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Cerium (IV) oxidation rate of p-chloromandelic acid in perchlorate and sulfate media

✍ Scribed by Giuseppe Calvaruso; F. Paolo Cavasino; Carmelo Sbriziolo

Publisher
John Wiley and Sons
Year
1981
Tongue
English
Weight
596 KB
Volume
13
Category
Article
ISSN
0538-8066

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✦ Synopsis

The rate of the cerium (IV) oxidation of p-chloromandelic acid has been studied in perchlorate media at an ionic strength of 1.50 mol/dm3 by the stopped-flow technique and in HzS04-MHS04 (M+ = Li+, Na+, K+) and H2S04-MC104 (M+ = H+, Li+, Na+) mixtures at constant total electrolyte concentrations of 1.00 and 2.00 mol/dm3 using the conventional spectrophotometric method. In perchlorate media the kinetic data indicate the formation of two intermediate complexes between cerium (IV) and the organic substrate, but only one is significantly involved in the intramolecular electron-transfer process. The oxidation rate is markedly lower in sulfate media, where two reaction paths have been found to contribute to the overall redox reaction. The univalent cations examined exhibit negative specific effects upon the overall oxidation rate increasing in the order H+ < Li+ < Na+ < K+. Activation parameters have been also estimated.

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