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On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. II. Applications to Data on the Rates of Isotopic Exchange Reactions

Marcus, R. A. (1957) On the Theory of Oxidation-Reduction Reactions Involving Electron Transfer. II. Applications to Data on the Rates of Isotopic Exchange Reactions. Journal of Chemical Physics, 26 (4). pp. 867-871. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20140505-144811265

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Abstract

The rates of some homogeneous isotopic exchange reactions in solution are considered in the light of a recently developed quantitative theory of redox processes (Part I). The relative importance of several factors influencing the rates of these reactions is discussed. These factors include the Coulombic repulsion between the ionic reactants and the extent of solvation of the ions. Free energies and entropies of activation of various reactions are calculated from the theory without the use of any adjustable parameters. The agreement with the experimental data is considered to be satisfactory. On the basis of the theory and of earlier experiments in heavy water an experimental method is tentatively suggested for distinguishing electron and atom transfer mechanisms. This method applies to halide‐catalyzed exchange reactions of metal aquo-ions, and to other anion‐catalyzed reactions of this type not involving breakable OH bonds.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.1743423DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/26/4/10.1063/1.1743423PublisherArticle
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 purposes of the U. S. Government.
Funders:
Funding AgencyGrant Number
Office of Naval Research (ONR)Nonr 839(09)
Subject Keywords:Exchange reactions; Atom transfer reactions; Chemical reaction theory; Redox; Electron transfer
Record Number:CaltechAUTHORS:20140505-144811265
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140505-144811265
Official Citation:Marcus, R. A. (1957). On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. II. Applications to Data on the Rates of Isotopic Exchange Reactions. The Journal of Chemical Physics, 26(4), 867-871. doi: doi:http://dx.doi.org/10.1063/1.1743423
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:45505
Collection:CaltechAUTHORS
Deposited By: Aucoeur Ngo
Deposited On:05 May 2014 22:50
Last Modified:13 Feb 2019 18:02

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