The determination of absolute rate constants in olefinic oxidations

Abstract

On the basis of the reaction mechanism established in the preceding paper (this volume, p. 376), the changes in rate of photo-oxidation observed in intermittent light when a rate contribution is made by a simultaneous dark reaction have been rigorously analyzed. Using this analysis and the relevant experimental data, the velocity coefficients of the rate con­trolling propagation and termination reactions have been separately evaluated for cyclo hexene, 1-methyl cyclo hexene, dihydromyrcene and ethyl linoleate. The significance of the results in interpreting the finer details of the oxidation mechanism is discussed; and the numerical values are compared with similar data reported for polymerization systems. A criterion for detecting anomalous effects due to intense light absorption is derived; further to the evidence presented in the preceding paper, ethyl linoleate undergoing oxidation in light of wave-length 2537 Å is found to exemplify this behaviour.