(II) complex.
The inner sphere reorganization energy is
6  149  416205  2212  1024
50:7 kJ mol1
2149 416
7:8:25

The above example illustrates the estimation of  Gis for a homonuclear reaction involving octahedral transition metal complexes. Most systems are more
complicated. However, if the details of the changes in bond lengths and bond
angles which accompany electron transfer are known, estimates of  Gis can be
made. Quantum-mechanical calculations are often required to obtain the necessary information.
 Gis 6:023  1023

C. The Outer Sphere Reorganization Energy


Estimation of the outer sphere reorganization energy is based on a continuum
description of the solvent around the reacting species and therefore is based on the
Born model of ionic solvation. Marcus [25] has described a two-step charging
process in which the non-equilibrium polarization of the dielectric medium is
produced in a reversible manner. The two reactants A and B with radii rA and
rB and charges zA and zB are imagined to be conducting spheres whose centers are
separated by a distance a at the moment of electron transfer. In step 1, the charge
on each reactant is changed from zi to zi0 , a value intermediate between what it has
as reactant and what it has as product. At the same time the surrounding solvent
molecules readjust their orientation to accommodate the change in charge. Since
the reversible work is estimated on the basis of a continuum model, it depends on
the static permittivity of the solvent es. In step 2, the charge on each reactant is
changed back from the intermediate value zi0 to the original value zi , holding the
solvent molecules xed. The medium can only respond to this change through its
polarizability. It follows that the reversible work associated with this step depends
on the optical permittivity of the solvent medium, eop. The Gibbs energy required
to produce the non-equilibrium polarization of the solvent in the transition state
for transfer of one electron was shown by Marcus [4, 25] to be



e2
1
1
1
1
1
7:8:26



Gl0 0
4pe0 2rA 2rB a eop es
where e0 is the permittivity of free space, and e0, the fundamental electronic
charge. The term involving the reciprocal relative permittivities is called the
Pekar factor. Since eop is so much smaller than es, the contribution of the
rapid polarization of the medium at optical frequencies dominates, especially in
solvents with high static permittivities such as water. The outer sphere contribution to the Gibbs energy of activation is equal to
 Gos NL m2 Gl0
where the fraction m is given by equation (7.8.22).

7:8:27

354

LIQUIDS, SOLUTIONS, AND INTERFACES

EXAMPLE

Estimate the outer sphere reorganization energy for the homonuclear electron
3
transfer between FeH2 O2
6 and FeH2 O6 assuming that the radii of the
reactants are 353 and 337 pm, respectively, and that the Coulombic work
terms CGR and CGP are zero. In the transition state the reactants are
assumed to be in contact, so that a is equal to rA rB.
The values of the radii of the aquo complexes are assumed to be 132 pm
larger than the MO bond lengths to account for the contribution of the water
molecules to the overall radius. The distance factor in equation (7.8.26) is
1
1
1
1
1
1


1:45  103 pm1


2rA 2rB a 706 674 690

7:8:28

The Pekar factor is


1
1
1
1

0:550

eop es 1:776 78:46

7:8:29

Thus, the outer sphere contribution to the Gibbs reorganization energy is


Gl0

1:602  1019 2
 1:451  109  0:550 1:840  1019 J molec1
4p  8:854  1012
7:8:30

For a homonuclear reaction G is zero. Since the Coulombic work terms
are neglected in this calculation, the factor m is equal to 1/2. It follows from
equation (7.8.27) that the outer sphere contribution to the Gibbs activation
energy is equal to
 Gos

6:022  1023  1:840  1019


27:7 kJ mol1
4

7:8:31

This is considerably less than the corresponding inner sphere contribution but
certainly not negligible.
On the basis of the analysis described by Marcus [25], the Gibbs energy Gl0
may be written as the dierence between a Born solvation term at static frequencies and one at optical frequencies. Thus, from equation (7.8.26)




e20
1
e20
1
Gl0

7:8:32
1
1
es
eop
4pe0 Ra
4pe0 Ra
where
1
1
1
1


Ra 2rA 2rB a

7:8:33

The Born model certainly overestimates the solvation term at static frequencies.
Using the MSA to account for the eects of dielectric saturation, equation
(7.8.32) can be rewritten as




