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5.5.3 Periodic methods 5.5.4 Coulometry 5.5.5 Electrode materials and surface treatment 5.5.6 Non-electrochemical methods 5.6 Chemical Reactions in Electrode Processes 5.6.1 Classification 5.6.2 Equilibrium of chemical reactions 5.6.3 Chemical volume reactions 5.6.4 Surface reactions 5.7 Adsorption and Electrode Processes 5.7.1 Electrocatalysis 5.7.2 Inhibition of electrode processes 5.8 Deposition and Oxidation of Metals 5.8.1 Deposition of a metal on a foreign substrate 5.8.2 Electrocrystallization on an identical metal substrate 5.8.3 Anodic oxidation of metals 5.8.4 Mixed potentials and corrosion phenomena 5.9 Organic Electrochemistry 5.10 Photoelectrochemistry 5.10.1 Classification of photoelectrochemical phenomena 5.10.2 Electrochemical photoemission 5.10.3 Homogeneous photoredox reactions and photogalvanic effects 5.10.4 Semiconductor photoelectrochemistry and photovoltaic effects 5.10.5 Sensitization of semiconductor electrodes 5.10.6 Photoelectrochemical solar energy conversion
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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
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Processes in the cells of excitable tissues Membrane principles of bioenergetics Recalculation Formulae for Concentrations and Activity Coefficients List of Symbols
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Appendix A Appendix Index
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Preface to the First Edition
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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 addressed 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, . . 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, . . Conway, E. Yeager and coworkers), 10 volumes, Plenum Press, 19801985, abbreviation CTE. Electrochemistry of Elements (Ed. A. J. Bard), M. Dekker, New York, a multivolume series published since 1973. xi
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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., Ionsy Electrodesy and Membranes, 2nd Ed., John Wiley & Sons, Chichester, 1991. Rieger, P. H., Electrochemistry, Prentice-Hall, Englewood Cliffs, N.J., 1987. The more important data compilations are: Conway, . ., 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, Chichester, 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
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materials (electrolytes, electrodes, non-aqueous electrochemistry in general), up-to-date charge transfer theory and biological aspects of electrochemistry. 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. HymanStulikova. 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
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