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Theory of electron-transfer rates across liquid-liquid interfaces. 2. Relationships and application

Marcus, R. A. (1991) Theory of electron-transfer rates across liquid-liquid interfaces. 2. Relationships and application. Journal of Physical Chemistry, 95 (5). pp. 2010-2013. ISSN 0022-3654. https://resolver.caltech.edu/CaltechAUTHORS:20150610-145333343

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Abstract

In part 1 an expression was obtained for the exchange current rate constant k^(ii)_(12) for an electron transfer between a reactant in one liquid and a second reactant in a second immiscible liquid, across an (assumed) sharp interfacial boundary. This expression is used to obtain a relation between k^(ii)_(12) and the self-exchange rate constants k_(11) and k_(22) for electron transfer in homogeneous solutions, each redox species being in its respective liquid phase. The relation provides an extension of the "cross-relation" for one-phase electron transfer to this two-phase case. An expression is also given relating k^(ii)_(12) to the usual metal-liquid electrochemical exchange current rate constants k^(el)_1 and k^(el)_2 these k^(el)’s referring to each reactant in its respective solvent phase. An alternative limiting model for the interfacial region is also considered, in which that region is now broad, instead of sharp. The results of both models are compared with the limited available kinetic data, and the desirability of further experimental studies is noted.


Item Type:Article
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http://dx.doi.org/10.1021/j100158a023 DOIArticle
http://pubs.acs.org/doi/abs/10.1021/j100158a023PublisherArticle
http://dx.doi.org/10.1021/j100015a067ErrataErratum
http://pubs.acs.org/doi/abs/10.1021/j100015a067ErrataErratum
Additional Information:© 1991 American Chemical Society. Received: July 19, 1990; In Final Form: November 12, 1990. It is a pleasure to participate in this commemorative issue of The Journal of Physical Chemistry honoring Professor Albert Weller, whose work I have admired over these many years. The support of this research by the Office of Naval Research is greatly appreciated.
Errata:Theory of Electron Transfer Rates across Liquid-Liquid Interfaces. 2. Relationships and Applications. [Erratum to document cited in CA114:110532] R. A. Marcus The Journal of Physical Chemistry 1995 99 (15), 5742-5742 DOI: 10.1021/j100015a067
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Funding AgencyGrant Number
Office of Naval Research (ONR)UNSPECIFIED
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Other Numbering System NameOther Numbering System ID
Caltech Arthur Amos Noyes Laboratory of Chemical Physics8182
Issue or Number:5
Record Number:CaltechAUTHORS:20150610-145333343
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150610-145333343
Official Citation:Theory of electron-transfer rates across liquid-liquid interfaces. 2. Relationships and application R. A. Marcus The Journal of Physical Chemistry 1991 95 (5), 2010-2013 DOI: 10.1021/j100158a023
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58172
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:11 Jun 2015 03:58
Last Modified:03 Oct 2019 08:33

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