e20
1
e20
1
Gl0
1
1

7:8:34
es
eop
4pe0 Ra ds
4pe0 Ra

CHEMICAL REACTION KINETICS IN SOLUTION

355

where ds is the MSA parameter which corrects the ionic radii to give a more
realistic estimate of solvation energies (see section 3.5). The parameter ds depends
mainly on the nature of the solvent but also on whether the ion is positive or
negative. This modication of the estimates of Gl0 has been used to discuss
experimentally observed dierences in the rates of one-electron oxidation and
reduction of the same molecule [26].
Other modications of the original Marcus model have been suggested [27].
Many reactants are not spherical in shape and are better approximated as ellipsoids. In this case a much more complex expression for the eective distance R is
obtained which depends on the length of the two axes which describe the shape of
the ellipsoid. Another improvement in the model is to describe each reactant as a
dielectric cavity with xed charges located within it. In this case, the calculation of
Gl0 requires a description of the charge distribution within the reactants and an
estimate of the local permittivity in the dielectric cavity.
Attempts have been made to test the Marcus estimate of Gl0 experimentally.
One way of doing this is to study the variation in electron transfer rate constant
with solvent nature. This results in a change in the Pekar factor and thus in Gl0 .
More will be said about these experiments in section 7.10.
D. The Pre-Exponential Factor
The pre-exponential factor is the most dicult part of the rate constant to estimate. Although fairly good estimates can be made of the Gibbs activation energy
using concepts based on transition state theory, this theory is not applicable to
estimation of the pre-exponential factor in a condensed medium. Factors that
need to be considered in a successful model include the electronic coupling parameter J and the role of solvent friction in determining the rate of crossing the
Gibbs energy barrier. These features were included in a model developed by
Zusman [28].
The pre-exponential factor may be expressed as
A Kp net

7:8:35

where Kp is the equilibrium constant for formation of the encounter complex


between the two reactants, and net is a frequency associated with electron transfer.
The parameter Kp can be estimated from the EigenFuoss model, which was
originally derived to estimate the ion pair formation constant (see section 3.10).
One of the ions is assumed to have a radius a which is equal to the distance
between the reactants at the reaction site. Other ions of the redox couple which
are within or on a sphere of radius a can react. The estimate of Kp also takes into
consideration any electrostatic work done to bring the reactants to the reaction
site. The equation for Kp in units of M1 is
Kp

w
4000pNL a3
el
exp
3
RT

7:8:36

where wel is the electrostatic work and NL , the Avogadro constant, the distance a
being expressed in meters. In innitely dilute solutions the electrostatic work is

356

LIQUIDS, SOLUTIONS, AND INTERFACES

wel

zA zB NL e20
8pe0 es a

7:8:37

where zA and zB are the valences associated with the reactants A and B, e0 , the
electronic charge, es , the relative permittivity of the solvent, and e0 , the permittivity of free space. At nite solution concentrations, the shielding eect of the
ionic atmosphere should be considered in estimating wel . This can be done using
the extended DebyeHuckel theory or the MSA.
EXAMPLE

Estimate the equilibrium constant for formation of the encounter complex


between the Fe3 and Fe2 ions in water at innite dilution and 25 C, assuming that the distance of closest approach is 690 pm.
The electrostatic work is equal to
wel

3  2  6:022  1023  1:602  1019 2


7:697 kJ mol1
8p  8:854  1012  78:46  6:9  1010

The value of Kp is
4000p  6:022  1023  6:9  1010 3
7:697  103
exp 
Kp
3
8:3145  298:2
0:0372 M1

7:8:38

7:8:39

The value of Kp for reactions in which wel is zero is close to unity. When the
reactants are charged with the same sign the repulsion results in a lower value of
Kp. In the estimate of wel made at zero ionic strength, the repulsive eect is
overestimated, and the estimate of Kp is too low.
The frequency associated with electron transfer, net, is estimated by quantum
mechanics and depends on the degree of reaction adiabacity as measured by the
coupling parameters, Jr and the reorganization energy, El. In the case of adiabatic
reactions it also depends on the longitudinal relaxation time of the solvent, tL. A
general expression for net is
nd
7:8:40
net
1 ga
where nd is the frequency associated with a diabatic electron transfer process, and
ga, the adiabacity factor. When ga  1, the value of net is nd/ga, which is the
frequency associated with an adiabatic electron transfer. From quantum
mechanics, the expression for nd is
nd

