Table Of ContentPrinciples of Electrochemistry
Second Edition
Jin Koryta
Institute of Physiology,
Czechoslovak Academy of Sciences, Prague
•Win Dvorak
Department of Physical Chemistry, Faculty of Science,
Charles University, Prague
Ladislav Kavan
/. Heyrovsky Institute of Physical Chemistry and Electrochemistry,
Czechoslovak Academy of Sciences, Prague
JOHN WILEY & SONS
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Library of Congress Cataloging-in-Publication Data
Koryta, Jifi.
Principles of electrochemistry.—2nd ed. / Jin Koryta, Jin
Dvorak, Ladislav Kavan.
p. cm.
Includes bibliographical references and index.
ISBN 0 471 93713 4 : ISBN 0 471 93838 6 (pbk)
1. Electrochemistry. I. Dvorak, Jin, II. Kavan, Ladislav.
III. Title.
QD553.K69 1993
541.37—dc20 92-24345
CIP
British Library Cataloguing in Publication Data
A catalogue record for this book is available
from the British Library
ISBN 0 471 93713 4 (cloth)
ISBN 0 471 93838 6 (paper)
Typeset in Times 10/12 pt by The Universities Press (Belfast) Ltd.
Printed and bound in Great Britain by Biddies Ltd, Guildford, Surrey
Contents
Preface to the First Edition xi
Preface to the Second Edition xv
Chapter 1 Equilibrium Properties of Electrolytes 1
1.1 Electrolytes: Elementary Concepts 1
1.1.1 Terminology 1
1.1.2 Electroneutrality and mean quantities 3
1.1.3 Non-ideal behaviour of electrolyte solutions 4
1.1.4 The Arrhenius theory of electrolytes 9
1.2 Structure of Solutions 13
1.2.1 Classification of solvents 13
1.2.2 Liquid structure 14
1.2.3 Ionsolvation 15
1.2.4 Ion association 23
1.3 Interionic Interactions 28
1.3.1 The Debye-Huckel limiting law 29
1.3.2 More rigorous Debye-Hiickel treatment of the activity
coefficient 34
1.3.3 The osmotic coefficient 38
1.3.4 Advanced theory of activity coefficients of electrolytes . . .. 38
1.3.5 Mixtures of strong electrolytes 41
1.3.6 Methods of measuring activity coefficients 44
1.4 Acids and Bases 45
1.4.1 Definitions 45
1.4.2 Solvents and self-ionization 47
1.4.3 Solutions of acids and bases 50
1.4.4 Generalization of the concept of acids and bases 59
1.4.5 Correlation of the properties of electrolytes in various solvents 61
1.4.6 The acidity scale 63
1.4.7 Acid-base indicators 65
1.5 Special Cases of Electrolytic Systems 69
1.5.1 Sparingly soluble electrolytes 69
v
VI
1.5.2 Ampholytes 70
1.5.3 Polyelectrolytes 73
Chapter 2 Transport Processes in Electrolyte Systems 79
2.1 Irreversible Processes 79
2.2 Common Properties of the Fluxes of Thermodynamic Quantities 81
2.3 Production of Entropy, the Driving Forces of Transport
Phenomena 84
2.4 Conduction of Electricity in Electrolytes 87
2.4.1 Classification of conductors 87
2.4.2 Conductivity of electrolytes 90
2.4.3 Interionic forces and conductivity 93
2.4.4 The Wien and Debye-Falkenhagen effects 98
2.4.5 Conductometry 100
2.4.6 Transport numbers 101
2.5 Diffusion and Migration in Electrolyte Solutions 104
2.5.1 The time dependence of diffusion 105
2.5.2 Simultaneous diffusion and migration 110
2.5.3 The diffusion potential and the liquid junction potential . . . Ill
2.5.4 The diffusion coefficient in electrolyte solutions 115
2.5.5 Methods of measurement of diffusion coefficients 118
2.6 The Mechanism of Ion Transport in Solutions, Solids, Melts, and
Polymers 120
2.6.1 Transport in solution 121
2.6.2 Transport in solids 124
2.6.3 Transport in melts 127
2.6.4 Ion transport in polymers 128
2.7 Transport in a flowing liquid 134
