The mechanism and kinetic analysis of C4H4 + C4H4 (but-1-ene-3-yne) reaction with features of H-transfer in combustion
The mechanism and kinetic analysis of C4H4 + C4H4 (but-1-ene-3-yne) reaction with features of H-transfer in combustion
复制标题
具有燃烧氢转移特征的C4H4 C4H4（丁-1-烯-3-炔）反应机理及动力学分析
DOI：
10.1016/j.ijhydene.2015.12.038
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发表时间：
2016-01
影响因子：
7.2
通讯作者：
Zhen Huang
中科院分区：
文献类型：
--
作者：
Peng Liu;He Lin;Zhen Huang
采用精确的从头算密度泛函理论B3 LYP/6-311 + G（d，p）和CBS-QB 3方法研究了C4 H4 + C4 H4反应的详细机理.发现C4 H4 + C4 H4反应中苯乙烯、苯乙炔和五元环结构的生成是通过5条平行竞争的反应途径进行的。三条反应途径主要是氢转移和脱氢反应，另外两条反应途径主要是C-C键的形成和断裂。氢转移反应在稳定中间体方面发挥着至关重要的作用。结果表明，氢转移反应与两个碳原子的相对位置、第二个碳原子的饱和度以及分子的电子环境密切相关。通常，具有相对小的正原子电荷的邻位不饱和C原子在H-转移反应中是优选的。采用Rice-Ramsperger-卡塞尔-Marcus理论，求解主方程，计算了不同燃烧温度和压力（T= 800-2500 K，P= 0.1 ~ 10 atm）下的产物收率和反应速率系数。动力学结果表明，在温度低于1600 K时，苯乙烯是主要产物，其它两种产物的生成可以忽略。苯乙炔和五元环结构的形成只在较高的温度下促进，但依赖于燃烧压力。具体地，苯乙炔在较高的压力和较高的温度下是有利的，而5元环结构在较低的压力和较高的温度下是有利的。
Detailed mechanisms of C4H4+ C4H4reaction were investigated by accurate ab initio density functional theory B3LYP/6-311 + G(d,p) calculations, as well as CBS-QB3 calculations. It was found that styrene, phenylacetylene and 5-membered ring structure can be formed in C4H4+ C4H4reaction through five parallel and competing pathways. Three pathways are featured with H-transfer and dehydrogenation reactions, and the other two pathways are characterized with the forming and breaking of C–C bond. The H-transfer reactions play a vital role in stabilizing intermediates. It was found that the H-transfer reaction is significantly dependent on the relative position of two C atoms, the degree of saturation of the second C atom, and the electronic environment of molecule. Generally, an ortho-position unsaturated C atom with relative small positive atomic charge is preferable in H-transfer reaction. The yield of products and reaction rate coefficients were evaluated by using Rice−Ramsperger−Kassel−Marcus theory with solving master equation at different combustion temperatures and pressures (T= 800–2500 K,P= 0.1–10 atm). The kinetic results indicate that styrene is the dominant product and the formation of other two products can be ignored when temperature is lower than 1600 K. The formations of phenylacetylene and 5-membered ring structure are only facilitated at higher temperature, but dependent on the combustion pressure. Specifically, phenylacetylene is favored by higher pressure and higher temperature, while 5-membered ring structure is favored by lower pressure and higher temperature.
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DOI：
10.1021/jp212338g
发表时间：
2012-04
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
V. Kislov;A. Mebel;J. Aguilera-Iparraguirre;W. Green
通讯作者：
V. Kislov;A. Mebel;J. Aguilera-Iparraguirre;W. Green
DOI：
10.1016/j.ijhydene.2010.12.002
发表时间：
2011-02
期刊：
Fuel and Energy Abstracts
影响因子：
--
作者：
Maryam Younessi Sinaki;E. Matida;F. Hamdullahpur
通讯作者：
Maryam Younessi Sinaki;E. Matida;F. Hamdullahpur
影响因子：
7.2
作者：
A. Choudhuri;S. Gollahalli
通讯作者：
A. Choudhuri;S. Gollahalli
影响因子：
4.4
作者：
Montgomery, JA;Frisch, MJ;Petersson, GA
通讯作者：
Petersson, GA
影响因子：
7.2
作者：
A. Loukou;I. Frenzel;J. Klein;D. Trimis
通讯作者：
A. Loukou;I. Frenzel;J. Klein;D. Trimis