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A study of the entropic and electrolyte effects in electron transfer reactions

Waisman, Eduardo and Worry, Gary and Marcus, R. A. (1977) A study of the entropic and electrolyte effects in electron transfer reactions. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 82 (1-2). pp. 9-28. ISSN 0022-0728. http://resolver.caltech.edu/CaltechAUTHORS:20150708-114400041

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Abstract

The entropy of activation ΔS^‡ for electron transfer reactions occurring in concentrated electrolyte solutions is calculated, taking into account the electrostatic and electronic contributions. By applying the mean spherical and exponential approximations to treat a simple model of electrolytes (hard charged spheres in a dielectric continuum), the pair distribution function is calculated. These approximations are also used to calculate the electrolyte reorganization term, since both quantities contribute to the electrostatic part of ΔS^‡. Numerical application is made to the ferrous-ferric exchange reaction in 0.55 M HClO_4. Results of a preliminary electron tunneling calculation for the electron transfer are included. Reasonable agreement between observed and calculated ΔS^‡ is obtained.


Item Type:Article
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http://dx.doi.org/10.1016/S0022-0728(77)80248-9DOIArticle
http://www.sciencedirect.com/science/article/pii/S0022072877802489PublisherArticle
Additional Information:© 1977 Published by Elsevier B.V. Received 1 February 1977, Available online 20 June 2006. We are particularly indebted to Professor David Chandler and Dr. Marshall Newton for helpful discussions on various aspects of the problem and to Professor Lesser Blum for discussing with us the Blum-Høye results [27b] prior to publication. It is a pleasure, too, to acknowledge support of this work by the Office of Naval Research.
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Office of Naval Research (ONR)UNSPECIFIED
Record Number:CaltechAUTHORS:20150708-114400041
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150708-114400041
Official Citation:Eduardo Waisman, Gary Worry, R.A. Marcus, A study of the entropic and electrolyte effects in electron transfer reactions, Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Volume 82, Issues 1–2, 9 September 1977, Pages 9-28, ISSN 0022-0728, http://dx.doi.org/10.1016/S0022-0728(77)80248-9. (http://www.sciencedirect.com/science/article/pii/S0022072877802489)
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ID Code:58810
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:08 Jul 2015 22:10
Last Modified:13 Feb 2019 18:06

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