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

Methyl radical reactions with matrix molecules in glasses C2H5OH, (CH2OH)2, n‐ and i‐C3H7OH, n‐ and i‐C4H9OH, n‐ and i‐C5H11OH, C2D5OH, and i‐C3D7OD, and the reactions of Ċ2H5, Ċ3H7, Ċ4H9, Ċ5H11 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 = c0 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.