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On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. III. Applications to Data on the Rates of Organic Redox Reactions

Marcus, R. A. (1957) On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. III. Applications to Data on the Rates of Organic Redox Reactions. Journal of Chemical Physics, 26 (4). pp. 872-877. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20140505-141531708

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Abstract

A recently developed theory of oxidation‐reduction reactions (Part I) is used to calculate the rates of organic redox reactions whose mechanism involves the transfer of an electron from one reactant to the other. The theory can be used to discuss factors affecting the rates of these reactions. These factors include a standard free energy of reaction, the Coulombic interaction of the ionic charges of the reactants, and the solvation of the charged reactants. Attention is focused on the relation between the rate of the redox step in the over‐all process and the standard free energy change, ΔF^0, of this step, rather than on the more usual but less fundamental one between the corresponding quantities of the over‐all process itself. An approximate method is described for applying the theory to a molecule whose charge is not located at its center. Essentially all organic molecules lie in this category. As an example of these considerations, several typical reactions are discussed. These reactions involve the oxidation of a series of hydroquinones by ferric ions and of a series of leucoindophenols by dissolved oxygen. They are assumed to possess electron transfer, rather than atom transfer, mechanisms. Free energies and entropies of activation of the redox step are calculated using the theoretical equation. The calculated results are considered to be in reasonable agreement with the experimental data, no adjustable parameters being employed.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.1743424DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/26/4/10.1063/1.1743424PublisherArticle
Additional Information:© 1957 American Institute of Physics. Received February 16, 1956. This research was supported by the Office of Naval Research, Contract Nonr 839(09). Reproduction in whole or in part is permitted for any purpose of the U. S. Government.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)Nonr 839(09)
Subject Keywords:Redox; Atom transfer reactions; Chemical reaction theory; Free energy; Electron transfer
Record Number:CaltechAUTHORS:20140505-141531708
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140505-141531708
Official Citation:Marcus, R. A. (1957). On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. III. Applications to Data on the Rates of Organic Redox Reactions. The Journal of Chemical Physics, 26(4), 872-877. doi: doi:http://dx.doi.org/10.1063/1.1743424
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:45503
Collection:CaltechAUTHORS
Deposited By: Aucoeur Ngo
Deposited On:05 May 2014 21:50
Last Modified:13 Feb 2019 18:02

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