Journal of Physical Chemistry A, Vol.101, No.13, 2436-2441, 1997
Rate Coefficients of Hydroxyl Radical Reaction with Dimethyl Ether and Methyl tert-Butyl Ether over an Extended Temperature-Range
Rate coefficients of the reaction of hydroxyl (OH) radicals with CH3OCH3 (k(1)) and CH3OC(CH3)(3) (k(2)) over an extended temperature range are reported. Measurements were performed using a laser photolysis-laser-induced fluorescence technique under slow flow conditions at a total pressure of 740 +/- 10 Torr. Arrhenius plots of the data exhibited significant curvature and were fitted in the form of k(T) = AT(B) exp(-C/T). The resulting modified Arrhenius expressions (error limits +/-2 sigma) that best described these extended temperature measurements and prior low-temperature measurements were (in units of cm(3) molecule(-1) s(-1)) k(1)(295-650 K) = (1.05 +/- 0.10) x 10(-17)T(2.0) exp[(328 +/- 32)/T] and k(2)(293-750 K) = (1.15 +/- 0.11) x 10(-17)T(2.04) exp[(266 +/- 41)/T]. Comparison of our measurements for k(1) with previous, overlapping low-temperature measurements indicated generally good agreement. Our measurements for k(2), although consistent with previous room temperature measurements, exhibited a larger temperature dependence than previously reported. High-temperature oxidation mechanisms for these oxygenated fuel components are proposed. Support for the mechanisms is presented in the form of product analysis studies in high-temperature tubular flow reactors. For CH3OC(CH3)(3), these studies suggest that H abstraction from the tert-butyl soup is an important high-temperature oxidation pathway.