18495-18-6Relevant articles and documents
Thermal reaction of (CH3)2C=C(CH3)2 in the presence of di-tert-butyl peroxide; reactions of the radicals ·CH3, (CH3)3C·C(CH3)2 and (CH3)2C=C(CH3)·CH2
Koertvelyesi,Seres
, p. 253 - 273 (2007/10/03)
A study of the thermal reaction of (CH3)2C=C(CH3)2 (23DMB2) in the presence of di-t-butyl peroxide (PODBT) at 389-451 K yielded kinetic data on some reactions of the radicals ·CH3, (CH3)3C·C(CH3)2 (1122TMP·) and (CH3)2C=C(CH3) ·CH2 (112TMA·). The ratio of the cross-combination ratios of the radicals o(112TMA·, 122TMP·)/φ(·CH3, 1122TMP·) and the rate constant for H-abstraction from 23DMB2 by ·CH3 relative to that of the recombination reaction, ·CH3 + (CH3)2C=C(CH3)2 → CH4 + (CH3)2C=C(CH3) ·CH2 (4) 2·CH3 → C2H6 (7) have been determined. The values are φ(1122TMP·, 112TMA·)/φ(·CH3, 1122TMP·) = 0.9 ± 0.3 log(k4/k71/2) = (3.74 ± 0.21) - (36.3 ± 2.2)/Θ where Θ = RT ln 10 and the units are dm3/2 mol-1/2 s-1/2 for k4/k71/2, and kJ mol-1 for the energy of activation.