The Kinetics of alkyl radical reactions with aliphatic alcohol glasses as studied by electron spin resonance

Abstract

Abstract Methyl radical reactions with matrix molecules in glasses C 2 H 5 OH, (CH 2 OH) 2 , n ‐ and i ‐C 3 H 7 OH, n ‐ and i ‐C 4 H 9 OH, n ‐ and i ‐C 5 H 11 OH, C 2 D 5 OH, and i ‐C 3 D 7 OD, and the reactions of Ċ 2 H 5 , Ċ 3 H 7 , Ċ 4 H 9 , Ċ 5 H 11 with methanol glasses have been studied. Alkyl radicals were produced by photolysis of diphenylamine–alkylhalide–alcohol mixtures using ultraviolet light. In all cases the alkyl radical decay follows the law c = c 0 exp(‐ k √ t ). The √ t law should not be associated with alkyl radical diffusion in a matrix. A method of processing the kinetics of those reactions in which one paramagnetic species changes into another with the total concentration being constant and the electron spin resonance spectra of both species overlapping, is described.