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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
Author(s) -
Howard J. A.,
Chenier J. H. B.
Publication year - 1974
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550060408
Subject(s) - chemistry , tetralin , autoxidation , reaction rate constant , hydrogen atom abstraction , hydrogen atom , photochemistry , hydroxyl radical , oxygen , hydrogen , organic chemistry , radical , kinetics , catalysis , alkyl , physics , quantum mechanics
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.