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亚甲基CH(X²π)自由基与C₂H₂、C₂H₄、C₃H₄(甲基乙炔和丙二烯)、C₃H₆(丙烯)和C₄H₈(反-丁烯)反应的速率常数和H原子分支比。

Rate constants and the H atom branching ratio of the reactions of the methylidyne CH(X2pi) radical with C2H2, C2H4, C3H4 (methylacetylene and allene), C3H6 (propene) and C4H8 (trans-butene).

作者信息

Loison Jean-Christophe, Bergeat Astrid

机构信息

Université de Bordeaux, UMR 5255, ISM, Groupe Astrochimie, 351 cours de la Libération, F-33405 Talence Cedex, France.

出版信息

Phys Chem Chem Phys. 2009 Jan 28;11(4):655-64. doi: 10.1039/b812810c.

Abstract

The reactions of the CH radical with several unsaturated hydrocarbons C2H2 (acetylene), C2H4 (ethylene), C3H4 (methyl-acetylene and allene), C3H6 (propene) and C4H8 (trans-butene) were studied at room temperature, in a low-pressure fast-flow reactor. CH(X2pi, v = 0) radicals were obtained from the reaction of CHBr3 with potassium atoms. The overall rate constants at 300 K are CH + C2H2: (3.6 +/- 0.6) x 10(-10), CH + C2H4: (3.1 +/- 0.6) x 10(-10), CH + C3H4 (methyl-acetylene): (3.4 +/- 0.6) x 10(-10), CH + C3H4 (allene): (3.6 +/- 0.6) x 10(-10), CH + C3H6 (propene): (4.2 +/- 0.8) x 10(-10) and CH + C4H8 (trans-butene): (4.0 +/- 0.80) x 10(-10) cm3 molecule(-1) s(-1) (errors are cited at the level of +/- 1 sigma). Absolute atomic hydrogen production was determined by vacuum ultra-violet (VUV) resonance fluorescence, H production from the CH + CH4 reaction being used as a reference. Observed H branching ratios for these CH reactions were: C2H2: 0.90 +/- 0.08, C2H4: 0.94 +/- 0.08, C3H4 (methyl-acetylene): 0.98 +/- 0.08, C3H4 (allene): 0.97 +/- 0.08, C3H6 (propene): 0.78 +/- 0.10, C4H8 (trans-butene): 0.69 +/- 0.12 (errors are cited at the level of +/- 1 sigma). A compilation of the available kinetic data on these reactions has been made in order to propose rate coefficients for each possible channel of the different reactions for astrochemical models.

摘要

在室温下,于低压快速流动反应器中研究了CH自由基与几种不饱和烃C2H2(乙炔)、C2H4(乙烯)、C3H4(甲基乙炔和丙二烯)、C3H6(丙烯)和C4H8(反-丁烯)的反应。CH(X2π, v = 0)自由基由CHBr3与钾原子的反应获得。300K时的总速率常数为:CH + C2H2:(3.6 ± 0.6)×10^(-10),CH + C2H4:(3.1 ± 0.6)×10^(-10),CH + C3H4(甲基乙炔):(3.4 ± 0.6)×10^(-10),CH + C3H4(丙二烯):(3.6 ± 0.6)×10^(-10),CH + C3H6(丙烯):(4.2 ± 0.8)×10^(-10),CH + C4H8(反-丁烯):(4.0 ± 0.80)×10^(-10) cm³·分子⁻¹·s⁻¹(误差为±1σ水平)。通过真空紫外(VUV)共振荧光测定绝对氢原子生成量,以CH + CH4反应产生的H作为参考。这些CH反应中观察到的H分支比为:C2H2:0.90 ± 0.08,C2H4:0.94 ± 0.08,C3H4(甲基乙炔):0.98 ± 0.08,C3H4(丙二烯):0.97 ± 0.08,C3H6(丙烯):0.78 ± 0.10,C4H8(反-丁烯):0.69 ± 0.12(误差为±1σ水平)。已对这些反应的现有动力学数据进行汇编,以便为天体化学模型中不同反应的每个可能通道提出速率系数。

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