Kinetics and pressure-dependence of the t-butoxyl radical decomposition

Abstract

The kinetics and pressure-dependence of the decomposition of t-butoxyl radicals have been studied in the gas phase between 373 and 423 K by pyrolysing di-t-butyl peroxide in the presence of difluoroamino-radicals. From a Hinshelwood–Lindemann treatment of the data and an assumption of the rate of combination of t-butoxyl radicals and difluoroamino-radicals, the high-pressure rate constant for decomposition of t-butoxyl radicals was found to be given by equation (i), where R= 8·314 J mol^–1 K^–1. The Arrhenius parameters for the formation of the t-butoxyl log k/s^–1= 13·37 ± 0·82 –(70,200 ± 6200)/2·3RT(i) radical from methyl radicals and acetone were calculated from thermochemical data. The rate coefficient was calculated to be log k_–1/ml mol^–1 s^–1= 9·24 ± 1·00 –(56,300 ± 7500)/2·3RT.