Electron spin resonance measurements of propagation and termination rate constants during the liquid-phase oxidation of hydrocarbons

Abstract

The application of e.s.r. spectroscopy has enabled alkylperoxyl radicals (the chain carriers) to be detected in several liquid hydrocarbons undergoing autoxidation at high temperatures. Quantitative measurements have been made for two hydrocarbons, decalin and 2,6,10,14-tetramethylpentadecane, and from the data obtained the propagation rate constants, k_p, have been calculated. The termination rate constants, 2k_t, have also been measured by e.s.r., the results being used to calculate the rate constants for initiation by the decomposition of hydroperoxide in decalin over a limited temperature range.