Free radicals in the reaction between t-butyl hydroperoxide and titanous ion: Some observations by electron spin resonance spectrometry

Abstract

The reaction between t-butyl hydroperoxide and titanous ion in aqueous solution produces free methyl radicals detectable by electron spin resonance spectrometry (Dixon and Norman). However, the presence of titanous ion in concentrations greater than 0.01M broadens the spectrum of the methyl radical, causing it effectively to disappear at titanous concentrations greater than 0.1M. At hydroperoxide concentrations above 0.25M t-butyl peroxy radicals (identified by a strong single-line spectrum with g-value 2.0136) are produced by the reaction            R^. + (CH₃)₃COOH → RH + (CH₃)₃COO^. Their concentration reaches a maximum about 1 sec after the concentration of the methyl radicals has fallen to an undetectable value and their half-life (≈ 5 sec) is about ten times that of the methyl radicals.