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Fifty years ago solution chemistry occupied a major fraction of physical chemistry textbooks, and dealt mainly with classical thermodynamics, phase equilibria, and non-equilibrium phenomena, especially those related to electrochemistry. Much has happened in the intervening period, with tremendous advances in theory and the development of important new experimental techniques. This book brings the reader through the developments from classical macroscopic descriptions to more modern microscopic details.

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From Classical Macroscopic Descriptions

to Modern Microscopic Details

W. RONALD FAWCETT

University of California, Davis

1

2004

Auckland Bangkok Buenos Aires Cape Town Chennai

Dar es Salaam Delhi Hong Kong Istanbul Karachi Kolkata

Kuala Lumpur Madrid Melbourne Mexico City Mumbai Nairobi

Sao Paulo Shanghai Taipei Tokyo Toronto

Published by Oxford University Press, Inc.

198 Madison Avenue, New York, New York, 10016

www.oup.com

Oxford is a registered trademark of Oxford University Press

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

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

on acid-free paper

To my three muses,

Zuzana, Natalka, and Tetiana

An Interplay of Slow and Fast

Of Silence . . .

And of Light and Dark

That Flickers with Hypnotic Rhythm

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

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

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.

Contents

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

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

2.1

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

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

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

4.2 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

4.10 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

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

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

304

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

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

383

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

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

9.10 p-Functions and the Denition of pH, 502

9.11 Concluding Remarks, 504

References, 505

Problems, 505

10.

508

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

Fourier Transforms, 584

Complex Numbers and Functions, 585

Power Series, 586

Appendix C. Numerical Methods of Data Analysis

C.1

C.2

C.3

C.4

C.5

C.6

C.7

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

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

xvi

Solutions

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.

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

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.

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

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

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

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.

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.

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

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

@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

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

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

A U TS

1:3:15

G U TS PV

1:3:16

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

dH TdS VdP

1:3:18

dA SdT PdV

1:3:19

dG SdT VdP

1:3:20

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).

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

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

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

nA dA nB dB 0

1:4:7

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

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

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

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

A Vm xB

@V ex

m

xB VmA VmB

@xB

1:4:19

m given by equation (1.4.17), this simplies to

A V ex

m xB

@V ex

m

VmA

@xB

1:4:20

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

B V ex

m xA

@V ex

m

VmB

@xA

1:4:21

EXAMPLE

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

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

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.

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

PB PB xB

1:5:2

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

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.

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

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

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

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

mix G nA RT ln xA nB RT ln xB

1:6:10

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

1:6:14

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.

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.

19

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

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.

21

Fig. 1.7 Vapor pressure of acetone and chloroform for acetonechloroform solutions at

35 C plotted against the mole fraction of acetone.

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

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

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

s;

msB ms;

B RT ln aB mB RT ln gB xB

1:8:6

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

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

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

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

gw

2:874

1:500

0:605 3:166

1:8:15

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

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

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.

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]

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

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

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

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

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

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

(equation (1.4.26)):

2

mA ms;

A RT ln xA cxB h

1:9:13

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

PB xB PB exp

cx2A h

RT

27

1:9:18

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

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

1:9:20

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

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

1:9:24

and

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.

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

ch

2

RT

1:9:31

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

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

1:10:1

Similarly, estimating the ratio of the number of BB interactions to AB interactions, one obtains

nBB nB exphBB =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 nB V mB exp hAB =RT

1:10:3

B

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

1:10:4

and

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

mix Gex

m RTxA ln1 rBA xB RTxB ln1 rAB xA

1:10:7

where

rBA 1

V mA exp hAB =RT

1:10:8

31

and

rAB 1

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

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

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

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).

0:52 0:6118

0:52 0:8287

1:10:15

Similarly, for carbon tetrachloride which is component B

ln B ln1 0:8287 0:5

0:52 0:8287

0:52 0:6118

1:10:16

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

1 rBA xB @T

1 rAB xA @T

1:10:18

33

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.

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

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.

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

35

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

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

H

s;

H

msB ms;

B RT ln aB mB RT ln gB cB

1:12:12

EXAMPLE

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

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.

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

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.

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

39

1:13:2

Sm dT Vm dP xA dmA xB dmB 0

1:13:3

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

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

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

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

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

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

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 .

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

44

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.

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.

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

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.

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.

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

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

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

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

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

!

@ 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

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

@ ln Q

G U TS PV kB T ln Q kB TV

@V T;N

2:2:14

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

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:

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

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

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.

