Ab initio kinetic study on the abstraction reactions of methylcyclohexane and implications for high-temperature ignition simulations from shock tube experiment

IF 1.5 4区 化学 Q4 CHEMISTRY, PHYSICAL
Jinhu Liang, Ming-Xu Jia, Qian Yao, Guo-Jun Kang, Yang Zhang, Fengqi Zhao, Quan-De Wang
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Abstract

Methylcyclohexane (MCH) is the simplest alkylated cyclohexane, and has been widely employed in surrogate models to represent the cycloalkanes in real fuels. Thus, extensive experimental and kinetic modeling studies have been performed to understanding the combustion chemistry of MCH. However, through a detailed literature analysis, there still lack a systematic theoretical study on the abstraction reactions of MCH, which are the main initial oxidation pathway of MCH. Herein, this work reports a systematic ab initio chemical kinetic study on the abstraction reactions of MCH with different radicals/species. Specifically, reaction rate constants of 30 abstraction reactions of MCH with H/O/OH/O2/HO2/CH3 at different sites are computed using transition state theory (TST) by using quantum chemistry calculation results at DLPNO-CCSD(T)/CBS//M06-2X/cc-pVTZ level. The computed results are incorporated into a detailed mechanism to simulate newly measured ignition delay times (IDTs) of MCH in this work at equivalence ratios of 0.5, 1.0, and 2.0, pressures of 2 and 5 bar, temperatures ranging from 1140 to 1640 K. The updated detailed mechanism demonstrates improvement in the prediction of IDTs, especially at fuel-rich conditions. The fuel concentration and dilution effect on the IDTs are discussed, and a general Arrhenius expression is adopted to fit the IDTs from both this work and literature work. This work should be valuable for further optimization of detailed kinetic mechanisms and also for gaining insight into the combustion chemistry of MCH.

关于甲基环己烷抽提反应的 Ab initio 动力学研究以及冲击管实验对高温点火模拟的影响
甲基环己烷(MCH)是最简单的烷基化环己烷,已被广泛用于替代模型,以代表实际燃料中的环烷烃。因此,为了了解 MCH 的燃烧化学性质,人们进行了大量的实验和动力学模型研究。然而,通过详细的文献分析,对于 MCH 的主要初始氧化途径,即 MCH 的抽提反应,仍然缺乏系统的理论研究。在此,本研究报告对 MCH 与不同自由基/物种的萃取反应进行了系统的 ab initio 化学动力学研究。具体地说,利用 DLPNO-CCSD(T)/CBS//M06-2X/cc-pVTZ 水平的量子化学计算结果,采用过渡态理论(TST)计算了 MCH 与不同位点的 H/O/OH/O2/HO2/CH3 发生的 30 个抽离反应的反应速率常数。计算结果被纳入一个详细的机制中,以模拟在等效比为 0.5、1.0 和 2.0,压力为 2 和 5 巴,温度为 1140 至 1640 K 时新测量的 MCH 的点火延迟时间(IDTs)。讨论了燃料浓度和稀释对 IDTs 的影响,并采用了一般阿伦尼乌斯表达式来拟合本研究和文献研究中的 IDTs。这项工作对于进一步优化详细的动力学机制以及深入了解 MCH 的燃烧化学过程都很有价值。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CiteScore
3.30
自引率
6.70%
发文量
74
审稿时长
3 months
期刊介绍: As the leading archival journal devoted exclusively to chemical kinetics, the International Journal of Chemical Kinetics publishes original research in gas phase, condensed phase, and polymer reaction kinetics, as well as biochemical and surface kinetics. The Journal seeks to be the primary archive for careful experimental measurements of reaction kinetics, in both simple and complex systems. The Journal also presents new developments in applied theoretical kinetics and publishes large kinetic models, and the algorithms and estimates used in these models. These include methods for handling the large reaction networks important in biochemistry, catalysis, and free radical chemistry. In addition, the Journal explores such topics as the quantitative relationships between molecular structure and chemical reactivity, organic/inorganic chemistry and reaction mechanisms, and the reactive chemistry at interfaces.
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