Implication of Sensitive Reactions to Ignition of Methyl Pentanoate: H-Abstraction Reactions by H and CH3 Radicals

doi:10.1007/s40242-020-0249-1

高等学校化学研究 ›› 2021, Vol. 37 ›› Issue (3): 711-717.doi: 10.1007/s40242-020-0249-1

Implication of Sensitive Reactions to Ignition of Methyl Pentanoate: H-Abstraction Reactions by H and CH₃ Radicals

SHANG Yanlei¹, NING Hongbo¹, SHI Jinchun², LUO S. N.¹

1. Key Laboratory of Advanced Technologies of Materials, Ministry of Education, Southwest Jiaotong University, Chengdu 610031, P. R. China;
2. The Peac Institute of Multiscale Sciences, Chengdu 610027, P. R. China

收稿日期:2020-09-26 修回日期:2020-11-26 出版日期:2021-06-01 发布日期:2021-05-31
通讯作者: NING Hongbo, SHI Jinchun E-mail:hbning@swjtu.edu.cn;jcshi@pims.ac.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (Nos.201903064, 11627901). We thank to the computational support by the Supercomputing Center of School of Materials Science and Engineering, Southwest Jiaotong University, China.

Implication of Sensitive Reactions to Ignition of Methyl Pentanoate: H-Abstraction Reactions by H and CH₃ Radicals

SHANG Yanlei¹, NING Hongbo¹, SHI Jinchun², LUO S. N.¹

1. Key Laboratory of Advanced Technologies of Materials, Ministry of Education, Southwest Jiaotong University, Chengdu 610031, P. R. China;
2. The Peac Institute of Multiscale Sciences, Chengdu 610027, P. R. China

Received:2020-09-26 Revised:2020-11-26 Online:2021-06-01 Published:2021-05-31
Contact: NING Hongbo, SHI Jinchun E-mail:hbning@swjtu.edu.cn;jcshi@pims.ac.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (Nos.201903064, 11627901). We thank to the computational support by the Supercomputing Center of School of Materials Science and Engineering, Southwest Jiaotong University, China.

摘要/Abstract

摘要： Methyl pentanoate(MP) was identified as a potential candidate. To facilitate the application of MP with high efficiency in engines, a comprehensive understanding of combustion chemical kinetics of MP is necessary. In this work, the H-abstraction reactions from MP by H and CH₃ radicals, critical in controlling the initial fuel consumption, are theoretically investigated at the DLPNO-CCSD(T)/CBS(T-Q)//M06-2X/cc-pVTZ level of theory. The multistructural torsional(MS-T) anharmonicity is characterized using the dual-level MS-T method; the HF/3-21G and M06-2X/cc-pVTZ methods are chosen as the low- and high-level methods, respectively. The conventional transition state theory(TST) is employed to calculate the high-pressure limit rate constants at 298-2000 K with the Eckart tunneling correction. Our calculations indicate that the hydrogen atoms of the methylene functional group are easier to be abstracted by H and CH₃ radicals. The multistructural torsional anharmonicities of H-abstraction reactions MP+H/CH₃ are significant within the temperature range investigated. The tunneling effects are more pronounced at low temperatures, and contribute considerably to the rate constants below 500 K. The model from the work of Diévart et al. is updated with our calculations, and the simulations of the updated model are in excellent agreement with the reported ignition delay time of MP/O₂/Ar and MP/Air mixtures. The sensitivity analysis indicates that the H-abstraction reactions, MP+H=CH₃CH₂CHCH₂C(=O)OCH₃/CH₃CHCH₂CH₂C(=O)OCH₃+H₂, are critical in controlling the initial fuel consumption and ignition delay time of MP.

关键词: Methyl pentanoate, H-Abstraction, Dual-level MS-T, Ignition delay time, Kinetic modeling

Abstract: Methyl pentanoate(MP) was identified as a potential candidate. To facilitate the application of MP with high efficiency in engines, a comprehensive understanding of combustion chemical kinetics of MP is necessary. In this work, the H-abstraction reactions from MP by H and CH₃ radicals, critical in controlling the initial fuel consumption, are theoretically investigated at the DLPNO-CCSD(T)/CBS(T-Q)//M06-2X/cc-pVTZ level of theory. The multistructural torsional(MS-T) anharmonicity is characterized using the dual-level MS-T method; the HF/3-21G and M06-2X/cc-pVTZ methods are chosen as the low- and high-level methods, respectively. The conventional transition state theory(TST) is employed to calculate the high-pressure limit rate constants at 298-2000 K with the Eckart tunneling correction. Our calculations indicate that the hydrogen atoms of the methylene functional group are easier to be abstracted by H and CH₃ radicals. The multistructural torsional anharmonicities of H-abstraction reactions MP+H/CH₃ are significant within the temperature range investigated. The tunneling effects are more pronounced at low temperatures, and contribute considerably to the rate constants below 500 K. The model from the work of Diévart et al. is updated with our calculations, and the simulations of the updated model are in excellent agreement with the reported ignition delay time of MP/O₂/Ar and MP/Air mixtures. The sensitivity analysis indicates that the H-abstraction reactions, MP+H=CH₃CH₂CHCH₂C(=O)OCH₃/CH₃CHCH₂CH₂C(=O)OCH₃+H₂, are critical in controlling the initial fuel consumption and ignition delay time of MP.

Key words: Methyl pentanoate, H-Abstraction, Dual-level MS-T, Ignition delay time, Kinetic modeling

SHANG Yanlei, NING Hongbo, SHI Jinchun, LUO S. N.. Implication of Sensitive Reactions to Ignition of Methyl Pentanoate: H-Abstraction Reactions by H and CH₃ Radicals[J]. 高等学校化学研究, 2021, 37(3): 711-717.

SHANG Yanlei, NING Hongbo, SHI Jinchun, LUO S. N.. Implication of Sensitive Reactions to Ignition of Methyl Pentanoate: H-Abstraction Reactions by H and CH₃ Radicals[J]. Chemical Research in Chinese Universities, 2021, 37(3): 711-717.

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Implication of Sensitive Reactions to Ignition of Methyl Pentanoate: H-Abstraction Reactions by H and CH₃ Radicals

Implication of Sensitive Reactions to Ignition of Methyl Pentanoate: H-Abstraction Reactions by H and CH₃ Radicals

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