Polarography is still the best known classical measuring method in electroanalytical chemistry. However, in recent years its position has been challenged by cyclic voltammetry (CV). Simple diagnostic criteria and relatively easily acquired measuring techniques have hastened this development. Cyclic voltammetry has the further attraction of providing information not only on the thermodynamics of redox processes but also on the kinetics of heterogeneous electron-transfer reactions and coupled chemical reactions. The characteristic shapes of the voltammetric waves and their unequivocal position on the potential scale virtually fingerprint the individual electrochemical properties of redox systems. For this reason the method has been labeled “electrochemical spectroscopy”.

Cyclic Voltammetry—“Electrochemical Spectroscopy”. New Analytical Methods (25)

Standard potential and kinetic parameters of the electrochemical reduction of carbon dioxide in dimethylformamide

Electrodimerization: I. One-electron irreversible dimerization. Diagnostic criteria and rate determination procedures for voltammetric studies

Adsorption and electrochemical oxidation behaviour of NADH at a clean platinum electrode

Publisher Summary This chapter discusses chemical oxidations, oxidations on acidic surfaces, and photoionizations. The formation of cation radicals in solution is also discussed. The chapter outlines the experimental techniques that have been used to study cation radicals and the type of information that can be obtained about their behavior. Examples of such investigations are provided. A large number of electrochemical techniques is available for producing and studying cation radicals (or other electrogenerated). Their instrumentation, techniques, and theory are described. The electrochemical techniques can be separated into two classes: the microelectrode or voltammetric techniques and the bulk electrolysis or coulometric techniques. Detailed descriptions of physical properties of cation radicals are presented in the chapter. Cation radicals react with a variety of nucleophiles. Substitution often occurs, but there are many examples in which electron transfer occurs either entirely or in part.

Formation, Properties and Reactions of Cation Radicals in Solution

Theory of cyclic voltammetry for a dimerization reaction initiated electrochemically

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Theory of cyclic voltammetry for a dimerization reaction initiated electrochemically