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On the accuracy of the hydroperoxide method of determining absolute rate constants for hydrogen atom abstraction by the tert-butylperoxy radical

✍ Scribed by J. A. Howard; J. H. B. Chenier

Publisher
John Wiley and Sons
Year
1974
Tongue
English
Weight
212 KB
Volume
6
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

Measurements of rates of oxygen absorption and steady‐state peroxy radical concentrations for the autoxidation of tetralin in the presence of tert‐butyl hydroperoxide have shown that the rate constant for reaction of the tert‐butylperoxy radical with tetralin at 60°C is approximately 11.0 M^−1^ s^−1^. This rate constant is about a factor of 4 larger than the value recently reported by Niki, Okayasu, and Kamiya for this reaction.

The present work emphasizes that great care should be taken when the hydroperoxide method is used to estimate cross‐propagation rate constants for a substrate as reactive as tetralin at a temperature as high as 60°C.

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