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

53

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

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

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

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 :

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

u12 r

2p1 p2

4pe0 r3

2:3:10

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

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

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

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

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

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 .

57

EXAMPLE

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

udd

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

2:3:21

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

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

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

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

58

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.

59

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

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

so that

r6e

2ALJ

BLJ

2:3:31

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

2:3:33

2:3:34

and

s 12

s6

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

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

r6e 2s6

2:3:37

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

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

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

B

has units of temperature.

61

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.

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

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

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

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

function gr for a uid

obeying the LennardJones

potential with LJ 1:69kB T

and a molecular density N=V

0:88s3 [3].

64

Fr1

@Wr kB T @gr

@r1

gr @r1

2:4:9

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

hr gr 1

2:4:10

zero (see g. 2.4).

From the total correlation function, one obtains the structure factor SkD by

Fourier transformation. Thus,

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.)

65

It follows that

Ur1 ; . . . ; rN

N

X

i<j1

urij

N

X

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.

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

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

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

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

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

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

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

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

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

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

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.

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

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

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

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.

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

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

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.

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

74

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

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.

75

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.

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

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

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

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

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

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

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

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

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

!

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.

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

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

yr gr;

rs

2:9:4

80

zero,

yr cr;

r s

2:9:5

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.

81

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

z

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).

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

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

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

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

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

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 entropy is given by

84

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

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.

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

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.

neutron diraction [8].

86

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-

neutron diraction [8].

87

neutron diraction [8].

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

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

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.

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

2:11:1

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

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

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

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

3NkB T

N2

8p

e s3

U

2

V mix mix

1

1

gyy2 dy

yn y m

2:11:7

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

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.

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-

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

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

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

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

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.

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

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.

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

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.

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

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

100

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

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

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

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

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

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.

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

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

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

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

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

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

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

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

106

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.

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

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

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

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

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.

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

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

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

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

where

coecient. On the mole fraction scale, one writes

mMX mMX 2RT ln f xe

D

3:6:8

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

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

114

n

m n m n m n n nn mne

3:6:16

g n g n g n

3:6:17

ae n n n n g n mne

3:6:18

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

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

3:6:21

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

ce

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

0:529

0:0995

ce

3:6:26

ELECTROLYTE SOLUTIONS

115

3:6:27

ae a3 5:83 104

3:6:28

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

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

mMX m

M mX

3:6:36

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.

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

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

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

Estimate the osmotic coecient and mean ionic activity coecients for the

118

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

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

3:7:12

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

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

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

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.

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

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, ci , because the

potential, , is dierent from the average potential. Using Boltzmann statistics

these quantities are connected by the relationship

cri ci expzi f

3:8:6

where ci 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 Fci expzi f

3:8:8

i1

equation for the system:

n

X

1 d 2 d

zi Fci

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 Fci

i1

n

X

z2i Ffci

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 ce and the charge numbers zi are 1 and 1. Then, the

ionic strength is also equal to the bulk concentration ce . For a 21 electrolyte,

such as ZnCl2, the cationic concentration is equal to ce , whereas the anionic

concentration is 2ce . In this case, the ionic strength is 3ce 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

dy

d

r

dr

dr

3:8:15

d2 y

d

d2

r 2

2

2

dr

dr

dr

3:8:16

and

1 d 2 d

2 d d2

r

2

dr

r dr

r2 dr

dr

3:8:17

d2 y

k2 y

dr2

3:8:18

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 Ffci 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

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

4pk1 es e0 kaeka eka zi e0

3:8:24

so that

k1

zi e0 eka

1

4pe0 es 1 ka

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

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 3:288 a I 1=2

3:8:31

1 BDH aI 1=2

3:8:32

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

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

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

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

ln y ADH jz z jI 1=2

3:8:44

ln y

ADH jz z jI 1=2

1 BDH aI 1=2

3:8:45

128

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

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

or

y 0:443

3:8:47

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

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.

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, ci times its valence zi must equal zero, that is

X

zi ci 0

3:9:1

i

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 ci

3:9:4

4e0 es i 1 2ri 2

The concentration ci 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

gij r

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 ci

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

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

ci

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

1 0:6635 0:36

3:9:19

From equation (3.9.13)

ln y es

4:741 105

0:382

2 8:3144 298:2 250

3:9:20

calculated rst:

z

7:36 103

6

3:9:21

ln y hs

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

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.

e

3:9:24

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 @ci

i

2NL I

NL es @ci

3:9:25

ln y es

2NL I

nNL es @ce

3:9:26

where

@es

@e

@e

n s n s

@ce

@c

@c

3:9:27

@es =@ce 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.

