Electrochemistry is a discipline of wide scientific and technological interest. Scientifically, it explores the electrical properties of materials and especially the interfaces between different kinds of matter. Technologically, electrochemistry touches our lives in many ways that few fully appreciate; for example, materials as diverse as aluminum, nylon, and bleach are manufactured electrochemically, while the batteries that power all manner of appliances, vehicles, and devices are the products of electrochemical research. Other realms in which electrochemical science plays a crucial role include corrosion, the disinfection of water, neurophysiology, sensors, energy storage, semiconductors, the physics of thunderstorms, biomedical analysis, and so on.
This book treats electrochemistry as a science in its own right, albeit resting firmly on foundations provided by chemistry, physics, and mathematics. Early chapters discuss the electrical and chemical properties of materials from which electrochemical cells are constructed. The behavior of such cells is addressed in later chapters, with emphasis on the electrodes and the reactions that occur on their surfaces. The role of transport to and from electrodes is a topic that commands attention, because it crucially determines cell efficiency. Final chapters deal with voltammetry, the methodology used to investigate electrode behavior. Interspersed among the more fundamental chapters are chapters devoted to applications of electrochemistry: electrosynthesis, power sources, green electrochemistry, and corrosion.
Electrochemical Science and Technology is addressed to all who have a need to come to grips with the fundamentals of electrochemistry and to learn about some of its applications. It will constitute a text for a senior undergraduate or graduate course in electrochemistry. It also serves as a source of material of interest to scientists and technologists in various fields throughout academia, industry, and government chemists, physicists, engineers, environmentalists, materials scientists, biologists, and those in related endeavors.
This book:
Provides a background to electrochemistry, as well as treating the topic itself.Is accessible to all with a foundation in physical science, not solely to chemists.Is addressed both to students and those later in their careers.Features web links (throughwww.wiley.com/go/EST) to extensive material that is of a more tangential, specialized, or mathematical nature.Includes questions as footnotes to support the readers evolving comprehension of the material, with fully worked answers provided on the web.Provides web access to Excel® spreadsheets which allow the reader to model electrochemical events.Has a copious Appendix of relevant data.
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.
Preface xi1 Electricity 1
Electric Charge 1
Charges at Rest 3
Capacitance and Conductance 8
Mobilities 18
Electrical Circuits 21
Alternating Electricity 23
Summary 28
2 Chemistry 29
Chemical Reactions 29
Gibbs Energy 30
Activity 33
Ionic Solutions 38
Ionic Activity Coefficients 41
Chemical Kinetics 46
Summary 52
3 Electrochemical Cells 55
Equilibrium Cells 55
Cells not at Equilibrium 60
Cells with Junctions 64
Summary 69
4 Electrosynthesis 71
Metal Production 71
The Chloralkali Industry 74
Organic Electrosynthesis 75
Electrolysis of Water 77
Selective Membranes 79
Summary 83
5 Electrochemical Power 85
Types of Electrochemical Power Source 85
Battery Characteristics 86
Primary Batteries 88
Secondary Batteries 94
Fuel Cells 100
Summary 104
6 Electrodes 105
Electrode Potentials 105
Standard Electrode Potentials 109
The Nernst Equation 111
Electrochemical Series 113
Working Electrodes 117
Summary 123
7 Electrode Reactions 125
Faradays Law 125
Kinetics of a Simple Electron Transfer 130
Multi-step Electrode Reactions 137
Summary 144
8 Transport 145
Flux Density 145
Three Transport Modes 148
Migration 149
Diffusion 154
Diffusion and Migration 158
Convection 161
Fluxes at Electrodes and in the Bulk 165
Summary 170
9 Green Electrochemistry 171
Sensors for Pollution Control 171
Stripping Analysis 177
Electrochemical Purification of Water 182
Electrochemistry of Biological Cells 186
Summary 192
10 Electrode Polarization 193
Three Causes of Electrode Polarization 193
Ohmic Polarization 197
Kinetic Polarization 200
Transport Polarization 202
Multiple Polarizations 205
Polarizations in Two- and Three-Electrode Cells 208
Summary 212
11 Corrosion 213
Vulnerable Metals 213
Corrosion Cells 215
Electrochemical Studies 217
Concentrated Corrosion 222
Fighting Corrosion 224
Extreme Corrosion 228
Summary 229
12 Steady-State Voltammetry 231
Features of Voltammetry 232
Microelectrodes and Macroelectrodes 234
Steady-State Potential-Step Voltammetry 237
The Disk Microelectrode 245
Rotating Disk Voltammetry 248
Shapes of Reversible Voltammograms 252
Summary 258
13 The Electrode Interface 259
Double Layers 259
Adsorption 266
The Interface in Voltammetry 271
Nucleation and Growth 281
Summary 285
14 Other Interfaces 287
Semiconductor Electrodes 287
Phenomena at Liquid*Liquid Interfaces 291
Electrokinetic Phenomena 298
Summary 302
15 Electrochemistry With Periodic Signals 303
Nonfaradaic Effects of A.C. 304
Faradaic Effects of A.C. 305
Equivalent Circuits 313
A.C. Voltammetry 318
Fourier-Transform Voltammetry 322
Summary 328
16 Transient Voltammetry 329
Modeling Transient Voltammetry 329
Potential-Step Voltammetry 334
Pulse Voltammetries 339
Ramped Potentials 346
Multiple Electron Transfers 355
Chemistry Combined with Electrochemistry 357
Controlling Current Instead of Potential 362
Summary 364
Appendix 365
Glossary 365
Absolute and Relative Permittivities 382
Properties of Liquid Water 383
Contents ix
Conductivities and Resistivities 384
Elements with Major Importance in Electrochemistry 386
Transport Properties 388
Standard Gibbs Energies 390
Standard Electrode Potentials 392
Index 393
