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The decomposition of dimethyl peroxide and the rate constant for CH3O + O2 → CH2O + HO2

✍ Scribed by John R. Barker; Sidney W. Benson; David M. Golden

Publisher
John Wiley and Sons
Year
1977
Tongue
English
Weight
951 KB
Volume
9
Category
Article
ISSN
0538-8066

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✦ Synopsis

The decomposition of dimethyl peroxide (DMP) was studied in the presence and absence of added NO, to determine rate constants k l and k z in the temperature range of 391-432OK:

The results reconcile the studies by Takezaki and Takeuchi, Hanst and Calvert, and Batt and McCulloch, giving log kl(sec-1) = (15.7 f 0.5) -(37.1 f 0.9)/2.3 RT and k , = 5 X 104MM-'sec-1. The disproportionation/recombination ratio k7t,/k7, = 0.30 f 0.05 was also determined: Me0 + NO, (+ &I) % MeONOz (+ M ) M e 0 + NO, 3 CH,O + HONO When 0 2 was added to DMP mixtures containing NO,, relative rate constants klZ/k?a CH,O + 0 2 3 CHIO + HOZ were obtained over the temperature range of 396-442'K: A review of literature data produced kTa = 109.s*~.~M-1~sec-1, giving log k12(M-1.sec-1) = (8.5 f 1.5) -(4.0 =k 2.8)/2.3 RT, where most of the uncertainty is due to the limited temperature range of the experiments.

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