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

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

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

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

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 cj expzj f

3:10:14

where cj 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

8prcj exp

4pr2 cj 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

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.

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

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

2NL I

nNL es @ce

3:11:3

where Ues is dened by equation (3.9.9) and ce 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

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 ce 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

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

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.

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

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.

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145

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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

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

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

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

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.

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.

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

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)

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

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

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

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.

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

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

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

4:3:5

expbp E cos y sin y dy

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

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

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

hpi

1:41 1030 C m

3 1:38 1023 298:2

4:3:11

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

spherical cavity within a

homogenous dielectric between

the plates of a parallel-plate

capacitor.

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

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

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

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,

ap

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

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

88:09 cm3 mol1

0:8830

4:3:26

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

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

Now one calculates the molar polarization due to the solute. For example,

when x2 0:0197,

Pm2

221:4 cm3 mol1

0:0197

4:3:29

Rm2

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

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

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

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

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.

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

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 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

a

3 4:91 1010 3

1:206

3 4:91 1010 3 4 7:99 1030 1:895

4:4:12

NL 6:022 1023

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

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

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

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

b2

6lop 1

lop 2

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.

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

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

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

Poe Pe Pd e0 E es e1

4:5:7

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

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

equation may also be written as

dD De

dt

D De

t

4:5:12

D De D0 De et=t

4:5:13

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

jotAD ejot e0 e1 Em ejot AD ejot e0 e1 Em ejot e0 Em ejot es e1

4:5:19

AD

e0 Em es j!te1 es o2 t2 e1

1 o2 t2

4:5:20

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

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

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

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

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

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

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.

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

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.

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

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

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.

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

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

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

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

e1 f 1

f2 1

tL1

es tD1 tD2

4:7:6

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

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

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.

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

Electrolyte

LiI

NaCl

KCl

KI

TAI

TATB

43.7

53.1

44.4

23.4

19.2

72.0

tr G TA tr G TB 72:0=2 36:0 kJ mol1

4:8:7

tr G I 19:2 36:0 16:8 kJ mol1

4:8:8

tr G Li 43:7 16:8 26:9 kJ mol1

1

4:8:9

4:8:10

tr G Cl 44:4 6:6 37:8 kJ mol1

4:8:11

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

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

estimated from experiment.

b

Estimated from polarographic halfwave potential data [40].

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

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

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].

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

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

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].

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

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

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 (4.9.2).

POLAR SOLVENTS

193

dene the AN scale.

ET 150:6 1:954 AN

4:9:1

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

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

dene the DN scale.

194

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

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

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

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

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

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

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

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

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

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.

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

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

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

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

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

Structure and Solvation

Gabor Palinkas

Erika Kalman

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

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.

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

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.

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

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

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

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.

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.

209

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

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

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

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.

dierence function GLi(r) for

LiCl in D2O as a function of

interatomic distance r. (From

reference 8, with permission.)

212

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

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.

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

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

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

215

(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

1:41 1026 J T1

2p

5:3:3

hn

1:325 1025 J

1=2

5:3:4

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

(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

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,

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

1:325 1025 J

2p

5:3:8

kB T 1:381 1023 298:2 4:118 1021 J

5:3:9

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

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).

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.

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

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

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

221

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

0.021

0.008

0.047

0.096

0.111

0.092

0.080

Electrolyte

NaBr

NaI

NaCN

NaNO3

NaBF4

NaSCN

NaClO4

0.128

0.175

0.113

0.081

0.123

0.143

0.140

222

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

223

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

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.

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

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.

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

6.5

7.5

6.0

4.0

3.0

7.5

7.4

6.3

6.9

5.0

tetrabutylammonium.

b

With respect to that for pure acetonitrile.

a

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

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.

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

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

n 918 2:998 1010 2:752 1013 s1

5:6:3

k 4p2 1:583 1026 2:752 1013 2 473 N m1 molec1

5:6:4

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

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.

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

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

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

wavelength is

lw

2:93 101

1:465 105 m

2000

229

5:6:8

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

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

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

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.

233

Frequencies for H2O, D2O,

and HOD from Gas Phase

Measurements

Frequency/cm1

Molecule Mode

H2O

HOD

D2O

n1

n2

n3

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

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

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

Fig. 5.17 Ball-and-stick diagram of an acetonitrile molecule together with its infrared

spectrum as a liquid. (From reference 26, with permission.)

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-

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

Fig. 5.19 Ball-and-stick diagram of dimethylformamide together with its infrared spectrum in the liquid state. (From reference 26, with permission.)

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.