4p2 J2r
NL h4pEl RT1=2

7:8:41

8p2 J2r tL
NL hEl

7:8:42

and that for ga,


ga

When Jr is large and the reaction adiabatic, the expression for net is

357

CHEMICAL REACTION KINETICS IN SOLUTION

net


1=2
nd
1
El

ga tL 16pRT

7:8:43

EXAMPLE

Estimate the electron transfer frequency for a reaction occurring in water at


25 C for which El is 314 kJ mol1, assuming that Jr is 0.1 kJ mol1. Repeat the
calculation for the case that Jr is 5 kJ mol1. Compare these estimates with the
value obtained for an adiabatic electron transfer.
The estimate of the diabatic frequency when Jr is 100 J mol1 .
nd

4p2  1002
6:022  1023  6:626  1034 4p  314  103  8:3145  298:21=2

1:00  1010 s1

(7.8.44)

The value of tL in water at 25 C is 0.4 ps (see section 4.7). Thus the adiabacity parameter is equal to
ga

8p2  1002  4  1013


2:5  103
6:022  1023  6:626  1034  314  103

7:8:45

Since ga is very small, the electron transfer frequency net is equal to the diabatic
frequency, that is, to 1:0  1010 s1 .
When Jr is 5000 J mol1 , the corresponding value of nd is 2:50  1013 s1 .
The adiabacity parameter also increases to 6.3. According to equation (7.8.40)
the electron transfer frequency is now
net

2:50  1013
3:42  1012 s1
1 6:3

7:8:46

For an adiabatic reaction


1
314  103
net
4  1013 16p  8:3145  298:2

!1=2
3:97  1012 s1

Thus, when Jr 5000 J mol1, the value of net


(7.8.40) is very close to the adiabatic value.

7:8:47

estimated by equation

Now, the rate constant for electron transfer may be calculated. All of the
examples considered in this section have related to the reaction between Fe3
and Fe2 , so that the rate constant for this process is estimated now.
EXAMPLE

Estimate the rate constant for electron transfer between Fe3 and Fe2 in
water at 25 C, assuming that Jr is 5 kJ mol1 and using the results obtained
above.
The inner and outer sphere reorganization energies for this reaction are 50.7
and 27.7 kJ mol1, respectively. This gives a value of El equal to 314 kJ mol1.
The lowering of the activation barrier due to interaction of the energy proles

358

LIQUIDS, SOLUTIONS, AND INTERFACES

for the reactants and products is considered in estimating the Boltzmann


factor. Thus, the Gibbs energy barrier is
 G 50:7 27:7  5:0 73:4 kJ mol1
and the Boltzmann factor is
!


 G
73:4  103
exp
exp
1:39  1013
RT
8:3145  298:2

7:8:48

7:8:49

The pre-exponential factor is


Kp net 0:0372  3:42  1012 1:27  1011 M1 s1

7:8:50

Thus, the electron transfer rate constant is


ket 1:27  1011  1:39  1013 0:018 M1 s1

7:8:51

This is two orders of magnitude smaller than the experimental value of


4.2 M1 s1 (table 7.1). If the eects of ionic strength on Kp were considered
the theoretical estimate would be higher and closer to the experimental value.
The calculations presented here show that many dierent factors must be
considered in estimating the rate constant. Nevertheless, electron transfer theory
is remarkably successful in describing this elementary solution reaction. Theory
has gone much further than described here, especially in developing the quantummechanical description of electron transfer. More details can be found in recent
reviews [29, 30]. There are other related topics which have not been discussed in
this section. They include, for example, photo-induced electron transfer [30], and
the Marcus cross-relation [5].

7.9 NMR Spectroscopy and Chemical Exchange


Reactions
When a proton is transferred from one molecule to another in solutions, it usually
nds itself in a dierent magnetic environment. As a result, if nite amounts of
both reactant and product are present in solution at equilibrium, the proton can
produce two lines in the NMR spectrum, one corresponding to the proton donor
and the other to the proton acceptor. A second feature of this system relates to the
rate with which the proton is exchanged between the donor and acceptor. If the
frequency with which the proton is transferred is comparable to the radio frequency associated with the NMR spectrometer, then the lines corresponding to
the two species are broadened. The extent of line broadening can be used to
determine the rate constants associated with the exchange process [31].
The most direct explanation of line broadening due to exchange processes is in
terms of the Heisenberg uncertainty principle. If t is the average lifetime associated with the proton in one location, then the uncertainty in the frequency of the
corresponding absorption line n is given by (2pt)1. Of course, the principle
involved here is general and applies to all spectroscopies, including UV-visible

