丁炔基自由基 C4H 与各种碳氢化合物反应的低温速率系数。第二部分：与烯烃（乙烯、丙烯、1-丁烯）、二烯（丙二烯、1,3-丁二烯）和炔烃（乙炔、丙炔和 1-丁炔）的反应。

Low temperature rate coefficients for reactions of the butadiynyl radical, C4H, with various hydrocarbons. Part II: reactions with alkenes (ethylene, propene, 1-butene), dienes (allene, 1,3-butadiene) and alkynes (acetylene, propyne and 1-butyne).

机构信息

Institut de Physique de Rennes, Equipe Astrochimie Expérimentale UMR 6251 du CNRS-Université de Rennes 1, Bât. 11c, Campus de Beaulieu, 35042 Rennes Cedex, France.

出版信息

Phys Chem Chem Phys. 2010 Apr 21;12(15):3677-89. doi: 10.1039/b923867k. Epub 2010 Mar 19.

DOI:10.1039/b923867k

PMID:20358064

Abstract

The kinetics of the reactions of the linear butadiynyl radical, C4H (CCCCH), with a variety of unsaturated hydrocarbons have been studied over the temperature range of 39-300 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, or reaction kinetics in uniform supersonic flow) apparatus combined with the pulsed laser photolysis-laser induced fluorescence technique. The rate coefficients for all the reactions studied are found to all be in excess of 10(-10) cm(3) molecule(-1) s(-1) over the entire temperature range. They can be fitted with the following expressions (valid from 39 K to 300 K, with RMS deviations of the experimental points from the predicted values shown, to which should be added 10% possible systematic error) for reaction of C4H with alkenes: k(C2H4) = (1.95 +/- 0.17) x 10(-10) (T/298 K)(-0.40) exp(9.4 K/T) cm3 molecule(-1) s(-1); k(C3H6) = (3.25 +/- 0.12) x 10(-10) (T/298 K)(-0.84) exp(-48.9 K/T) cm3 molecule(-1) s(-1); k(1-C4H8) = (6.30 +/- 0.35) x 10(-10) (T/298 K)(-0.61) exp(-65.0 K/T) cm3 molecule(-1) s(-1), for reaction of C4H with dienes: k(C3H4) = (3.70 +/- 0.34) x 10(-10) (T/298 K)(-1.18) exp(-91.1 K/T) cm3 molecule(-1) s(-1); k(1,3-C4H6) = (5.37 +/- 0.30) x 10(-10) (T/298 K)(-1.25) exp(-116.8 K/T) cm3 molecule(-1) s(-1), and for reaction of C4H with alkynes: k(C2H2) = (1.82 +/- 0.19) x 10(-10) (T/298 K)(-1.06) exp(-65.9 K/T) cm3 molecule(-1) s(-1); k(C3H4) = (3.20 +/- 0.08) x 10(-10) (T/298 K)(-0.82) exp(-47.5 K/T) cm3 molecule(-1) s(-1); k(1-C4H6) = (3.48 +/- 0.14) x 10(-10) (T/298 K)(-0.65) exp(-58.4 K/T) cm3 molecule(-1) s(-1). Possible reaction mechanisms and product channels are discussed in detail for each of these reactions. Potential implications of these results for models of low temperature chemical environments, in particular cold interstellar clouds and star-forming regions, are considered.

摘要

C4H（CCCCH）与各种不饱和烃的反应动力学在 39-300 K 的温度范围内使用 CRESU（均匀超音速反应的动力学或均匀超音速流动中的反应动力学）装置和脉冲激光光解-激光诱导荧光技术进行了研究。所有研究反应的速率系数都在整个温度范围内超过 10(-10) cm(3) molecule(-1) s(-1)。它们可以用以下表达式拟合（有效范围为 39 K 至 300 K，显示实验点与预测值的 RMS 偏差，应在此基础上加上 10%可能的系统误差）：C4H 与烯烃的反应：k(C2H4) = (1.95 +/- 0.17) x 10(-10) (T/298 K)(-0.40) exp(9.4 K/T) cm3 molecule(-1) s(-1)；k(C3H6) = (3.25 +/- 0.12) x 10(-10) (T/298 K)(-0.84) exp(-48.9 K/T) cm3 molecule(-1) s(-1)；k(1-C4H8) = (6.30 +/- 0.35) x 10(-10) (T/298 K)(-0.61) exp(-65.0 K/T) cm3 molecule(-1) s(-1)，C4H 与二烯的反应：k(C3H4) = (3.70 +/- 0.34) x 10(-10) (T/298 K)(-1.18) exp(-91.1 K/T) cm3 molecule(-1) s(-1)；k(1,3-C4H6) = (5.37 +/- 0.30) x 10(-10) (T/298 K)(-1.25) exp(-116.8 K/T) cm3 molecule(-1) s(-1)，C4H 与炔烃的反应：k(C2H2) = (1.82 +/- 0.19) x 10(-10) (T/298 K)(-1.06) exp(-65.9 K/T) cm3 molecule(-1) s(-1)；k(C3H4) = (3.20 +/- 0.08) x 10(-10) (T/298 K)(-0.82) exp(-47.5 K/T) cm3 molecule(-1) s(-1)；k(1-C4H6) = (3.48 +/- 0.14) x 10(-10) (T/298 K)(-0.65) exp(-58.4 K/T) cm3 molecule(-1) s(-1)。详细讨论了这些反应中的每一种反应的可能反应机制和产物通道。考虑了这些结果对低温化学环境模型的潜在影响，特别是冷星际云和恒星形成区。