Investigating the kinetics of the intramolecular H-migration reaction class of methyl-ester peroxy radicals in low-temperature oxidation mechanisms of biodiesel

Li, Tao; Li, Juanqin; Chen, Siyu; Zhu, Quan; Li, Zerong

doi:10.1039/d3cp03376g

Phys. Chem. Chem. Phys.

2023

DOI: 10.1039/d3cp03376g

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Investigating the kinetics of the intramolecular H-migration reaction class of methyl-ester peroxy radicals in low-temperature oxidation mechanisms of biodiesel

Tao Li,

Juanqin Li,

Siyu Chen

et al.

Abstract: Accurate rate rules of 20 subclasses for intramolecular H-migration reactions of methyl-ester peroxide radicals are developed, considering the influence of the ester group.

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2024

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Cited by 2 publications

References 85 publications

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Kinetic investigations on the β-scission reactions of hydroperoxy methyl-ester radicals and the concerted HO2 elimination reactions of methyl-ester peroxy radicals: Implication for low-temperature combustion modeling of methyl esters

Li,

Chen,

et al. 2024

Combustion and Flame

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Kinetic investigations on the β-scission reactions of hydroperoxy methyl-ester radicals and the concerted HO2 elimination reactions of methyl-ester peroxy radicals: Implication for low-temperature combustion modeling of methyl esters

Li,

Chen,

et al. 2024

Combustion and Flame

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Reaction Rate Rules of Intramolecular H-Migration Reaction Class for RIORIIOO·Radicals in Ether Combustion

Sun,

2024

Molecules

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The intramolecular H-migration reaction of RIORIIOO· radicals constitute a key class of reactions in the low-temperature combustion mechanism of ethers. Despite this, there is a dearth of direct computations regarding the potential energy surface and rate constants specific to ethers, especially when considering large molecular systems and intricate branched-chain structures. Furthermore, combustion kinetic models for large molecular ethers generally utilize rate constants derived from those of structurally similar alcohols or alkane fuels. Consequently, chemical kinetic studies involve the calculation of energy barriers and rate rules for the intramolecular H-migration reaction class of RIORIIOO· radicals, which are systematically conducted using the isodesmic reaction method (IRM). The geometries of the species participating in these reactions are optimized, and frequency calculations are executed using the M06–X method in tandem with the 6–31+G(d,p) basis set by the Gaussian 16 program. Moreover, the M06–2X/6–31+G(d,p) method acts as the low-level ab initio method, while the CBS–QB3 method is utilized as the high-level ab initio method for calculating single-point energies. Rate constants at the high-pressure-limit are computed based on the reaction class transition state theory (RC-TST) by ChemRate program, incorporating asymmetric Eckart tunneling corrections for intramolecular H-migration reactions across a temperature range of 500 to 2000 K. It was found that the isodesmic reaction method gives accurate energy barriers and rate constants, and the rate constants of the H-migration reaction for RIORIIOO· radicals diverge from those of comparable reactions in alkanes and alcohol fuels. There are significant disparities in energy barriers and rate constants across the entire reaction classes of the H-migration reaction for RIORIIOO· radicals, necessitating the subdivision of the H-migration reaction into subclasses. Rate rules are established by averaging the rate constants of representative reactions for each subclass, which is pivotal for the advancement of accurate low-temperature combustion reaction mechanisms for ethers.

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Investigating the kinetics of the intramolecular H-migration reaction class of methyl-ester peroxy radicals in low-temperature oxidation mechanisms of biodiesel

Abstract: Accurate rate rules of 20 subclasses for intramolecular H-migration reactions of methyl-ester peroxide radicals are developed, considering the influence of the ester group.

Cited by 2 publications

References 85 publications

Kinetic investigations on the β-scission reactions of hydroperoxy methyl-ester radicals and the concerted HO2 elimination reactions of methyl-ester peroxy radicals: Implication for low-temperature combustion modeling of methyl esters

Kinetic investigations on the β-scission reactions of hydroperoxy methyl-ester radicals and the concerted HO2 elimination reactions of methyl-ester peroxy radicals: Implication for low-temperature combustion modeling of methyl esters

Reaction Rate Rules of Intramolecular H-Migration Reaction Class for RIORIIOO·Radicals in Ether Combustion

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