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

The decomposition of dimethyl peroxide (DMP) was studied in the presence and absence of added NO2 to determine rate constants k1 and k2 in the temperature range of 391–432°K: The results reconcile the studies by Takezaki and Takeuchi, Hanst and Calvert, and Batt and McCulloch, giving log k1(sec−1) = (15.7 ± 0.5) - (37.1 ± 0.9)/2.3 RT and k2 ≈ 5 × 104M−1· sec−1. The disproportionation/recombination ratio k7b/k7a = 0.30 ± 0.05 was also determined: When O2 was added to DMP mixtures containing NO2, relative rate constants k12/k7a were obtained over the temperature range of 396–442°K: A review of literature data produced k7a = 109.8±0.5M−1·sec−1, giving log k12(M−1·sec−1) = (8.5 ± 1.5) - (4.0 ± 2.8)/2.3 RT, where most of the uncertainty is due to the limited temperature range of the experiments.

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