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

✍ Scribed by Lászloó Seres; Ágnes Nacsa; Neville L. Arthur

Publisher
John Wiley and Sons
Year
1994
Tongue
English
Weight
1024 KB
Volume
26
Category
Article
ISSN
0538-8066

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✦ Synopsis

A study of the reaction initiated by the thermal decomposition of di-t-butyl peroxide (DTBP) in the presence of (CHa)?C=CHz (B) at 391-444 K has yielded kinetic data on a number of reactions involving CH3 (M.), (CH&CCHzCH3 (MB.) and ( C H ~) ~C C H ~C ( C H ~) Z C H ~C H ~ (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, +(M.,MB.) = (2.3 -t 0.2) log(kz/kp) = (3.18 2 0.32) -(28.0 t 1.3)/0 log(ks/k~z) = (2.2 -t 0.9) -(24.4 t 2.5)/0 iog(ko) = (15.57 2 0.23) -(156.3 -+ 2.z)ie

where 0 = RT In 10 and the units are dm3'2 mol-1'2 s-l'z for kZ/kT and k s / k y l , s-l for ko, and k J mol-l for E .

Various disproportionation-combination ratios involving M., MB-, and MBB. radicals have been evaluated. The values obtained are: Al(M.,MB-) = 0.79 ? 0.35, Al(MB.,MB.) = 3.0 5 1.0, AI(MBB.,MB.) = 0.7 5 0.4, Al(M.,MBB-) = 4.1 2 1.0, AI(MB-,MBB.) = 6.2 2 1.4, and Al(MBB.,MBB.) = 3.9 -t 2.3, where A1 refers to H-abstraction from the CH3 group adjacent to the center of the second radical, yielding a 1-olefin.

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