2.7.1 Basic concepts 134
2.7.2 The theory of convective diffusion 136
2.7.3 The mass transfer approach to convective diffusion 141
Chapter 3 Equilibria of Charge Transfer in Heterogeneous
Electrochemical Systems 144
3.1 Structure and Electrical Properties of Interfacial Regions . . .. 144
3.1.1 Classification of electrical potentials at interfaces 145
3.1.2 The Galvani potential difference 148
3.1.3 The Volta potential difference 153
3.1.4 The EMF of galvanic cells 157
3.1.5 The electrode potential 163
3.2 Reversible Electrodes 169
3.2.1 Electrodes of the first kind 170
3.2.2 Electrodes of the second kind 175
Vll
3.2.3 Oxidation-reduction electrodes 177
3.2.4 The additivity of electrode potentials, disproportionation . . . 180
3.2.5 Organic redox electrodes 182
3.2.6 Electrode potentials in non-aqueous media 184
3.2.7 Potentials at the interface of two immiscible electrolyte
solutions 188
3.3 Potentiometry 191
3.3.1 The principle of measurement of the EMF 191
3.3.2 Measurement of pH 192
3.3.3 Measurement of activity coefficients 195
3.3.4 Measurement of dissociation constants 195
Chapter 4 The Electrical Double Layer 198
4.1 General Properties 198
4.2 Electrocapillarity 203
4.3 Structure of the Electrical Double Layer 213
4.3.1 Diffuse electrical layer 214
4.3.2 Compact electrical layer 217
4.3.3 Adsorption of electroneutral molecules 224
4.4 Methods of the Electrical Double-layer Study 231
4.5 The Electrical Double Layer at the Electrolyte-Non-metallic
Phase Interface 235
4.5.1 Semiconductor-electrolyte interfaces 235
4.5.2 Interfaces between two electrolytes 240
4.5.3 Electrokinetic phenomena 242
Chapter 5 Processes in Heterogeneous Electrochemical Systems . . 245
5.1 Basic Concepts and Definitions 245
5.2 Elementary outline for simple electrode reactions 253
5.2.1 Formal approach 253
5.2.2 The phenomenological theory of the electrode reaction . . .. 254
5.3 The Theory of Electron Transfer 266
5.3.1 The elementary step in electron transfer 266
5.3.2 The effect of the electrical double-layer structure on the rate of
the electrode reaction 274
5.4 Transport in Electrode Processes 279
5.4.1 Material flux and the rate of electrode processes 279
5.4.2 Analysis of polarization curves (voltammograms) 284
5.4.3 Potential-sweep voltammetry 288
5.4.4 The concentration overpotential 289
5.5 Methods and Materials 290
5.5.1 The ohmic electrical potential difference 291
5.5.2 Transition and steady-state methods 293
Vlll
5.5.3 Periodic methods 301
5.5.4 Coulometry 303
5.5.5 Electrode materials and surface treatment 305
5.5.6 Non-electrochemical methods 328
5.6 Chemical Reactions in Electrode Processes 344
5.6.1 Classification 345
5.6.2 Equilibrium of chemical reactions 346
5.6.3 Chemical volume reactions 347
5.6.4 Surface reactions 350
5.7 Adsorption and Electrode Processes 352
5.7.1 Electrocatalysis 352
5.7.2 Inhibition of electrode processes 361
5.8 Deposition and Oxidation of Metals 368
5.8.1 Deposition of a metal on a foreign substrate 369
5.8.2 Electrocrystallization on an identical metal substrate 372
5.8.3 Anodic oxidation of metals 377
5.8.4 Mixed potentials and corrosion phenomena 381
5.9 Organic Electrochemistry 384
5.10 Photoelectrochemistry 390
5.10.1 Classification of photoelectrochemical phenomena 390
5.10.2 Electrochemical photoemission 392
5.10.3 Homogeneous photoredox reactions and photogalvanic effects 393
5.10.4 Semiconductor photoelectrochemistry and photovoltaic effects 397
