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A Shock-Tube Study of the CO plus OH Reaction Near the Low-Pressure Limit

机译:低压极限附近的CO + OH反应的冲击管研究

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Rate coefficients for the reaction between carbon monoxide and hydroxyl radical were measured behind reflected shock waves over 700-1230 K and 1.2-9.8 bar. The temperature/pressure conditions correspond to the predicted low-pressure limit of this reaction, where the channel leading to carbon dioxide formation is dominant. The reaction rate coefficients were inferred by measuring the formation of carbon dioxide using quantum cascade laser absorption near 4.2 mu m. Experiments were performed under pseudo-first-order conditions with tert-butyl hydroperoxide (TBHP) as the OH precursor. Using ultraviolet laser absorption by OH radicals, the TBHP decomposition rate was measured to quantify potential facility effects under extremely dilute conditions used here. The measured CO + OH rate coefficients are provided in Arrhenius form for three different pressure ranges: k(CO+OH)(1.2-1.6 bar) = (9.14 +/- 2.17) X 10(-13) exp( (1265 +/- 190)/T) cm(3) molecule(-1) s(-1); k(CO+OH)(43-5.1 bar) = (8.70 +/- 0.84) X 10(-13) exp( (1156 +/- 83)/T) cm(3) molecule(-1) s(-1); and k(CO+OH)(9.6-9.8 bar) = (7.48 +/- 1.92) x 10(-13) exp(-(929 +/- 192)/T) cm(3) molecule(-1) s(-1). The measured rate coefficients are found to be lower than the master equation modeling results by Weston et al. [J. Phys. Chem. A, 2013, 117, 821] at 819 K and in closer agreement with the expression provided by Joshi and Wang [Int. J. Chem. Kinet., 2006, 38, 57].
机译:在700-1230 K和1.2-9.8 bar的反射冲击波后,测量一氧化碳与羟基自由基之间反应的速率系数。温度/压力条件对应于该反应的预计低压极限,其中导致二氧化碳形成的通道占主导。通过使用4.2μm附近的量子级联激光吸收测量二氧化碳的形成来推断反应速率系数。实验是在拟一级条件下使用叔丁基氢过氧化物(TBHP)作为OH前体进行的。使用OH自由基对紫外线的吸收,可测量TBHP分解速率,以量化此处使用的极稀条件下潜在的设施效应。针对三个不同的压力范围,以Arrhenius形式提供了测量的CO + OH速率系数:k(CO + OH)(1.2-1.6 bar)=(9.14 +/- 2.17)X 10(-13)exp((1265 + / -190)/ T)cm(3)分子(-1)s(-1); k(CO + OH)(43-5.1 bar)=(8.70 +/- 0.84)X 10(-13)exp((1156 +/- 83)/ T)cm(3)分子(-1)s(- 1);和k(CO + OH)(9.6-9.8 bar)=(7.48 +/- 1.92)x 10(-13)exp(-(929 +/- 192)/ T)cm(3)分子(-1)s (-1)。发现测得的速率系数低于Weston等人的主方程建模结果。 [J.物理化学A,2013,117,821]在819 K,并且与Joshi和Wang [Int。 J.化学Kinet。,2006,38,57]。

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