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.

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

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.)

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

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.

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

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

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

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

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-

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

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

245

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.

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

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

splitting of the d orbitals in

a transition metal ion in an

octahedral eld and a

tetrahedral eld due to

surrounding ligands (Lewis

bases).

247

Table 5.10 Crystal Field Data for the Complex Ions M(H2O)n

6 from the First

Transition Series

Ion

d Electrons

Ti3+

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

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

molecules can interact with the electron

density on the cyano groups.

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

acetoacetonate. Solvent molecules can

interact as Lewis bases with the axial sites

in the complex as shown.

250

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].

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

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.

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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.

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36.

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Spaziante, P. M.; Gutmann, V. Inorg. Chim. Acta 1971, 5, 273.

Mayer, U.; Gutmann, V.; Gerger, W. Monatsh. Chem. 1975, 106, 1235.

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Lin-Vien, D.; Colthrup, N. B.; Fateley, W. G.; Grasselli, J. G. The Handbook of

Infrared and Raman Characterstici Frequencies of Organic Molecules; Academic

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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

Estimate the chemical shift for 23 Na in nitrobenzene, benzonitrile, and butyronitrile using the DN data in table 4.10.

253

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

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

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.

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

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.

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

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

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

@x @y @z

6:2:4

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

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

dni

@ci

dV Ji

dA divJi dV

dt

@t

V

6:2:7

257

It follows that

@ci

div Ji

@t

6:2:8

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

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

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

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

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

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

units of rmi are J m1 mol1 or N mol1 . Thus the units of Li are mol2 m2

N1 s1 .

259

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].

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

liquid owing between two parallel

plates. The arrows indicate the

magnitude of the velocity and the

direction of the ow.

260

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

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

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

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.

263

tD

1:86 1011 s

1:38 1023 298:2

6:3:10

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

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.

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

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

@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

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

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

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 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.

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

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

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

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

c~

where

DAu DB Au B

2

Du2 s

u v2

6:5:17

v2

s

D

269

6:5:18

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

abA

6:5:21

vb a B

6:5:22

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

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

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

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 .

271

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

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,

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].

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

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

m~ aM maM Ffa

6:6:2

m~ aX maX Ffa

6:6:3

division of the electrochemical potential of

species i in phase a into chemical and electrical

contributions.

273

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

where

section 3.8). The relationship between fa and ai is

ai fa ia

6:6:7

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

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.

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:

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

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.

a conductivity cell (a) and its

impedance representation as an

equivalent circuit (b).

Capacitances C1 and C2 are at

the electrode|solution

276

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

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

numbers with associated circuitry. Circuit element C

is a coulometer. The three compartments are labeled

L (left), M (middle), and R (right).

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

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

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

li

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

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

uMg2

50:98

2:64 104 cm2 s1 V1

2 96;485

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

this can be written as

L RT

r ln yi

1

6:7:17

rci Li zi Frf

Ji i

ci

r ln ci

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

Ji Di rci

z i ui c i

rf

jzi j

6:7:20

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

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

jz je

ui i 0

6pZri

In terms of the diusion coecient, one obtains

kT

Di

6pZri

6:7:26

6:7:27

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

7:24 1010 m 724 pm

ri

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

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

6:7:31

and

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

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

6:7:37

FJM FJX 0

6:7:38

6:7:39

It follows that

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

JM JX

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

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

De

RT

LMM LXX L2MX

e

ce

LMM 2LMX LXX

6:7:47:

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

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

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.

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

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

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 .

li li0 1

ki c1=2

e

li0

285

6:8:3

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

in Water at 258C [7]*

Cation

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

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-

287

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

Ka

aM aX

y2 a2 ce

aMX

yMX 1 a

6:8:7

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

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

Fig. 6.9 Plot of 1/ at 258C against ce for two weak electrolytes, namely, acetic acid (^)

and NH4 OH (*).

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.

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

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 ci expzi f

6:9:2

ci

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 ci ci

1

X

1n

n1

n!

zi fn

6:9:3

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 ci zi ci 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 ci 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

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

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 ce

e

f f ekr dr

v

6pe0 es Z 1 ka

6:9:10

v

z2 fe0 ce f f

6pe0 es Z k1 ka

6:9:11

For a symmetrical zz electrolyte the ionic strength is equal to z2 ce . 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

291

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

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

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

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

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

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

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.

293

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

6:9:29

The estimate of is

426:2 0:2292 426:2 60:57 0:2153 392:1

6:9:30

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

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.

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

295

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

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

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.

