Electrochemical Science and Technology Fundamentals and Applications

by Oldham, Keith; Myland, Jan; Bond, Alan

• ISBN13: 9780470710845
• ISBN10: 0470710845
• Edition: 1st
• Format: Paperback
• Copyright: 2011-12-12
• Publisher: Wiley

Summary

The book addresses the scientific principles underlying electrochemistry. Starting with the basic concepts of electricity, the early chapters discuss the physics and chemistry of the materials from which electrochemical cells are constructed and the properties that make these materials appropriate as cell components. Much of the importance of electrochemistry lies in the conversion of electrical energy into chemical energy and vice versa; the thermodynamics of these processes is described, in the context of a wide range of applications of these interconversions. An electrode is a surface at which an ionic conductor meets an electronic conductor and the book describes a wide variety of such interfaces, including many non-traditional examples. The structure of the ionic/electronic junction is examined and the reactions that occur there are discussed from molecular, energetic and kinetic viewpoints. Polarizations are phenomena that inhibit the free passage of electricity across electrodes and much of electrochemical research is devoted to understanding these processes and to reducing (or sometimes enhancing) their effect. Electroanalytical chemistry and voltammetric methods are described, but not unduly emphasized, in this text. Where appropriate, the mathematical underpinnings of electrochemical science are described, but the more difficult aspects are presented via the web. Much tangential material is made accessible in a similar fashion, as are answers to the problems that copiously illustrate the material.

Author Biography

Keith B. Oldham is Emeritus Professor at Trent University in Canada. His research interests are drawn from the fields of electrochemistry, applied mathematics and environmental issues focusing on the electrochemical applications of mathematical and computational techniques. He has co-authored several books, contributed to numerous others, and has published over 200 articles.

Alan Bond is based in the School of Chemistry at Monash University and teaches undergraduate electrochemistry and redox chemistry His research focuses on applications of modern electroanalytical techniques to solve problems in inorganic, analytical and biological chemistry. He has authored over 500 papers, patents and books. Recipient of a Fulbright Fellowship (1972), the Rennie Medal (1975) of the Royal Australian Chemical Institute, the David Syme Prize (1977), the Analytical Chemistry Division Medal of the Royal Australian Chemical Institute (1989), the Stokes medal awarded by the Electrochemistry Division of the Royal Australian Chemical Institute (1992), the Liversidge Award (The Australian New Zealand Association for the Advancement of Science), the Federation of Asian Chemical Societies Foundation Lectureship (1993) and a range of other awards. Membership of Council of the Academy of Science and the Australian Research Council.

Jan Myland is a Research Associate within Professor Oldhams' research group and has co-authored several books and accompanying software with Professor Oldham.

Table of Contents

Preface	p. xi
Electricity	p. 1
Electric Charge
Charges at Rest	p. 3
Capacitance and Conductance	p. 8
Mobilities	p. 18
Electrical Circuits	p. 21
Alternating Electricity	p. 23
Summary	p. 28
Chemistry	p. 29
Chemical Reactions	p. 29
Gibbs Energy	p. 30
Activity	p. 33
Ionic Solutions	p. 38
Ionic Activity Coefficients	p. 41
Chemical Kinetics	p. 46
Summary	p. 52
Electrochemical Cells	p. 55
Equilibrium Cells	p. 55
Cells not at Equilibrium	p. 60
Cells with Junctions	p. 64
Summary	p. 69
Electrosynthesis	p. 71
Metal Production	p. 71
The Chloralkali Industry	p. 74
Organic Electrosynthesis	p. 75
Electrolysis of Water	p. 77
Selective Membranes	p. 79
Summary	p. 83
Electrochemical Power	p. 85
Types of Electrochemical Power Source	p. 85
Battery Characteristics	p. 86
Primary Batteries	p. 88
Secondary Batteries	p. 94
Fuel Cells	p. 100
Summary	p. 104
Electrodes	p. 105
Electrode Potentials	p. 105
Standard Electrode Potentials	p. 109
The Nernst Equation	p. 111
Electrochemical Series	p. 113
Working Electrodes	p. 117
Summary	p. 123
Electrode Reactions	p. 125
Faraday's Law	p. 125
Kinetics of a Simple Electron Transfer	p. 130
Multi-step Electrode Reactions	p. 137
Summary	p. 144
Transport	p. 145
Flux Density	p. 145
Three Transport Modes	p. 148
Migration	p. 149
Diffusion	p. 154
Diffusion and Migration	p. 158
Convection	p. 161
Fluxes at Electrodes and in the Bulk	p. 165
Summary	p. 170
Green Electrochemistry	p. 171
Sensors for Pollution Control	p. 171
Stripping Analysis	p. 177
Electrochemical Purification of Water	p. 182
Electrochemistry of Biological Cells	p. 186
Summary	p. 192
Electrode Polarization	p. 193
Three Causes of Electrode Polarization	p. 193
Ohmic Polarization	p. 197
Kinetic Polarization	p. 200
Transport Polarization	p. 202
Multiple Polarizations	p. 205
Polarizations in Two- and Three-Electrode Cells	p. 208
Summary	p. 212
Corrosion	p. 213
Vulnerable Metals	p. 213
Corrosion Cells	p. 215
Electrochemical Studies	p. 217
Concentrated Corrosion	p. 222
Fighting Corrosion	p. 224
Extreme Corrosion	p. 228
Summary	p. 229
Steady-State Voltammetry	p. 231
Features of Voltammetry	p. 232
Microelectrodes and Macroelectrodes	p. 234
Steady-State Potential-Step Voltammetry	p. 237
The Disk Microelectrode	p. 245
Rotating Disk Voltammetry	p. 248
Shapes of Reversible Voltammograms	p. 252
Summary	p. 258
The Electrode Interface	p. 259
Double Layers	p. 259
Adsorption	p. 266
The Interface in Voltammetry	p. 271
Nucleation and Growth	p. 281
Summary	p. 285
Other Interfaces	p. 287
Semiconductor Electrodes	p. 287
Phenomena at Liquid*Liquid Interfaces	p. 291
Electrokinetic Phenomena	p. 298
Summary	p. 302
Electrochemistry With Periodic Signals	p. 303
Nonfaradaic Effects of A.C	p. 304
Faradaic Effects of A.C	p. 305
Equivalent Circuits	p. 313
A.C. Voltammetry	p. 318
Fourier-Transform Voltammetry	p. 322
Summary	p. 328
Transient Voltammetry	p. 329
Modeling Transient Voltammetry	p. 329
Potential-Step Voltammetry	p. 334
Pulse Voltammetries	p. 339
Ramped Potentials	p. 346
Multiple Electron Transfers	p. 355
Chemistry Combined with Electrochemistry	p. 357
Controlling Current Instead of Potential	p. 362
Summary	p. 364
Appendix	p. 365
Glossary	p. 365
Absolute and Relative Permittivities	p. 382
Properties of Liquid Water	p. 383
Contents ix Conductivities and Resistivities	p. 384
Elements with Major Importance in Electrochemistry	p. 386
Transport Properties	p. 388
Standard Gibbs Energies	p. 390
Standard Electrode Potentials	p. 392
Index	p. 393
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