Pressure-dependence of decomposition of tert-butoxyl radical

Abstract

The thermal decomposition of the tert-butoxyl radical has been studied in the gas phase in the range 398–436°K at pressures of 10–60 mm using di-tert-butyl peroxide + nitric oxide mixtures. The reaction is pressure dependent and the following Arrhenius parameters for the high and low-pressure limiting rates have been determined by a Hinshelwood-Lindemann treatment logA_∞(sec^–1)= 14.7, E_∞(kcal mole^–1)= 22.8, log A₀(mole^–1 cm³ sec^–1)= 15.7 and E₀(kcal mole^–1)= 13.4. The half-rate pressure at 436°K is 112 mm, and the results have been explained in terms of a model corresponding to about 23 effective oscillators in the activated state.