Absolute rate constants for hydrocarbon autoxidation. XIV. Termination rate constants for tertiary peroxy radicals

Abstract

Absolute rate constants for chain termination by ten t-peroxy radicals have been measured at 30° by the rotating sector technique, the photochemical pre- and after-effect method, and by electron spin resonance. The different methods generally give results in good agreement with one another. The termination rate constants vary from a low of ∼4 × 10² M⁻¹ s⁻¹ for t-butylperoxy to a high of ∼3 × 10⁴ M⁻¹ s⁻¹ for 1,1-diphenylethylperoxy radicals.