5.10.5 Sensitization of semiconductor electrodes 403
5.10.6 Photoelectrochemical solar energy conversion 406
Chapter 6 Membrane Electrochemistry and Bioelectrochemistry . . 410
6.1 Basic Concepts and Definitions 410
6.1.1 Classification of membranes 411
6.1.2 Membrane potentials 411
6.2 Ion-exchanger Membranes 415
6.2.1 Classification of porous membranes 415
6.2.2 The potential of ion-exchanger membranes 417
6.2.3 Transport through a fine-pore membrane 419
6.3 Ion-selective Electrodes 425
6.3.1 Liquid-membrane ion-selective electrodes 425
6.3.2 Ion-selective electrodes with fixed ion-exchanger sites . . .. 428
6.3.3 Calibration of ion-selective electrodes 431
6.3.4 Biosensors and other composite systems 431
6.4 Biological Membranes 433
6.4.1 Composition of biological membranes 434
6.4.2 The structure of biological membranes 438
6.4.3 Experimental models of biological membranes 439
6.4.4 Membrane transport 442
6.5 Examples of Biological Membrane Processes 454
IX
6.5.1 Processes in the cells of excitable tissues 454
6.5.2 Membrane principles of bioenergetics 464
Appendix A Recalculation Formulae for Concentrations and
Activity Coefficients 473
Appendix В List of Symbols 474
Index 477
Preface to the First Edition
Although electrochemistry has become increasingly important in society
and in science the proportion of physical chemistry textbooks devoted to
electrochemistry has declined both in extent and in quality (with notable
exceptions, e.g. W. J. Moore's Physical Chemistry).
As recent books dealing with electrochemistry have mainly been ad-
dressed to the specialist it has seemed appropriate to prepare a textbook of
electrochemistry which assumes a knowledge of basic physical chemistry at
the undergraduate level. Thus, the present text will benefit the more
advanced undergraduate and postgraduate students and research workers
specializing in physical chemistry, biology, materials science and their
applications. An attempt has been made to include as much material as
possible so that the book becomes a starting point for the study of
monographs and original papers.
Monographs and reviews (mainly published after 1970) pertaining to
individual sections of the book are quoted at the end of each section. Many
reviews have appeared in monographic series, namely:
Advances in Electrochemistry and Electrochemical Engineering (Eds P.
Delahay, H. Gerischer and C. W. Tobias), Wiley-Interscience, New
York, published since 1961, abbreviation in References AE.
Electroanalytical Chemistry (Ed. A. J. Bard), M. Dekker, New York,
published since 1966.
Modern Aspects of Electrochemistry (Eds J. O'M. Bockris, В. Е. Conway
and coworkers), Butterworths, London, later Plenum Press, New York,
published since 1954, abbreviation MAE.
Electrochemical compendia include:
The Encyclopedia of Electrochemistry (Ed. C. A. Hempel), Reinhold, New
York, 1961.
Comprehensive Treatise of Electrochemistry (Eds J. O'M. Bockris, В. Е.
Conway, E. Yeager and coworkers), 10 volumes, Plenum Press, 1980-
1985, abbreviation CTE.
Electrochemistry of Elements (Ed. A. J. Bard), M. Dekker, New York, a
multivolume series published since 1973.
xi
Xll
Physical Chemistry. An Advanced Treatise (Eds H. Eyring, D. Henderson
and W. Jost), Vol. IXA,B, Electrochemistry, Academic Press, New
York, 1970, abbreviation PChAT.
Hibbert, D. B. and A. M. James, Dictionary of Electrochemistry,
Macmillan, London, 1984.
