On the theory of oxidation-reduction reactions and of related processes

Abstract

Recent years have witnessed the elucidation of the mechanisms of many organic and inorganic chemical reactions. Several principal factors have contributed to this development. Among these may be listed the detailed kinetic study of numerous reactions, and the use of isotopic tracers, in some cases, to map the migration of specific atoms between the reacting molecules. Another factor is the deep insight into reaction mechanisms afforded by qualitative application of the ideas of modern valence theory, such as those embodied in the conception of the activated complex. Oxidation-reduction reactions provide typical examples of this trend. Detailed kinetic studies have shown that they frequently involve a number of successive reaction steps. Attention has become focused on the rates and mechanisms of these elementary reactions, some of which are equilibria involving the formation, or disappearance, of the species participating in the actual redox step. Similar remarks apply to electrode processes, whose slow rate is one cause of overvoltage and of polarographic irreversibility. Detailed studies of the mechanism of these processes, frequently by alternating current techniques, are comparatively fewer, but they have begun to reveal the complexities and trends involved. These processes, too, may involve several successive steps, some of which are associated with the formation or disappearance of the reacting particle undergoing electron or atom transfer with the electrode. Isotopic tracer techniques have been employed here also.

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