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Isotopic tracer studies of the thermal decomposition of tert . -butyl hydroperoxide

1966; Royal Society; Volume: 291; Issue: 1425 Linguagem: Inglês

10.1098/rspa.1966.0091

2053-9169

C. F. Cullis, J. A. García Domínguez, D. Kiraly, D.L. Trimm,

Atmospheric chemistry and aerosols

The thermal decomposition of tert . -butyl hydroperoxide has been investigated at temperatures from 245 to 440 °C and the effects of added oxygen and acetone on the nature and distribution of the reaction products have been determined. Experiments in the presence of [1, 3- 14 C] acetone at 340 °C show that the major part of the methyl ethyl ketone formed from tert . -butyl hydroperoxide is produced via further reactions of acetone, and degradation of the labelled methyl ethyl ketone indicates the distribution of activity throughout the molecule. These results yield valuable information regarding the probable mechanism of formation of the ketone. The measurements carried out, when considered in relation to earlier work on the slow combustion of isobutane, suggest that tert . -butyl hydroperoxide does not play an important part as an intermediate during the oxidation of the corresponding hydrocarbon.