Kinetics of radical decomposition of di(tert-butyl) trioxide

The kinetics of radical decomposition of di(tert-butyl) trioxide was studied by spectrophotometry from the consumption of an acceptor of free radicals, 2,6-di(tert-butyl)-4-methylphenol, in CFCl₃ and CH₂Cl₂ (in the latter case, in the presence of 0.1M Bu^tOOH). The activation parameters of the reaction (log(A/s ⁻¹)=14.8±1.2 and 14.1±1.6,E _a=21.6±1.4 and 20.1±1.9 kcal mol⁻¹ in CFCl₃ and CH₂Cl₂, respectively) and the probability of radical escape to the bulk (e=0.9±0.1) were determined. The known experimental and calculated values of the O−OO bond strength in trioxides were analyzed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 61–65, January, 1999.