Marcus, R. A. (1963) On the theory of oxidation—Reduction reactions involving electron transfer. V. Comparison and properties of electrochemical and chemical rate constants. Journal of Physical Chemistry, 67 (4). pp. 853-857. ISSN 0022-3654. doi:10.1021/j100798a033. https://resolver.caltech.edu/CaltechAUTHORS:20150812-164543423
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Abstract
Using a theory of electron transfers which takes cognizance of reorganization of the medium outside the inner coordination shell and of changes of bond lengths inside it, relations between electrochemical and related chemical rate constants are deduced and compared with the experimental data. A correlation is found, without the use of arbitrary parameters. Effects of weak complexes with added electrolytes are included under specified conditions. The deductions offer a way of coordinating a variety of data in the two fields, internally as well as with each other, and a way of predicting results in one field from those in another. For example, the rate of oxidation or reduction of a series of related reactants by one reagent is correlated with that of another and with that of the corresponding electrochemical oxidation-reduction reaction, under certain specified conditions. These correlations may also provide a test for distinguishing an electron from an atom transfer mechanism.
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| Additional Information: | © 1963 American Chemical Society. Received October 11, 1962. The author has benefitted considerably from the many stimulating discussions on this subject with Dr. N. Sutin of Brookhaven National Laboratory. He is also particularly indebted to Drs. R. W. Dodson and J. Jordan for their very helpful comments, and to Dr. Dodson and his department for their hospitality during the author's stay at Brookhaven. This work was supported by the U. S. Atomic Energy Commission, the National Science Foundation, and the Alfred P. Sloan Foundation, a support which the author deeply appreciates. Research performed in part under the auspices of the U. S. Atomic Energy Commission. Presented at the “Symposium on Mechanisms of Electrode Reactions,” 142nd American Chemical Society National Meeting, Atlantic City, 1962 | |||||||||
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| Issue or Number: | 4 | |||||||||
| DOI: | 10.1021/j100798a033 | |||||||||
| Record Number: | CaltechAUTHORS:20150812-164543423 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20150812-164543423 | |||||||||
| Official Citation: | ON THE THEORY OF OXIDATION—REDUCTION REACTIONS INVOLVING ELECTRON TRANSFER. V. COMPARISON AND PROPERTIES OF ELECTROCHEMICAL AND CHEMICAL RATE CONSTANTS R. A. Marcus The Journal of Physical Chemistry 1963 67 (4), 853-857 DOI: 10.1021/j100798a033 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 59469 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | George Porter | |||||||||
| Deposited On: | 14 Aug 2015 01:36 | |||||||||
| Last Modified: | 10 Nov 2021 22:21 |
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