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Theory of electron-transfer rates across liquid-liquid interfaces

Marcus, R. A. (1990) Theory of electron-transfer rates across liquid-liquid interfaces. Journal of Physical Chemistry, 94 (10). pp. 4152-4155. ISSN 0022-3654. doi:10.1021/j100373a051.

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The theory developed in a previous paper for the geometry of the encounter complex, the reorganization energy, and the electron-transfer rate constant at a liquid-liquid interface is applied to existing data on the rate constant. To treat cyclic voltammetric (CV) studies of electron transfer across the interface, the nature of the encounters is examined and a bimolecular-type rate treatment is used. When one redox pair is in large excess, it has been pointed out that a single-phase CV analysis for diffusion/reaction can be utilized. In the present paper we avoid in this analysis the assumption that the second ("concentrated") phase is metallike. The experimental result deduced in this way for the true exchange current electron-transfer rate constant at the interface is compared with that estimated from the present theory of the rate constant, using metal-liquid electrochemical exchange rate constants. The type of agreement found is encouraging, considering the various approximations involved, and further experimental studies and tests would be of interest.

Item Type:Article
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URLURL TypeDescription ErrataErratum
Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1990 American Chemical Society. Received: October 6, 1989; In Final Form: December 21, 1989. It is a pleasure to acknowledge the support of this research by the Office of Naval Research and by the National Science Foundation.
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Office of Naval Research (ONR)UNSPECIFIED
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Caltech Noyes Laboratory of Chemical Physics8037
Issue or Number:10
Record Number:CaltechAUTHORS:20150514-111330363
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Official Citation:Theory of electron-transfer rates across liquid-liquid interfaces R. A. Marcus The Journal of Physical Chemistry 1990 94 (10), 4152-4155 DOI: 10.1021/j100373a051
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:57530
Deposited By: Tony Diaz
Deposited On:14 May 2015 18:21
Last Modified:10 Nov 2021 21:51

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