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Preface

1 Equilibrium Electrochemistry and the Nernst Equation

1.1 Chemical Equilibrium

1.2 Electrochemical Equilibrium: Introduction

1.3 Electrochemical Equilibrium: Electron Transfer at the Solution-Electrode Interface

1.4 Electrochemical Equilibrium: The Nernst Equation

1.5 Walther Hermann Nernst

1.6 Reference Electrodes and the Measurement of Electrode Potentials

1.7 The Hydrogen Electrode as a Reference Electrode

1.8 Standard Electrode Potentials and Formal Potentials

1.9 Formal Potentials and Experimental Voltammetry

1.10 Electrode Processes: Kinetics vs. Thermodynamics

2 Electrode Kinetics

2.1 Currents and Reaction Fluxes

2.2 Studying Electrode Kinetics Requires Three Electrodes

2.3 Butler-Volmer Kinetics

2.4 Standard Electrochemical Rate Constants and Formal Potentials

2.5 The Need for Supporting Electrolyte

2.6 The Tafel Law

2.7 Julius Tafel

2.8 Multistep Electron Transfer Processes

2.9 Tafel Analysis and the Hydrogen Evolution Reaction

2.10 B. Stanley Pons

2.11 Cold Fusion -- The Musical!

2.12 Why Are Some Standard Electrochemical Rate Constants Large but Others Slow? The Marcus Theory of Electron Transfer: An Introduction

2.13 Marcus Theory: Taking it Further. Inner and Outer Sphere Electron Transfer

2.14 Marcus Theory: Taking it Further. Adiabatic and Non-Adiabatic Reactions

2.15 Marcus Theory: Taking it Further. Calculating the Gibbs Energy of Activation

2.16 Relationship between Marcus Theory and Butler-Volmer Kinetics

2.17 Marcus Theory and Experiment. Success!

3 Diffusion

3.1 Fick's 1st Law of Diffusion

3.2 Fick's 2nd Law of Diffusion

3.3 The Molecular Basis of Fick's Laws

3.4 How Did Fick Discover His Laws?

3.5 The Cottrell Equation: Solving Fick's 2nd Law

3.6 The Cottrell Problem: The Case of Unequal Diffusion Coefficients

3.7 The Nernst Diffusion Layer

3.8 Mass Transfer vs. Electrode Kinetics: Steady-State Current-Voltage Waveshapes

3.9 Mass Transport Corrected Tafel Relationships

4 Cyclic Voltammetry at Macroelectrodes

4.1 Cyclic Voltammetry: The Experiment

4.2 Cyclic Voltammetry: Solving the Transport Equations

4.3 Cyclic Voltammetry: Reversible and Irreversible Kinetics

4.4 What Dictates'Reversible' and'Irreversible' Behaviour?

4.5 Reversible and Irreversible Behaviour: The Effect of Voltage Scan Rate

4.6 Reversible versus Irreversible Voltammetry: A Summary

4.7 The Measurement of Cyclic Voltammograms: Three Practical Considerations

……

5 Voltammetry at Microelectrodes

6 Voltammetry at Heterogeneous Surfaces

7 Cyclic Voltammetry: Coupled Homogeneous Kinetics and Adsorption

8 Hydrodynamic Electrodes

9 Voltammetry for Electroanalysis

10 Voltammetry in Weakly Supported Media: Migration and Other Effects

11 Voltammetry at the Nanoscale

Appendix: Simulation of Electrode Processes

Index

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