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1 Equilibrium Electrochemistry and the Nernst Equation1

1.1 Cell Thermodynamics1

1.2 The Nernst Equation2

1.3 The Nernst Equation3

1.4 The Nernst Equation5

1.5 Theory of the Nernst Equation5

1.6 The Debye-Hückel Limiting Law7

1.7 Cell Reaction and Equilibrium Constant10

1.8 Cell Reaction and Equilibrium Constant11

1.9 Cell Reaction and Solubility Product12

1.10 Cell Reaction and pKa13

1.11 Cell Thermodynamics and Temperature14

1.12 Cell Thermodynamics and Temperature15

1.13 Cell Energetics16

1.14 Cell EMF and pH17

1.15 Cell Reaction and Equilibria18

1.16 Cell Reaction and Kw19

1.17 Cell Reaction and Disproportionation20

1.18 Fuel Cell Energetics21

1.19 Fuel Cell Energetics22

1.20 The Influence of Temperature on the Self-Ionisation of Water23

1.21 Cell Reaction and Complexation24

1.22 Reference Electrodes26

1.23 Formal Potentials27

1.24 Formal Potentials28

1.25 Standard Potentials and pH29

1.26 Standard Potentials and pH30

1.27 Standard Potentials and pH31

2 Electrode Kinetics35

2.1 Faraday's Laws of Electrolysis35

2.2 Electrodeposition36

2.3 Tafel Analysis:One-Electron Processes39

2.4 Tafel Analysis:Electrochemically Reversible Processes39

2.5 Tafel Analysis:Mass Transport Correction41

2.6 Tafel Analysis:Two-Electron Processes42

2.7 The Butler-Volmer Equation and the Nernst Equation45

2.8 The Hydrogen Evolution Reaction46

2.9 Requirement for Supporting Electrolyte47

2.10 Frumkin Corrections49

2.11 Marcus Theory and Standard Electrochemical Rate Constants51

2.12 Marcus Theory and Butler-Volmer Kinetics52

2.13 Marcus Theory and the Role of Solvent54

2.14 Marcus Theory and the Inverted Region55

3 Diffusion57

3.1 Fick's Laws of Diffusion57

3.2 Fick's Laws of Diffusion58

3.3 Diffusion Distances59

3.4 The Cottrell Equation60

3.5 Derivation of the Cottrell Equation62

3.6 Diffusion and Root-Mean-Square Displacement66

4 Cyclic Voltammetry at Macroelectrodes67

4.1 Cyclic Voltammetry:Electrochemically Reversible Voltammetry67

4.2 Cyclic Voltammetry:Electrochemically Irreversible Voltammetry69

4.3 Reversible vs Irreversible Voltammetry71

4.4 Voltammetric Diagnostics72

4.5 Voltammetry and Scan Rate Effects73

4.6 Ferrocene Voltammetry75

4.7 Ferrocene Voltammetry75

4.8 Features of Cyclic Voltammograms76

4.9 Derivation of the Randles-？ev？ík Equation77

4.10 Reversible Two-Electron Transfer81

4.11 The Influence of pH on Cyclic Voltammetry82

4.12 The Scheme of Squares84

4.13 The EE-Comproportionation Mechanism86

5 Voltammetry at Microelectrodes91

5.1 Steady-State Concentration Profile in Spherical Space91

5.2 Current Transients at a Spherical Electrode93

5.3 Linear vs Convergent Diffusion94

5.4 Dissolution of Microparticles95

5.5 Steady-State Limiting Current at a Microdisc97

5.6 Microdisc vs Planar Electrode98

5.7 The Shoup-Szabo Equation98

5.8 Steady-State Electrolysis100

5.9 Effect of Unequal Diffusion Coefficients101

5.10 Temperature Effects on Steady-State Currents101

5.11 ECE Mechanism at a Microdisc Electrode103

5.12 EC' Mechanism at a Microdisc Electrode105

5.13 Size Effects on Half-Wave Potentials106

5.14 Extracting Parameters from Microdisc Chronoamperometry107

5.15 Extracting Parameters from Microdisc Chronoamperometry109

6 Voltammetry at Heterogeneous Surfaces111

6.1 Graphitic Electrodes111

