Electrochemical Science and Technology

Preface xi 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 Faraday s 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 LiquidLiquid 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