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Electron Transfer in Homogeneous and Heterogeneous Systems

Marcus, R. A. (1975) Electron Transfer in Homogeneous and Heterogeneous Systems. In: The Nature of Seawater. Physical and Chemical Sciences Research Report . No.1. , Berlin, Germany, pp. 477-504. ISBN 978-3820012019. http://resolver.caltech.edu/CaltechAUTHORS:20150929-075236138

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Abstract

The mechanism o f electron transfer in solution and at electrodes is described. A theoretical analysis involving the fluctuations in the chemical bond distances and in the dielectric polarization of the partially oriented solvent molecules about the reactants leads to an expression for the rate constant of these reactions. Relations are obtained between the rate constants of cross reactions k_(12) self-exchange reactions k_(11), [e.g., k_(12)≅ (k_(11)k_(22)K_(12)f_(12)1/2, and reactions at surfaces (electrodes, both metal and semiconductor type). There are many comparisons between theory and experiment and a survey is given. The effect of standard free energy of reaction and of electrode potential is included, as in the Co^(+3) (aq) anomaly, and the occurrence of chemiluminescence. The discussion is preceded by a brief description of reaction rate theory in general and of atom versus electron transfer mechanisms in particular.


Item Type:Book Section
Additional Information:© 1975 Berlin, Germany.
Record Number:CaltechAUTHORS:20150929-075236138
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150929-075236138
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:60586
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:29 Sep 2015 18:41
Last Modified:29 Sep 2015 18:41

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