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Rapid Oxidation of Ru(NH_3)_6^(3+) by Os(bpy)_3^(3+) within Nafion Coatings on Electrodes

Shi, Minglian and Anson, Fred C. (1996) Rapid Oxidation of Ru(NH_3)_6^(3+) by Os(bpy)_3^(3+) within Nafion Coatings on Electrodes. Langmuir, 12 (8). pp. 2068-2075. ISSN 0743-7463. https://resolver.caltech.edu/CaltechAUTHORS:20180719-163135834

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Abstract

The oxidation of Ru(NH_3)_6^(3+) by Os(bpy)_3^(3+) is a very slow process in aqueous acid. The rate increases with pH but the reaction remains slow at pH 7. However, when the two reactants are incorporated in Nafion coatings on electrodes the oxidation can proceed much more rapidly, especially with Nafion coatings that are not fully hydrated. Rotating disk and cyclic voltammetry were employed to determine the stoichiometry of the reaction and to measure its kinetics both in solution and in Nafion coatings. The Ru(NH_3)_6^(3+) is oxidized to Ru(VII) at a rate that is first order in Ru(NH_3)_6^(3+) and Os(bpy)_3^(3+) and inverse first order in H^+. The reaction rate constant evaluated in solution was similar to that evaluated in Nafion. The higher reaction rate obtained when the reactants are incorporated in Nafion results from their higher concentrations, not from significant enhancement of their reactivities. The higher reaction rate obtained from partially dehydrated Nafion coatings is believed to result from a breakdown in cation permselectivity that permits the ionic current inside the coating during anodic current flow to be carried by anions instead of by the ejection of Ru(NH_3)_6^(3+) cations from the Nafion.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/la950863jDOIArticle
Alternate Title:Rapid Oxidation of Ru(NH3)63+ by Os(bpy)33+ within Nafion Coatings on Electrodes
Additional Information:© 1996 American Chemical Society. Received October 12, 1995. In Final Form: January 9, 1996. This work was supported by the National Science Foundation.
Funders:
Funding AgencyGrant Number
NSFUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Arthur Amos Noyes Laboratory of Chemical Physics9147
Issue or Number:8
Record Number:CaltechAUTHORS:20180719-163135834
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180719-163135834
Official Citation:Rapid Oxidation of Ru(NH3)63+ by Os(bpy)33+ within Nafion Coatings on Electrodes Minglian Shi and Fred C. Anson Langmuir 1996 12 (8), 2068-2075 DOI: 10.1021/la950863j
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:88043
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:23 Jul 2018 16:35
Last Modified:03 Oct 2019 20:02

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