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

Stokes radius or of the Walden product. Ion size and structure both determine the

extent to which the ion moves with associated solvent molecules.

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.

299

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

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

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.

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

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

"

#

@cr; t

@2 cr; t 2 @cr; t

D

@t

r @r

@r2

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

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

303

0:2264 M1=2 and B2 50:99 cm2 M1=2 1 mol1 .

ce /M

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

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

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.

in Solution

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).

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

305

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.

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

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

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

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

307

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

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

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

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

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

k1 k1 dcA

k1 k1 dt

k1 k1 cA k1 cA0

7:2:18

function of time is

cA

k1 k1

7:2:19

cAe

k1 cA0

k1 k1

7:2:20

cBe

k1 cA0

k1 k1

7:2:21

and that of B,

Ke

cBe

k

1

cAe k1

7:2:22

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.

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.

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

cB

k1 cA0 k1 t

e

ek2 t

k2 k1

7:2:28

310

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

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

cBss

k 1 cA k 1

cA0 ek1 t

k2

k2

7:2:31

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)).

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

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

dcS

k1 cE cS k1 cES

dt

7:2:39

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

dcP

k1 k2 cS cE0

dt

k1 k2 k1 cS

7:2:44

simplies to

dcS

dc

k k c c

P 1 2 S E0

dt

dt

k1 k1 cS

7:2:45

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.

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

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

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.

315

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

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

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

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).

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

H3 O OH (

+2H2 O

7:3:13

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

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

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

transfer between the acid HA and base

B in water illustrating the role of

protolysis (P) and hydrolysis (H)

reactions.

319

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

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

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

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

an activated complex in a unimolecular reaction step.

322

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).

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.

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

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

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.

+X6

A B(

7:4:2

X ! products

7:4:3

dcA

dc

B k6 cX6

dt

dt

7:4:4

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

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):

K6

q6

qA qB

325

7:4:8

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

h6 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

h6 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

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

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

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

15.0

24.8

40.1

60.0

8:24 106

1:80 105

5:55 105

2:13 104

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

327

Ea

RT

7:4:20

6:969 103

T

7:4:21

ln kr ln Ar

The result is

ln kr 12:46

Ea 6:97 103 8:314 58:0 kJ mol1

7:4:22

Ar exp12:456 2:57 105 M1 s1

7:4:23

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

150 J K1 mol1

298:2

T

7:4:26

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

"

#

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.

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.

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

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:

dnA

4pDA DB a y cA cB

dt

331

7:5:15

kr 4pNL DA DB a y

7:5:16

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

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

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

EXAMPLE

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

7:5:26

1:429

The electrostatic factor y is

y

1:429

1:879

exp1:429 1

7:5:27

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.

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

333

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

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

dx

kf cAe xcBe x kb cCe x

dt

kf cAe cBe kf xcAe cBe kf x2 kb cCe kb x

7:6:5

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

Reactions Involving One Step

Reaction

Relaxation Time/t

kf

kf kb 1

A B

kb

kf

4kf cAe kb 1

2A B

kb

kf

AB C

kb

kf

AB CD

kb

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

xA xAB xC 0

The rate of reaction of A is

7:6:14

dcA

k1f cA cB k1b cAB

dt

335

7:6:15

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

dcAB

k1f cA cB k1b cAB k2f cAB k2b cC

dt

7:6:19

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

7:6:24

a12 k1b

7:6:25

a22 k1b k2f k2b

7:6:26

7:6:27

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

11 t1

2 a11 a22 a12 a21

7:6:29

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

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-

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

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

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

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

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.

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.

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

339

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

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

341

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

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

343

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

(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

tL /ps

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

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

twisting of the stilbene molecule in

the ground state S0 and rst excited

singlet state S1 .

345

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.

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

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

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

347

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

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

qC

qP qR

G

2

kf qP qR

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

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

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

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

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

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

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

209 pm

149 416

7:8:24

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

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

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

1

1

1

1

0:550

eop es 1:776 78:46

7:8:29

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

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

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

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

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

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

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

ga

When Jr is large and the reaction adiabatic, the expression for net is

357

net

1=2

nd

1

El

ga tL 16pRT

7:8:43

EXAMPLE

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

(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

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

1

314 103

net

4 1013 16p 8:3145 298:2

!1=2

3:97 1012 s1

(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

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

Kp net 0:0372 3:42 1012 1:27 1011 M1 s1

7:8:50

ket 1:27 1011 1:39 1013 0:018 M1 s1

7:8:51

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].

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

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

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

n1=2 i n1=2 i

1

pti

7:9:11

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

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

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

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