ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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)2ĊCH2C(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, \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c} {\phi \left({{\rm M} \cdot {\rm, MB} \cdot} \right) = \left({2.3 \pm 0.2} \right)} \\ {\log \left({{{k_2} \mathord{\left/ {\vphantom {{k_2} {k_5^{1/2}}}} \right. \kern-\nulldelimiterspace} {k_5^{1/2}}}} \right) = \left({3.18 \pm 0.32} \right) - {{\left({28.0 \pm 1.3} \right)} \mathord{\left/ {\vphantom {{\left({28.0 \pm 1.3} \right)} \theta}} \right. \kern-\nulldelimiterspace} \theta}} \\ {\log \left({{{k_9} \mathord{\left/ {\vphantom {{k_9} {k_{15}^{1/2}}}} \right. \kern-\nulldelimiterspace} {k_{15}^{1/2}}}} \right) = \left({2.2 \pm 0.9} \right) - {{\left({24.4 \pm 2.5} \right)} \mathord{\left/ {\vphantom {{\left({24.4 \pm 2.5} \right)} \theta}} \right. \kern-\nulldelimiterspace} \theta}} \\ {\log \left({k_0} \right) = \left({15.57 \pm 0.23} \right) - {{\left({156.3 \pm 2.2} \right)} \mathord{\left/ {\vphantom {{\left({156.3 \pm 2.2} \right)} \theta}} \right. \kern-\nulldelimiterspace} \theta}} \\\end{array} $$\end{document} where θ = RT ln 10 and the units are dm3/2 mol-1/2 s-1/2 for k2/k51/2 and k9/k151/2, 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.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550260202
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