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:

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.

1 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