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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Analysis of some reaction pathways active during cyclopentadiene pyrolysis
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Analysis of some reaction pathways active during cyclopentadiene pyrolysis

机译：环戊二烯热解过程中一些活跃的反应途径的分析

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The cyclopentadienyl radical (cC _5H _5) is among the most stable radical species that can be generated during the combustion and pyrolysis of hydrocarbons and it is generally agreed that its contribution to the gas phase reactivity is significant. In this study the kinetics of one key cC _5H _5 reaction channel, namely the reaction between cC _5H _5 and cyclopentadiene (cC _5H _6), was investigated using ab initio calculations and RRKM/Master Equation theory. It was found that most of the excited C _5H _5-C _5H _6 adducts formed by the addition of cC _5H _5 to cC _5H _6 decompose back to reactants and that the major reaction products are, in order of importance, indene, vinylfulvene (a most probable styrene precursor), phenylbutadiene, and benzene. The preferred reaction pathway of the C _5H _5-C _5H _6 adduct is started by the migration of the tertiary hydrogen of the C _5H _5 ring to a vicinal carbon and followed by the β-opening of the C _5H _6 ring, which is the rate determining step. Successive molecular rearrangements lead to decomposition to the four possible products. The kinetic constants for the four reaction channels, calculated at atmospheric pressure and interpolated in cm ~3 mol ~(-1) s ~(-1) between 900 and 2000 K, are k indene = 10 ~(25.197)T ~(-3.935)exp(-11630/T(K)), k _(vinylfulvene) = 10 ~(65.077)T ~(-14.20)exp(-37567/T(K)), k _(benzene) = 10 ~(29.172)T ~(-4.515)exp(-20570/T(K)), and k _(phenylbutadiene) = 10 ~(16.743)T ~(-1.407)exp(-11804/ T(K)). The predictive capability of the reaction set so determined was tested through the simulations of recent cC _5H -6 pyrolysis and combustion experiments using a detailed kinetic mechanism. A quantitative agreement with experimental data was obtained by assuming that vinylfulvene converts rapidly to stryrene, increasing its reaction channel by a factor of 2, and assuming that phenylbutadiene rapidly decomposes with equal probability to styrene and benzene.
机译：环戊二烯基自由基（cC _5H _5）是在烃的燃烧和热解过程中可以生成的最稳定的自由基，通常认为其对气相反应性的贡献很大。在这项研究中，使用从头算和RRKM /主方程理论研究了一个关键的cC _5H _5反应通道的动力学，即cC _5H _5与环戊二烯（cC _5H _6）之间的反应。发现通过将cC _5H _5加到cC _5H _6中形成的大多数受激C _5H _5-C _5H _6加合物分解回反应物，并且从重要性上讲，主要的反应产物是茚，乙烯基富勒烯（最可能的苯乙烯前体），苯基丁二烯和苯。 C _5H _5-C _5H _6加合物的优选反应途径是通过C _5H _5环的叔氢迁移到邻位碳开始的，然后是C _5H _6环的β开口，即速率确定步骤。连续的分子重排导致分解为四种可能的产物。四个反应通道的动力学常数在大气压下计算并以cm〜3 mol〜（-1）s〜（-1）内插在900和2000 K之间，k茚= 10〜（25.197）T〜（- 3.935）exp（-11630 / T（K）），k _（乙烯基富烯）= 10〜（65.077）T〜（-14.20）exp（-37567 / T（K）），k_（苯）= 10〜（ 29.172）T〜（-4.515）exp（-20570 / T（K）），k_（苯基丁二烯）= 10〜（16.743）T〜（-1.407）exp（-11804 / T（K））。通过详细的动力学机理，通过最近cC _5H -6热解和燃烧实验的模拟测试了如此确定的反应组的预测能力。通过假设乙烯基富勒烯迅速转化为苯乙烯，将其反应通道增加2倍，并假设苯基丁二烯以与苯乙烯和苯同等的概率迅速分解，获得了与实验数据的定量一致性。

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