Thermal decomposition of di‐t‐butyl peroxide in the presence of (CH₃)₂CCH₂: Reactions of CH₃, (CH₃)₂ĊCH₂CH₃, and (CH₃)₂ĊCH₂C(CH₃)₂CH₂CH₃ radicals

Abstract

Abstract A study of the reaction initiated by the thermal decomposition of di‐ t ‐butyl peroxide (DTBP) in the presence of (CH 3 ) 2 CCH 2 (B) at 391–444 K has yielded kinetic data on a number of reactions involving CH 3 (M·), (CH 3 ) 2 CCH 2 CH 3 (MB·) and (CH 3 ) 2 ĊCH 2 C(CH 3 ) 2 CH 2 CH 3 (MBB·) radicals. The cross‐combination ratio for M· and MB· radicals, rate constants for the addition to B of M· and MB· radicals relative to those for their recombination reactions, and rate constants for the decomposition of DTBP, have been determined. The values are, respectively, where θ = RT ln 10 and the units are dm 3/2 mol −1/2 s −1/2 for k 2 / k and k 9 / k , s −1 for k 0 , and kJ mol −1 for E . Various disproportionation‐combination ratios involving M·, MB·, and MBB· radicals have been evaluated. The values obtained are: Δ 1 (M·, MB·) = 0.79 ± 0.35, Δ 1 (MB·, MB·) = 3.0 ± 1.0, Δ 1 (MBB·, MB·) = 0.7 ± 0.4, Δ 1 (M·, MBB·) = 4.1 ± 1.0, Δ 1 (MB·, MBB·) = 6.2 ± 1.4, and Δ 1 (MBB·, MBB·) = 3.9 ± 2.3, where Δ 1 refers to H‐abstraction from the CH 3 group adjacent to the center of the second radical, yielding a 1‐olefin. © 1994 John Wiley & Sons, Inc.