Mechanism of OH radical-induced oxidation of p-cresol to p-methylphenoxyl radical

Mechanism of OH radical-induced oxidation of p-cresol to p-methylphenoxyl radical The OH radical-induced oxidation of p-cresol to p-methylphenoxyl radical was studied in aqueous solution in a wide pH range by means of pulse radiolysis combined with optical spectroscopy. OH-adduct cyclohexadienyl type radicals were identified as intermediates of the reaction. In the acidic pH range the first-order rate coefficient of phenoxyl radical formation was found linearly dependent on the H3O+ concentration yielding a bimolecular rate coefficient of 1.8 × 108 mol–1 dm3 s–1. In the alkaline range a linear dependence was found on the OH– concentration with rate coefficient of 4.9 × 1010 mol–1 dm3 s–1. These findings were interpreted in terms of acid-base catalysis of the H2O elimination from the OH-adduct. With the time resolution applied, 30 ns, the radical cation p-CH3C6H4OH+. was not observed as intermediate. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Mechanism of OH radical-induced oxidation of p-cresol to p-methylphenoxyl radical

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Publisher
Brill Academic Publishers
Copyright
Copyright © 2002 by VSP 2002
Subject
Chemistry; Inorganic Chemistry; Physical Chemistry; Catalysis
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1163/15685670260188674
Publisher site
See Article on Publisher Site

Abstract

The OH radical-induced oxidation of p-cresol to p-methylphenoxyl radical was studied in aqueous solution in a wide pH range by means of pulse radiolysis combined with optical spectroscopy. OH-adduct cyclohexadienyl type radicals were identified as intermediates of the reaction. In the acidic pH range the first-order rate coefficient of phenoxyl radical formation was found linearly dependent on the H3O+ concentration yielding a bimolecular rate coefficient of 1.8 × 108 mol–1 dm3 s–1. In the alkaline range a linear dependence was found on the OH– concentration with rate coefficient of 4.9 × 1010 mol–1 dm3 s–1. These findings were interpreted in terms of acid-base catalysis of the H2O elimination from the OH-adduct. With the time resolution applied, 30 ns, the radical cation p-CH3C6H4OH+. was not observed as intermediate.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Oct 13, 2004

References

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