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High-pressure limit rate rules for intramolecular H-migration reactions of α,β-hydroxyalkylperoxy radicals

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Abstract

The hydroxyalkylperoxy radicals are important intermediates in the low-temperature combustion for alkenes and alcohols, and H-migration reactions of hydroxyalkylperoxy radicals are one of the key reaction classes in their low-temperature combustion mechanisms. However, there are lack of accurate high-pressure limit rate constants for such class of reactions in the literature. In this paper, 104 reactions are selected to study, and they are divided into different subclasses according to the ring size of the transition states, the migration site of H atom, the types of carbons from which the hydrogen atoms are transferred and whether the OH group is located within or outside the ring of the transition states. The geometric optimization and the electronic structure calculations of all the species involved in the reactions are performed at the M06-2X/6-311++G(d,p) level. The high-pressure limit rate constants are calculated by using canonical transition state theory (TST). The rate constants of all reactions in the temperature range from 300 to 1500 K are given by the modified Arrhenius formula. It is found that the energy barriers and rate constants of H-migration reactions between hydroxyalkylperoxy radicals and alkylperoxy radicals are quite different. So it is necessary to provide kinetic parameters for the H-migration reactions of hydroxyalkylperoxy radicals through quantum chemistry calculation, instead of taking values from similar reactions in alkanes. In this paper, the high-pressure limit rate rules for each subclass are established by averaging the rate constants of the reactions in a reaction class. The construction of rate rules for the H-migration reactions of hydroxyalkylperoxy radicals is of great significance for the low-temperature combustion model and the automatic mechanism generation of alkenes and alcohols.

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Acknowledgements

This work is supported by the National Natural Science Foundation of China (Nos. 91441114).

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Authors and Affiliations

  1. College of Chemistry, Sichuan University, Chengdu, 610064, People’s Republic of China

    Jinfeng Pu & Zerong Li

  2. College of Chemical Engineering, Sichuan University, Chengdu, 610065, People’s Republic of China

    Xiaoxia Yao & Xiangyuan Li

  3. Engineering Research Center of Combustion and Cooling for Aerospace Power, Ministry of Education, Sichuan University, Chengdu, 610065, Sichuan, People’s Republic of China

    Xiangyuan Li

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  1. Jinfeng Pu
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Pu, J., Yao, X., Li, Z. et al. High-pressure limit rate rules for intramolecular H-migration reactions of α,β-hydroxyalkylperoxy radicals. Theor Chem Acc 140, 147 (2021). https://doi.org/10.1007/s00214-021-02849-3

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