Square-wave voltammetry : theory and application

Square-wave voltammetry is a technique readily available to every researcher, scientist, engineer and practitioner applying modern electrochemical measurement systems. It is of beneficial use in analytical applications and in fundamental studies of electrode mechanisms. But the optimised exploitation of this technique is only possible for those with a detailed knowledge of signal generation and of the thermodynamics and kinetics involved. This volume, written by three distinguished experts, systematically delivers the complete and in-depth information that enables both researchers and users of square-wave voltammetry to apply this technique effectively. Square-Wave Voltammetry also offers an appendix on mathematical modeling and a chapter on the most important electrode mechanisms which briefly reviews the underlying theory and numerical formulae intrinsic for simulating experiments with popular software tools , e.g. Mathcad (R).

1 Introduction	p. 1
1.1 From Square-Wave Polarography to Modern Square-Wave Voltammetry	p. 1
1.2 Square-Wave Voltammetry: Calculations and Instrumentation	p. 6
References	p. 11
2 Electrode Mechanisms	p. 13
2.1 Electrode Reactions of Dissolved Species on Stationary Planar Electrodes	p. 13
2.1.1 Reversible Electrode Reactions	p. 13
2.1.2 Kinetically Controlled Electrode Reaction	p. 17
2.2 Reactions of Dissolved Species on Spherical Electrodes and Microelectrodes	p. 25
2.3 Reactions of Amalgam-Forming Metals on Thin Mercury Film Electrodes	p. 32
2.3.1 Reversible Reduction of Metal Ions on Stationary Electrode	p. 32
2.3.2 Anodic Stripping Square-Wave Voltammetry of Metal Ions	p. 35
2.4 Chemical Reactions Coupled to Electrode Reactions	p. 39
2.4.1 CE Mechanism	p. 40
2.4.2 EC Mechanism	p. 45
2.4.3 ECE Mechanism	p. 49
2.4.4 EC' Catalytic Mechanism	p. 54
2.5 Surface Electrode Reactions	p. 60
2.5.1 Simple Surface Electrode Reaction	p. 60
2.5.2 Surface Electrode Reaction Involving Interactions Between Immobilized Species	p. 77
2.5.3 Surface Electrode Reactions Coupled with Chemical Reactions	p. 81
2.5.4 Two-Step Surface Electrode Reaction	p. 91
2.6 Mixed-Electrode Reactions	p. 97
2.6.1 Electrode Reactions Coupled with Adsorption of the Reactant and Product of the Electrode Reaction	p. 97
2.6.2 Electrode Reactions Coupled with Adsorption and Chemical Reactions	p. 110
2.6.3 Electrode Reactions of Insoluble Salts	p. 121
2.7 Square-Wave Voltammetry Applied to Thin-Layer Cell	p. 130
References	p. 139
3 Applications	p. 143
3.1 Quantitative Analysis	p. 143
3.2 Qualitative Identification of Phases	p. 149
3.3 Mechanistic and Kinetic Studies	p. 150
References	p. 157
4 Square-Wave Voltammetry at Liquid-Liquid Interface	p. 163
4.1 Three-Phase Electrodes and Their Application to Measure the Energy of Ion Transfer Across Liquid-Liquid Interface	p. 163
4.2 Analyzing the Kinetics of the Ion Transfer Across Liquid-Liquid Interface with Thin-Film Electrodes	p. 169
References	p. 177
A Mathematical Modeling of Electrode Reaction in a Thin-Layer Cell with the Modified Step-Function Method	p. 179
References	p. 185
Index	p. 197

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