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Electron spin resonance kinetic studies of malonyl radical self-decay and oxidation reactions by cerium(IV) and bromate in acid aqueous media. The role of free radicals in the Belousov-Zhabotinskii oscillator

Brusa, M. A. and Perissinotti, L. J. and Colussi, A. J. (1985) Electron spin resonance kinetic studies of malonyl radical self-decay and oxidation reactions by cerium(IV) and bromate in acid aqueous media. The role of free radicals in the Belousov-Zhabotinskii oscillator. Journal of Physical Chemistry, 89 (9). pp. 1572-1574. ISSN 0022-3654 . http://resolver.caltech.edu/CaltechAUTHORS:20150623-154812181

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Abstract

Kinetics of selected reactions involving malonyl radicals (M), generated by Ce(IV) oxidation of malonic acid in acid aqueous media, have been studied by steady-state electron spin resonance under stopped-flow conditions. Rate constants for second-order radical self-decay, k_2(M+M) = 3.2 x 10^9, oxidation by bromate, k_4(M+BrO_3^-) = 6.7 x 10^3, and an upper limit for its oxidation by Ce(IV), k_3(M+Ce(Iv)) ≤ 1.2 x 10^5 M^(-1) s^(+1), have been obtained at 298 K. Some of the consequences of the present results on the mechanism of the Belousov-Zhabotinskii oscillator are examined.


Item Type:Article
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http://dx.doi.org/10.1021/j100255a006DOIArticle
http://pubs.acs.org/doi/abs/10.1021/j100255a006PublisherArticle
ORCID:
AuthorORCID
Colussi, A. J.0000-0002-3400-4101
Additional Information:© 1985 American Chemical Society. (Received: January 4, 1985) Generous support by CIC of Argentina is gratefully acknowledged.
Funders:
Funding AgencyGrant Number
Comision de Investigaciones Cientificas de la Provincia de Buenos AiresUNSPECIFIED
Record Number:CaltechAUTHORS:20150623-154812181
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20150623-154812181
Official Citation:Electron spin resonance kinetic studies of malonyl radical self-decay and oxidation reactions by cerium(IV) and bromate in acid aqueous media. The role of free radicals in the Belousov-Zhabotinskii oscillator M. A. Brusa, L. J. Perissinotti, and A. J. Colussi The Journal of Physical Chemistry 1985 89 (9), 1572-1574 DOI: 10.1021/j100255a006
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58537
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:24 Jun 2015 20:45
Last Modified:24 Jun 2015 20:45

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