Electrochemistry

Preface xiii
List of Symbols and Units xv

1 Foundations, Definitions and Concepts 1
1.1 Ions, Electrolytes and the Quantisation of Electrical Charge 1
1.2 Transition from Electronic to Ionic Conductivity in an Electrochemical Cell 3
1.3 Electrolysis Cells and Galvanic Cells: The Decomposition Potential and the Concept of EMF 4
1.4 Faraday's Laws 7
1.5 Systems of Units 9

2 Electrical Conductivity and Interionic Interactions 13
2.1 Fundamentals 13
2.2 Empirical Laws of Electrolyte Conductivity 21
2.3 Ionic Mobility and Hittorf Transport 27
2.4 The Theory of Electrolyte Conductivity: The Debye-Hückel-Onsager Theory of Dilute Electrolytes 38
2.5 The Concept of Activity from the Electrochemical Viewpoint 46
2.6 The Properties of Weak Electrolytes 61
2.7 The Concept of pH and the Idea of Buffer Solutions 64
2.8 Non-aqueous Solutions 66
2.9 Simple Applications of Conductivity Measurements 71

3 Electrode Potentials and Double-Layer Structure at Phase Boundaries 77
3.1 Electrode Potentials and their Dependence on Concentration, Gas Pressure and Temperature 77
3.2 Liquid-junction Potentials 105
3.3 Membrane Potentials 112
3.4 The Electrolyte Double-Layer and Electrokinetic Effects 115
3.5 Potential and Phase Boundary Behaviour at Semiconductor Electrodes 133
3.6 Simple Applications of Potential Difference Measurements 139

4 Electrical Potentials and Electrical Current 157
4.1 Cell Voltage and Electrode Potential during Current Flow: an Overview 157
4.2 The Electron-transfer Region of the Current-Potential Curve 162
4.3 The Concentration Overpotential – The Effect of Transport of Material on the Current-Voltage Curve 185
4.4 The Effect of Simultaneous Chemical Processes on the Current Voltage Curve 203
4.5 Adsorption Processes 207
4.6 Electrocrystallisation – Metal Deposition and Dissolution 213
4.7 Mixed Electrodes and Corrosion 225
4.8 Current Flows on Semiconductor Electrodes 231
4.9 Bioelectrochemistry 241

5 Methods for the Study of the Electrode/Electrolyte Interface 251
5.1 The Measurement of Stationary Current-Potential Curves 251
5.2 Quasi-Stationary Methods 260
5.3 Electrochemical Methods for the Study of Electrode Films 291
5.4 Spectroelectrochemical and other Non-classical Methods 295
5.5 Preparation of Nanostructures, Combination of STM and UHV-Transfer 326
5.6 Optical Methods 328

6 Electrocatalysis and Reaction Mechanisms 339
6.1 On Electrocatalysis 339
6.2 The Hydrogen Electrode 341
6.3 The Oxygen Electrode 346
6.4 Methanol Oxidation 348
6.5 Carbon Monoxide Oxidation at Platinum Surfaces 358
6.6 Conversion of Chemical Energy of Ethanol into Electricity 364
6.7 Reaction Mechanisms in Electro-organic Chemistry 366
6.8 Oscillations in Electrochemical Systems 375

7 Solid and Molten-salt Ionic Conductors as Electrolytes 381
7.1 Ionically Conducting Solids 381
7.2 Solid Polymer Electrolytes (SPE's) 386
7.3 Ionically-conducting Melts 392