There are several more recent textbooks, namely:
Bockris, J. O'M. and A. K. N. Reddy, Modern Electrochemistry, Plenum
Press, New York, 1970.
Hertz, H. G., Electrochemistry—A Reformulation of Basic Principles,
Springer-Verlag, Berlin, 1980.
Besson, J., Precis de Thermodynamique et Cinetique Electrochimique,
Ellipses, Paris, 1984, and an introductory text.
Koryta, J., Ions Electrodes and Membranes, 2nd Ed., John Wiley & Sons,
y y
Chichester, 1991.
Rieger, P. H., Electrochemistry, Prentice-Hall, Englewood Cliffs, N.J.,
1987.
The more important data compilations are:
Conway, В. Е., Electrochemical Data, Elsevier, Amsterdam, 1952.
CRC Handbook of Chemistry and Physics (Ed. R. C. Weast), CRC Press,
Boca Raton, 1985.
CRC Handbook Series in Inorganic Electrochemistry (Eds L. Meites, P.
Zuman, E. B. Rupp and A. Narayanan), CRC Press, Boca Raton, a
multivolume series published since 1980.
CRC Handbook Series in Organic Electrochemistry (Eds L. Meites and P.
Zuman), CRC Press, Boca Raton, a multivolume series published since
1977.
Horvath, A. L., Handbook of Aqueous Electrolyte Solutions, Physical
Properties, Estimation and Correlation Methods, Ellis Horwood, Chiches-
ter, 1985.
Oxidation-Reduction Potentials in Aqueous Solutions (Eds A. J. Bard, J.
Jordan and R. Parsons), Blackwell, Oxford, 1986.
Parsons, R., Handbook of Electrochemical Data, Butterworths, London,
1959.
Perrin, D. D., Dissociation Constants of Inorganic Acids and Bases in
Aqueous Solutions, Butterworths, London, 1969.
Standard Potentials in Aqueous Solutions (Eds A. J. Bard, R. Parsons and
J. Jordan), M. Dekker, New York, 1985.
The present authors, together with the late (Miss) Dr V. Bohackova,
published their Electrochemistry, Methuen, London, in 1970. In spite of the
favourable attitude of the readers, reviewers and publishers to that book
(German, Russian, Polish, and Czech editions have appeared since then) we
now consider it out of date and therefore present a text which has been
largely rewritten. In particular we have stressed modern electrochemical
хш
materials (electrolytes, electrodes, non-aqueous electrochemistry in gene-
ral), up-to-date charge transfer theory and biological aspects of electro-
chemistry. On the other hand, the presentation of electrochemical methods
is quite short as the reader has access to excellent monographs on the
subject (see page 301).
The Czech manuscript has been kindly translated by Dr M. Hyman-
Stulikova. We are much indebted to the late Dr A Ryvolova, Mrs M.
Kozlova and Mrs D. Tumova for their expert help in preparing the
manuscript. Professor E. Budevski, Dr J. Ludvik, Dr L. Novotny and Dr J.
Weber have supplied excellent photographs and drawings.
Dr K. Janacek, Dr L. Kavan, Dr K. Micka, Dr P. Novak, Dr Z. Samec
and Dr J. Weber read individual chapters of the manuscript and made
valuable comments and suggestions for improving the book. Dr L. Kavan is
the author of the section on non-electrochemical methods (pages 319 to
329).
We are also grateful to Professor V. Pokorny, Vice-president of the
Czechoslovak Academy of Sciences and chairman of the Editorial Council
of the Academy, for his support.
Lastly we would like to mention with devotion our teachers, the late
Professor J. Heyrovsky and the late Professor R. Brdicka, for the
inspiration we received from them for our research and teaching of
electrochemistry, and our colleague and friend, the late Dr V. Bohackova,
for all her assistance in the past.
Prague, March 1986 Jifi Koryta
Jin Dvorak
