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Shifts in Redox Formal Potentials Accompanying the Incorporation of Cationic Complexes in Perfluoro Polycarboxylate and Polysulfonate Coatings on Graphite Electrodes

Tsou, Yu-Min and Anson, Fred C. (1984) Shifts in Redox Formal Potentials Accompanying the Incorporation of Cationic Complexes in Perfluoro Polycarboxylate and Polysulfonate Coatings on Graphite Electrodes. Journal of the Electrochemical Society, 131 (3). pp. 595-601. ISSN 0013-4651. http://resolver.caltech.edu/CaltechAUTHORS:TSOjes84

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Abstract

The formal potentials of several redox couples incorporated in coatings of a perfluoropolycarboxylate on graphite electrodes were measured and compared with the formal potentials of the same couples in homogeneous solution. The differences observed agreed with those calculated from the Nernst equation with the independently measured incorporationcoefficients for both halves of the redox couples. The dependences of the shifts in formal potentials on the nature of theincorporating complex ion, the ionic strength, and the temperature were determined and indicated that the incorporationequilibrium is governed by electrostatic and hydrophobic interactions that act in opposite directions. The incorporation ofmost cations examined was driven by large increases in entropy which overcame the usually unfavorable enthalpy changes.


Item Type:Article
Additional Information:©1984 The Electrochemical Society, Inc. Manuscript submitted May 20, 1983; revised manuscript received Sept. 23, 1983. This work was supported by the U.S. Army Research Office. Dr. H. Zumbrunnen offered many helpful suggestions during early stages of this work. We thank Asahi Glass Company, Tokyo, for a sample of polyelectrolyte II.
Subject Keywords:polymer electrolytes; polymer films; graphite; electrochemical electrodes; positive ions; reduction (chemical); oxidation; electric potential
Record Number:CaltechAUTHORS:TSOjes84
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:TSOjes84
Alternative URL:http://dx.doi.org/10.1149/1.2115632
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:4934
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:13 Sep 2006
Last Modified:26 Dec 2012 09:02

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