Cyclic Voltammetry; Simulation and Analysis of Reaction Mechanisms

Abstract

Useful Equations 1. The Reduction Potential and Electrode Kinetics 1.1 The Reduction Potential 1.2 Electrode Kinetics References 2. The Cyclic Voltammetric Experiment 2.1 An Overview 2.2 The Electrochemical Cell 2.3 Electrochemical Mechanisms: E&C Notation 2.4 Distortions of the Faradaic Response 2.5 Microelectrodes and Fast Scan Voltammetry 2.6 Potential Step Methods and Cyclic Voltammetry 2.7 Construction of a Fast Potentiostat 2.8 Determination of the Number of Electrons References 3. A Survey of Electrochemical Mechanisms 3.1 The CE Mechanism 3.2 Multielectron Transfer 3.3 Protonations at Equilibrium 3.4 Catalytic Mechanisms 3.5 The Reduction of Nitrobenzoic Acid 3.6 Reduction of the Nit rosonium Cation and Its Complexes 3.7 Reactivity of 17--, 18--, and 19--Electron Tungsten Complexes 3.8 Mechanisms Involving Adsorption References 4. The Simulation of Electrochemical Experiments 4.1 The Discretized Diffusion Equation 4.2 Evaluation of the Boundary Conditions 4.3 Dimensionless Units 4.4 Solution Chemical Kinetics 4.5 A Sample Simulation Program References 5. CVSIM: A General Program for the Simulation of Cyclic Voltammetry Experiments 5.1 An Overview of CVSIM 5.2 Extensions of the Simulation Method 5.3 Accuracy of Simulations 5.4 Installation and Use of CVSIM and CVGRAF 5.5 Examples References 6. CVFIT: Simplex Data Analysis with CVSIM 6.1 CVFIT: Simplex Data Analysis with CVSIM 6.2 Instructions for the use of CVFIT 6.3 A Prototype Analysis: The EC Mechanism 6.4 Some Final Comments on Simulation Analysis References Appendix: Summary of Instructions for CVSIM, CVGRAF, CVFIT, and DSTEP Index