Absolute rate constants have been measured for the reactions of cumylperoxy radicals with a number of hydrocarbons. The cumylperoxy radicals were produced from cumene hydroperoxide. Sufficient hydroperoxide was present to ensure that only cumylperoxy radicals were involved in the rate-determining propagation reaction.Primary and secondary deuterium isotope effects have been measured for propagation and termination in the oxidation of cumene. The rate of hydrogen atom abstraction from ring-substituted cumenes by cumylperoxy radicals can be correlated by the Hammett equation using σ+ substituent constants, ρ = −0.29. Primary and secondary peroxy radicals are about 3–5 times more reactive in hydrogen abstraction than tertiary peroxy radicals.
No takes yet. Share an insight, caveat, or question.
Howard et al. (1968) studied this question.