CHEMICAL REACTION KINETICS IN SOLUTION

359

and infrared spectroscopies. However, the frequencies associated with the latter
experiments are the order of 1013 to 1015 s1. This is much higher than the frequency associated with most chemical exchange processes. As a result, any line
broadening due to chemical exchange is too small to be seen experimentally. On
the other hand, an NMR spectrometer operating at 100 MHz has a frequency
which is the order of 106 times smaller. Under these conditions the relaxation time
associated with chemical exchange is often shorter than that of relaxation processes due to interaction of the radio frequency eld with the magnetic nuclei in
the system.
In the NMR experiment, the sample is exposed to a magnetic eld B0 which is
imagined to act along the z-axis (see section 5.3). As a result, some of the magnetic
nuclei are in energy levels higher than the lowest level. In the case of protons,
there are two levels (m 12), and the relative population at equilibrium is given
by the Boltzmann fraction, which depends on the magnitude of B0 (equation
(5.35)). The system is now exposed to a rotating magnetic eld B1 in the (x; y)plane that is produced by a radio-frequency wave. The frequency of this eld is
swept over a small range which encompases the Larmor frequencies which characterize the nuclei being studied. When the radio frequency corresponds exactly to
the Larmor frequency of a given nucleus, transitions occur and the equilibrium
Boltzmann distribution is altered. Interactions with uctuating local magnetic
elds in the sample cause relaxation. The relaxation in which the system returns
to equilibrium is characterized by two processes, namely, spinlattice relaxation
which has a relaxation time T1 and spinspin relaxation with a characteristic time
T2. T1 corresponds to relaxation of Mz, the component of the magnetization
along the z-axis in the direction of the eld B0. On the other hand, T2 corresponds
to relaxation of Mx and My, the components of the magnetization in the (x; y)plane (see g. 5.7). For small molecules in solution, local eld uctuations, which
are caused by molecular motions, are fast and occur in the time range 1100 ps;
thus, they are considerably faster than the time characterizing the rotating magnetic eld B1 (10 ns). Under these circumstances T1 and T2 are equal. In viscous
media or in solids where T1 and T2 are longer, the relationship between them is
more complex. In order to obtain quantitative relationships characterizing the
time dependence of Mx, My, and Mz, one must solve the Block equations, which
are described in more detail elsewhere [G2, G4]. A more molecular description of
spinlattice and spinspin relaxation is given in section 5.3.
When a chemical exchange reaction occurs in solution, it can lead to a broadening of the related NMR peaks, as described in the following discussion.
Consider rst of all a proton exchange reaction between protons in dierent
environments denoted as HA and HB:
HA(
+HB

7:9:1

Since the protons are in dierent environments they are expected to produce two
distinct lines in the NMR spectrum. The intensities of these lines reect the
relative concentrations of the protons at equilibrium. On the basis of the theory
of chemical relaxation (section 7.6), the relaxation time associated with proton
exchange is

360

LIQUIDS, SOLUTIONS, AND INTERFACES

t kf kb 1

7:9:2

Here, kf and kb are the rate constants associated with the forward and backward
reactions in equilibrium (7.9.1). The experiment is usually designed so that the
total proton concentration is very small with respect to the concentration of other
solution components, for example, the solvent. Then the expression for the relaxation time can be rewritten as
1 1
1

t tf tb

7:9:3

where
tf

1
kf

7:9:4

tb

1
kb

7:9:5

and

are the relaxation times associated with the forward and backward processes,
respectively. Equation (7.9.3) can be rearranged as
tt
7:9:6
t f b
tf tb
The fraction of molecules present in the HA environment at any time is
tf
xA
7:9:7
tf tb
and that in the HB environment is
xB

tb
tf tb

7:9:8

At this point it is necessary to relate the relaxation time for the chemical
process to the spinspin relaxation process which is always present when the
system absorbs energy from the radio frequency wave. Both processes lead to
broadening of the NMR absorption peak. If Ti is the total relaxation time for
process i, it may be estimated from T2 and ti using the relationship
1
1
1

Ti T2 ti

7:9:9

The relaxation time is now related to the peak width at half height, (n1/2)i as
follows:
n1=2 i

