Add time:08/09/2019         Source:sciencedirect.com

The thermal decomposition of 2-, 3-, and 4-methylbenzyl radicals was studied behind reflected shock waves. α-Bromo- ortho (meta- and para)-xylenes were used as precursors for a series of experiments with temperatures ranging from 1150 to 1600 K and pressures between 1.5 and 4 bar. Mixtures of 1–5.5 ppm of the precursor diluted in argon were used for the investigations. Initiated by the fast thermal dissociation of the precursor CH3C6H4CH2Br→CH3C6H4CH2+Br (R3) the methylbenzyl radicals subsequently decomposed. 2-methylbenzyl→o-CH2C6H4CH2+H (R2o) 3-methylbenzyl→m-CH2C6H4CH2+H (R2m) 4-methylbenzyl→p-CH2C6H4CH2+H (R2P) We followed the rate of H-atom formation by using atom resonance absorption spectroscopy (H-ARAS) at 121.6 nm. We report the first directly measured rate coefficients for the decomposition of methylbenzyl radicals: k2o=5×1015 exp {−(310±4)kJ mol−1/RT} s−1, k2m=5×1015 exp{−(340±4) kJ mol−1/RT} s−1, and k2p=5×1015 exp{−(295±4) kJ mol−1/RT} s−1 These rate coefficients are about a factor of 4 below the high-pressure limit, and the accuracy is estimated to be 30%. The complete H-atom concentration-time profiles were successfully modeled using a simple mechanism.

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