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 ?₂H₅, ?₃H₇, ?₄H₉, ?₅H₁₁ 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.