Determination of rate constants for a thermoneutral H-abstraction reaction: Allylic hydrogen abstraction from 1,5-hexadiene by allyl radical
Determination of rate constants for a thermoneutral H-abstraction reaction: Allylic hydrogen abstraction from 1,5-hexadiene by allyl radical
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热中性夺氢反应速率常数的测定：通过烯丙基自由基从 1,5-己二烯中夺取烯丙基氢
DOI：
10.1016/j.proci.2020.07.054
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发表时间：
2020-09
影响因子：
3.4
通讯作者：
Bin Yang
中科院分区：
文献类型：
--
作者：
Can Huang;Peng Zhang;Jiaxing Wang;Shiqing Kang;Feng Zhang;Chung K. Law;Bin Yang
最近发现热中性H-提取反应在高温燃烧中是重要的，该反应涉及通过共振稳定的自由基从烯烃中提取以形成其它共振稳定的自由基。它们将改变共振稳定自由基的分布，影响分子量增长动力学，从而改变对芳族物种的预测。本文首次对典型的热中性夺氢反应C3 H5-A +1，5-C6 H10 = C3 H6 + C6 H9-A（R1）进行了实验研究。采用快速压片机和快速进样技术研究了1，5-己二烯的高温动力学。实验条件，可以用来获得速率常数的R1的第一次确定的1，5-己二烯燃烧的动力学模型的灵敏度分析。发现丙烯的浓度对R1在893-1007 K的温度范围内在25 bar下的速率常数高度敏感。通过拟合测定的丙烯曲线，在选定的条件下推导出R1的速率常数。此外，来自Wang等人（Fuel 208，779-790，2017）的流动反应器测量的1，5-己二烯热解和来自Vermeire等人（Proc. Combust. Inst. 37，1091-1098，2019）也用于推导R1在更宽温度范围内的速率常数。用从头算过渡态理论计算了R1的速率系数，能量计算在DLPNO-CCSD（T）/aug-cc-pVTZ//B2 PLYP/cc-pVTZ水平.理论预测被发现是在良好的协议与实验推导的速率常数。最终确定的速率系数为：k R1 = 15。058 × T 3 . 425 exp（-14492。073 / RT）c m 3 mol −1 s −1（500 − 2000 K），估计不确定度为1.5倍。
Thermoneutral H-abstraction reactions, which involve the abstraction by resonantly stabilized radicals from olefins to form other resonantly stabilized radicals, have recently been found to be important in high-temperature combustion. They will shift the distribution of resonantly stabilized radicals and affect the molecular weight growth kinetics, thus changing the prediction for aromatic species. The present work provides the first experimental study on a typical thermoneutral H-abstraction reaction: C 3 H 5 -A + 1,5- C 6 H 10 = C 3 H 6 + C 6 H 9 -A (R1). A rapid compression machine, together with a fast sampling technique, was used to study the high temperature kinetics of 1,5-hexadiene. Experimental conditions that can be used to derive the rate constant of R1 were first identified by sensitivity analysis of a kinetic model for 1,5- hexadiene combustion. The concentration of propene was found to be highly sensitive to the rate constant of R1 over the temperature range of 893–1007 K at 25 bar. By fitting the measured propene profiles, the rate constant of R1 was deduced under selected conditions. Furthermore, the concentration profiles of propene in 1,5-hexadiene pyrolysis from a flow reactor measurement by Wang et al. ( Fuel 208, 779–790, 2017 ) and oxidation from a jet stirred reactor measurement by Vermeire et al. ( Proc. Combust. Inst. 37, 1091–1098, 2019 ) were also used to derive the rate constant of R1 over wider temperature ranges. The rate coefficient of R1 was further calculated by ab initio transition state theory, with energies obtained at the level of DLPNO-CCSD(T)/aug-cc-pVTZ//B2PLYP/cc-pVTZ. The theoretical predictions were found to be in good agreement with the experimentally derived rate constants. The final rate coefficient determined is: k R1 = 15 . 058 × T 3 . 425 exp( −14492 . 073 / RT ) c m 3 mo l −1 s −1 ( 500 − 2000 K ) , with an estimated uncertainty of a factor of 1.5.
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影响因子：
4.4
作者：
Riplinger, Christoph;Sandhoefer, Barbara;Neese, Frank
通讯作者：
Neese, Frank
DOI：
10.1002/cphc.201500396
发表时间：
2015-08
期刊：
Chemphyschem : a European journal of chemical physics and physical chemistry
影响因子：
--
作者：
Kun Wang;Stephanie M. Villano;A. Dean
通讯作者：
Kun Wang;Stephanie M. Villano;A. Dean
缓冲气体组成对异辛烷和正庚烷低温着火的影响
影响因子：
4.4
作者：
Haisheng Di;Xin He;Peng Zhang;Zhi Wang;Margaret S. Wooldridge;Chung K. Law;Cuiping Wang;Shijin Shuai;Jianxin Wang
通讯作者：
Jianxin Wang
DOI：
10.1021/jp402391n
发表时间：
2013-06
期刊：
The journal of physical chemistry. A
影响因子：
--
作者：
A. Fridlyand;P. Lynch;R. Tranter;K. Brezinsky
通讯作者：
A. Fridlyand;P. Lynch;R. Tranter;K. Brezinsky
影响因子：
2.9
作者：
Kashinski, D. O.;Chase, G. M.;Byrd, E. F. C.
通讯作者：
Byrd, E. F. C.