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Chemical and Electrochemical Electron-Transfer Theory

Chemical and Electrochemical Electron-Transfer Theory One of the active areas in reaction kinetics during the post-war years has been that of electron-transfer reactions. These reactions constitute one type of oxidation-reduction process and include both chemical and electro­ chemical systems. Many rate constants have now been measured ( 1-8) and they have stimulated a variety of t heoretical studies (9-37). The field has been characterized by a strong interplay of theory and experiment, which now includes the testing of theoretically predicted quantitative correlations (34) . Because of a certain unique feature of the purely electron-transfer reactions-the absence of bond rupture in the reaction step--these corre­ lations are unusual. They do not have the arbitrary parameters that occur in theoretical studies of most other reactions in chemical kinetics. This re­ view will be limited to purely electron transfer reactions. A variety of factors have contributed to the growth of this research. The ready availability of isotopes after the war facilitated the extensive study of isotopic exchange reactions. Some of these exchanges proceed via e1ec tron transfer mechanisms and, in this case, form the simplest group of all electron­ transfer reactions. Their study permitted a concentration on the major structural feature of the inorganic reactants-the composition http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Annual Review of Physical Chemistry Annual Reviews

Chemical and Electrochemical Electron-Transfer Theory

Marcus, R A
Annual Review of Physical Chemistry , Volume 15 (1) – Oct 1, 1964
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Publisher
Annual Reviews
Copyright
Copyright 1964 Annual Reviews. All rights reserved
Subject
Review Articles
ISSN
0066-426X
eISSN
1545-1593
DOI
10.1146/annurev.pc.15.100164.001103
Publisher site
See Article on Publisher Site

Abstract

One of the active areas in reaction kinetics during the post-war years has been that of electron-transfer reactions. These reactions constitute one type of oxidation-reduction process and include both chemical and electro­ chemical systems. Many rate constants have now been measured ( 1-8) and they have stimulated a variety of t heoretical studies (9-37). The field has been characterized by a strong interplay of theory and experiment, which now includes the testing of theoretically predicted quantitative correlations (34) . Because of a certain unique feature of the purely electron-transfer reactions-the absence of bond rupture in the reaction step--these corre­ lations are unusual. They do not have the arbitrary parameters that occur in theoretical studies of most other reactions in chemical kinetics. This re­ view will be limited to purely electron transfer reactions. A variety of factors have contributed to the growth of this research. The ready availability of isotopes after the war facilitated the extensive study of isotopic exchange reactions. Some of these exchanges proceed via e1ec tron transfer mechanisms and, in this case, form the simplest group of all electron­ transfer reactions. Their study permitted a concentration on the major structural feature of the inorganic reactants-the composition

Journal

Annual Review of Physical Chemistry – Annual Reviews

Published: Oct 1, 1964

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