1
pTi

7:9:10

Thus, from equation (7.9.9)


n1=2 i n1=2 i

1
pti

7:9:11

CHEMICAL REACTION KINETICS IN SOLUTION

361

where ( 1=2 i is the peak width at half height for process i in the absence of
chemical exchange. If ( 1=2 i can be determined in an experiment without the
system undergoing chemical exchange, then the value of ti can be calculated from
the increase in peak width.
Further analysis requires consideration of the frequencies of the two lines
corresponding to HA and HB, and how the system behaves under conditions
of slow and fast chemical exchange. If these frequencies are designated as nA
and nB then one may dene a frequency n0 which is a weighted average depending
on the fractions of protons present as HA and HB:
n 0 xA n A x B n B

7:9:12

n0 falls in between nA and nB and can be used as a point of reference to discuss


precession of the magnetic vectors of the protons at the two sites. At site A, the
magnetic vector is imagined to precess at a frequency n0  nA ; at B, it precesses in
the opposite direction with a frequency nB  n0 . Now the eect of the chemical
exchange on the appearance of the NMR spectrum can be considered in greater
detail (see g. 7.18). Four representative situations are considered from a qualitative point of view, namely, very slow, moderately slow, moderately fast, and
very fast exchange processes.
When the chemical exchange process is very slow, the relaxation times tf and tb
are long. This means that protons at sites A and B precess many times before they
exchange. Thus, there is time for the absorption of energy from the radio frequency eld B1 and sharp lines are seen in the spectrum at nA and nB (g. 7.18
(A)). When the exchange process is moderately slow, two eects are seen (g. 7.18
(B)). The lines for the protons at sites A and B are broader, and the positions of

Fig. 7.18 NMR spectra for chemical


exchange between two symmetrical sites
for the cases of (A) very slow, (B)
moderately slow, (C) moderately fast, and
(D) very fast exchange processes.

362

LIQUIDS, SOLUTIONS, AND INTERFACES

the maxima shift. The band broadening can be attributed to the uncertainty
principle, which plays a more important role as the lifetime of the proton in a
given state decreases. At the same time, the position of the band changes due to a
corresponding change in the average environment of each proton. The value of
the relaxation time t can be found from the peak separation nA  nB . If nA  nB 0
is the peak separation in the absence of exchange broadening (t 1), then
"
#1=2
A  nB
1
1 2 2
nA  nB 0
2p t nA  nB 20

7:9:13

If the process is symmetrical (tf tb), then the relaxation time in each direction is
equal to t/2. In writing equation (7.9.13) it is assumed that the absorption peaks
have a Lorentzian shape. In addition, the line-broadening eects illustrated in g.
7.18 are those for a symmetrical process.
Eventually, as the exchange process becomes faster, the two bands coalesce to
form one peak at frequency n0. The relaxation time for this condition, tc is given
by
tc

1
21=2 pn

 nB 0

7:9:14

Further increase in the exchange rate results in sharpening of the band at n0.
When this process is very fast a sharp line is observed at frequency n0 whose
width is determined by spinspin relaxation in the absence of chemical relaxation
(t 0). Under these circumstances a nucleus in site A cannot precess to a signicant extent before it leaves A to enter site B. From the point of view of the
rotating frame of reference dened with respect to n0, the proton is essentially
stationary. An important method of observing the eects of chemical exchange
illustrated in g. 7.18 is to change the temperature of the system. At low temperatures, the exchange is very slow. As the temperature increases, the exchange
speeds up and the various stages from very slow to very fast are seen.
It is important to understand what time range for kinetic experiments is accessible by NMR. The frequency dierence n which can be resolved in 1H NMR is
of the order of 101000 Hz. When the exchange process is very slow, the relaxation time t is very much greater than n1 (1030.1 s); for a very fast process t is
much less than n1. Thus, values of t in the range 1041 s can be measured
using line-broadening experiments. Other methods are used to determine rates
which cannot be measured by line broadening experiments. One of these is
based on observation of the absorption signal intensity at one of the sites in an
exchanging system, while absorption at the other site is saturated by using a
second radio frequency eld tuned at the required frequency. During the irradiation the absorption intensity falls o to a new steady-state value due to transfer
from the irradiated site. The rate constant for the decay process can be used to
calculate the lifetim