Kinetics for the reactions of C6H5 with CH3OH and C2H5OH: Comparison of theory and experiment

J. Park, Z. F. Xu, K. Xu, Ming-Chang Lin

研究成果: Conference contribution同行評審


The kinetics of the C6H5 reactions with CH3OH and C2H5OH have been measured by pulsed-laser photolysis/mass-spectrometry (PLP/MS) employing acetophenone as the radical source. Kinetic modeling of the benzene formed in the reactions over the temperature range 483-771 K allows us to reliably determine the total rate constants for H-abstraction reactions. In order to extend our temperature range down to 304 K we have also applied the cavity ring-down spectrometric technique using nitrosobenzene as the radical source. Both sets of data agree closely. A weighted least-squares analysis of the two complementary sets of data for the two reactions gave the total rate constants k(CH3OH) = (7.82 ± 0.44) × 1011 exp [-(853 ± 30)/T] and k(C2H5OH) = (5.73 ± 0.58) × 1011 exp [-(1103 ± 44)/T] cm3 mol-1 s-1 for the temperature range studied. Theoretically, four possible product channels of the C6H5 + CH3OH reaction producing C6H6 + CH3O, C6H6 + CH2OH, C6H5OH + CH3 and C6H5COCH3 + H and five possible product channels of the C6H5 + C2H5OH reaction producing C6H6 + C2H5O, C6H6 + CH2CH2OH, C6H6 + CH3CHOH, C6H5OH + CH3CH2 and C6H5OCH3 + H have been computed at the G2M//B3LYP/6-311+G(d, p) level of theory. The hydrogen abstraction channels were predicted to have lower energy barriers and their rate constants were calculated by the microcanonical variational transition state theory at 200-3000 K. The predicted rate constants are in good agreement with the experimental values.

主出版物標題5th US Combustion Meeting 2007
發行者Combustion Institute
出版狀態Published - 2007
事件5th US Combustion Meeting 2007 - San Diego, United States
持續時間: 25 3月 200728 3月 2007


名字5th US Combustion Meeting 2007


Conference5th US Combustion Meeting 2007
國家/地區United States
城市San Diego


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