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Oxidation of hydrocarbons in the presence of added hydroperoxide. On the determination of rate constants by the hydroperoxide method

✍ Scribed by Etsuo Niki; Kisaburo Okayasu; Yoshio Kamiya

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

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✦ Synopsis

Abstract

Oxidation of tetralin in the presence of tert‐butyl hydroperoxide and tetralyl hydroperoxide, initiated with azobisisobutyronitrile, was studied at 60°C in order to examine the complications involved in the hydroperoxide method devised by Howard and Ingold. From literature data on absolute rate constants and our rates of oxidation, cross termination rate constants and contributions of each elementary propagation and termination step were computed. It was confirmed that this method was quite useful in determining the cross propagation rate constant, but it was also demonstrated that the rate of oxidation should be measured at very low conversion and with quite high concentrations of hydroperoxide, especially when the peroxy radical derived from the added hydroperoxide has a much lower termination rate constant than that from the oxidizing substrate.

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