Combustion and Flame, Vol.149, No.1-2, 104-111, 2007
Experimental and theoretical rate constants for CH4+O-2 -> CH3+HO2
In this study, rate constants for the primary initiation process in low to moderate temperature CH4 oxidation CH4 + O-2 -> CH3 + HO2 have been measured in a reflected shock tube apparatus between 1655 and 1822 K using multipass absorption spectrometric detection of OH radicals at 308 nm. After rapid dissociation of HO2 yielding H atoms, which are instantaneously converted to OH by H + O-2 -> OH + O, the temporal concentration of OH radicals was observed as the final product from the rate-controlling title reaction. The present work utilizes 18 optical passes corresponding to a total path length of 1.6 m. This configuration gives a signal to noise ratio of unity at similar to 3 x 10(12) radicals cm(-3). Hence, kinetics experiments could be performed at conditions of low [CH4](0) (60-70 ppm), thereby substantially reducing secondary chemistry. Possible implications of CH4 dissociation contributing to the OH formation rates were considered. The present experimental results agree with a priori variational transition state theoretical (VTST) calculations, k(th) = 3.37 x 10(-19)T(2.745) exp(-26,041 K/T) cm(3) molecule(-1) s(-1), clearly showing overlap of experiment and theory, within experimental error. The new rate constant values obtained in this study are 8-10 times higher than the values used in the popular mechanisms GRI-Mech 3.0 and Leeds Methane Mechanism, version 1.5. (c) 2007 Published by Elsevier Inc. on behalf of The Combustion Institute.