6.2 Carbon Nanotubes and Their Reactivity113

6.3 Highly Ordered Pyrolytic Graphite and the Influence of Defects114

6.4 Advantages of Arrays115

6.5 Diffusional'Cases'116

6.6 Geometry of a Regular Array117

6.7 Analysis of Diffusion to Electrode Arrays119

6.8 Partially Blocked Electrodes121

7 Cyclic Voltammetry:Coupled Homogeneous Kinetics and Adsorption123

7.1 EE Mechanism and Comproportionation123

7.2 EE mechanism:The Reduction of [(η6-C6Me6)2Ru][BF4]2124

7.3 EC2 Mechanism:The Reduction of the 2,6-Diphenyl Pyrylium Cation126

7.4 Analysis of an Unknown Reaction Mechanism128

7.5 EC Mechanism:Diethyl Maleate130

7.6 ECE Mechanism:p-chlorobenzonitrile133

7.7 ECE vs DISP 1:Voltammetry of Fluorescein135

7.8 Reduction of Anthracene in DMF137

7.9 CE Mechanism140

7.10 EC' Mechanism142

7.11 EC' Mechanism:Cysteine and Ferrocyanide143

7.12 EC' Mechanism:Oxygen and Anthraquinone145

7.13 Chronoamperometry of Adsorbed Species146

7.14 Voltammetry of an Ideal Adsorbed Species147

7.15 Non-Ideal Adsorbed Species150

7.16 Irreversible Electron Transfer and Adsorbed Redox Species153

7.17 Voltammetry of Ferrocyanide/Ferricyanide157

8 Hydrodynamic Electrodes159

8.1 Channel Electrodes and Limiting Currents159

8.2 Channel Electrodes and Reynolds Number160

8.3 Flow to Rotating Discs and in Channels161

8.4 Channel Electrodes and ECE Processes162

8.5 Channel Electrodes and ECE Processes164

8.6 Channel Electrodes and Entry Length167

8.7 Channel Electrodes and Diffusion Coefficients167

8.8 Channel Electrodes and Current Distribution169

8.9 Wall-Jet Electrodes and Current Distribution170

8.10 Wall-Jet Electrodes and Diffusion Coefficients170

8.11 Wall-Jet Electrode and a DISP 1 Process172

8.12 Wall-Jet Electrode and EC Processes173

8.13 Sono-Voltammetry177

8.14 Rotating Disc Electrodes and Reynolds Number178

8.15 Wall-Jet and Rotating Disc Electrodes178

8.16 Rotating Disc Electrodes and ECE Processes180

9 Voltammetry for Electroanalysis183

9.1 Electrochemical Sizing of Gold Surfaces183

9.2 Differential Pulse Voltammetry185

9.3 Square-Wave Voltammetry186

9.4 Square-Wave Voltammetry and Dissolved Oxygen187

9.5 Stripping Voltammetry188

9.6 Analysis of DNA189

9.7 The Clark Cell191

9.8 Calibration and Limits of Detection193

9.9 Enzyme Electrodes195

9.10 Glucose Biosensors196

9.11 Detection of Vitamin B12198

9.12 The Anodic Stripping Voltammetry of Industrial Effluent200

9.13 Adsorptive Stripping Voltammetry at Carbon Nanotube Modified Electrodes202

9.14 Surface Modified Electrodes205

9.15 Electron Transfer Rates at Carbon Electrodes208

10 Voltammetry in Weakly Supported Media:Migration and Other Effects211

10.1 Coulomb's Law211

10.2 The Nernst-Planck Equation212

10.3 Migration and the Electric Field215

10.4 Transport Numbers and Liquid Junction Potentials217

10.5 Transport Numbers and the Hittorf Method220

10.6 The Gouy-Chapman Equation221

10.7 Ohmic Drop225

10.8 The Zero-Field Approximation227

10.9 Self-Supported Reduction of the Cobaltocenium Cation228

11 Voltammetry at the Nanoscale233

11.1 Debye Length vs Diffusion Layer Thickness233

11.2 Altered Electrode Kinetics and Reactivity at the Nanoscale235

11.3 Nanoparticles:Case 4 Behaviour236

11.4 'Coulomb Staircase'Effects238

11.5 Ultrafast'Single Molecule'Voltammetry239

11.6 Thin-Layer Effects in Nanoscale Voltammetry242

11.7 Voltammetry in a Nanochannel244

Index249