The initial process of the oxidation of the methyl radical in reflected shock waves

The oxidation of the methyl radical was investigated in mixtures of C/sub 2/H/sub 6/-O/sub 2/-Ar and CH/sub 3/I-O/sub 2/-Ar behind reflected shock waves by monitoring the O atom, and OH radical in the temperature range from 1430 to 2150 K. Computer kinetic modeling of the experimental profiles yielded a rate constant for CH/sub 3/ + O/sub 2/ ..-->.. CH/sub 3/O + O (2) of k/sub 2/ = 10/sup 14.35/ exp(-33.7 kcal mol/sup -1//RT) cm/sup 3/ mol/sup -1/ s/sup -1/. This value was essentially the same as those reported previously. For the competing reaction CH/sub 3/ + O/sub 2/ ..-->.. CH/sub 2/O + OH (3) experiments showed a low sensitivity to the assumed k/sub 3/ value and the following rate constant was evaluated with an uncertainty factor of 5: k/sub 3/ = 10/sup 11.50/ exp(-9.0 kcal mol/sup -1//RT) cm/sup 3/mol/sup -1/s/sup -1/. These results were discussed in terms of ab initio MO calculations by Kamiya et al. 27 references, 12 figures, 2 tables.