Very low-pressure pyrolysis. VIII. The decomposition of Di-t-amyl peroxide

The very low-pressure pyrolysis (VLPP) technique has been applied to the pyrolysis of di-t-amyl peroxide (DTAP) over the temperature range 523-633°K. VLPP yields a low-pressure rate constant, k_uni The conversion of k_uni to k_∞ which must be made to calculate the Arrhenius parameters, is accomplished via the RRKM theory. The transition state model used in the RRKM calculations was based on a transition state model which accurately reproduced the VLPP data for di-t-butyl peroxide for which the Arrhenius parameters are well known. For the decomposition of DTAP it was found that log k_∞(300°K) = 15.8 - 36.4/θ, where θ = 2.303RT, in kcal/mole, and the units of k_∞, are sec^?1.