Thermal decomposition of di-t-butyl peroxide in the presence of (CH3)2CCH2: Reactions of CH3, (CH3)2ĊCH2CH3, and (CH3)2ĊCH2C(CH3)2CH2CH3 radicals |
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Authors: | L szlo Seres, gnes Nacsa,Neville L. Arthur |
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Affiliation: | Lászloó Seres,Ágnes Nacsa,Neville L. Arthur |
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Abstract: | A study of the reaction initiated by the thermal decomposition of di-t-butyl peroxide (DTBP) in the presence of (CH3)2C?CH2 (B) at 391–444 K has yielded kinetic data on a number of reactions involving CH3 (M·), (CH3)2CCH2CH3 (MB·) and (CH3)2?CH2C(CH3)2CH2CH3 (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 dm3/2 mol?1/2 s?1/2 for k2/k and k9/k , s?1 for k0, and kJ mol?1 for E. Various disproportionation-combination ratios involving M·, MB·, and MBB· radicals have been evaluated. The values obtained are: Δ1(M·, MB·) = 0.79 ± 0.35, Δ1(MB·, MB·) = 3.0 ± 1.0, Δ1(MBB·, MB·) = 0.7 ± 0.4, Δ1(M·, MBB·) = 4.1 ± 1.0, Δ1(MB·, MBB·) = 6.2 ± 1.4, and Δ1(MBB·, MBB·) = 3.9 ± 2.3, where Δ1 refers to H-abstraction from the CH3 group adjacent to the center of the second radical, yielding a 1-olefin. © 1994 John Wiley & Sons, Inc. |
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