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Mechanisms and kinetics of the low-temperature oxidation of 2-methylfuran: insight from DFT calculations and kinetic simulations.

Abstract

The low-temperature oxidation (LTO) mechanisms of the 2-methylfuran (2-MF) biofuel and the corresponding thermodynamic and kinetic properties have been explored by density functional theory (DFT) and composite G4 methodologies as well as kinetic simulations. The O2 addition to the main furylCH2 radical from the methyl dehydrogenation in 2-MF forms three peroxide radicals PO1, PO2, and PO3 with the energy barriers of 15.1, 19.3, and 20.6 kcal mol-1 and the reaction ΔG of -8.2, 5.7, and -0.1 kcal mol-1 (298 K and 1 atm), respectively. Through hydrogen transfer followed by dehydroxylation, these nascent products evolve into stable aldehydes and cyclic ketones, which may further decompose into smaller species under the action of OH. Calculations and simulations show that the product P1 from the dehydroxylation of PO1 has a dominant population (higher than 96%) among the final products, although the temperature and pressure may influence the species profiles and rate constants to some extent. Based on the G4-calibrated thermodynamic parameters, the temperature and pressure dependence of the rate constants and the two- and three-parameter Arrhenius coefficients for all reactions considered here have been determined by using the transition state theory (TST) and Rice-Ramsperger-Kassel-Marcus (RRKM) methods. The present results provide a comprehensive understanding of the mechanisms and kinetics of the LTO process of the 2-MF biofuel.

Authors+Show Affiliations

State Key Laboratory of Physical Chemistry of Solid Surfaces and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China. zxcao@xmu.edu.cn.State Key Laboratory of Physical Chemistry of Solid Surfaces and Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China. zxcao@xmu.edu.cn.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31970347

Citation

Li, Yuanyuan, and Zexing Cao. "Mechanisms and Kinetics of the Low-temperature Oxidation of 2-methylfuran: Insight From DFT Calculations and Kinetic Simulations." Physical Chemistry Chemical Physics : PCCP, 2020.
Li Y, Cao Z. Mechanisms and kinetics of the low-temperature oxidation of 2-methylfuran: insight from DFT calculations and kinetic simulations. Phys Chem Chem Phys. 2020.
Li, Y., & Cao, Z. (2020). Mechanisms and kinetics of the low-temperature oxidation of 2-methylfuran: insight from DFT calculations and kinetic simulations. Physical Chemistry Chemical Physics : PCCP, doi:10.1039/c9cp05937g.
Li Y, Cao Z. Mechanisms and Kinetics of the Low-temperature Oxidation of 2-methylfuran: Insight From DFT Calculations and Kinetic Simulations. Phys Chem Chem Phys. 2020 Jan 23; PubMed PMID: 31970347.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Mechanisms and kinetics of the low-temperature oxidation of 2-methylfuran: insight from DFT calculations and kinetic simulations. AU - Li,Yuanyuan, AU - Cao,Zexing, Y1 - 2020/01/23/ PY - 2020/1/24/entrez JF - Physical chemistry chemical physics : PCCP JO - Phys Chem Chem Phys N2 - The low-temperature oxidation (LTO) mechanisms of the 2-methylfuran (2-MF) biofuel and the corresponding thermodynamic and kinetic properties have been explored by density functional theory (DFT) and composite G4 methodologies as well as kinetic simulations. The O2 addition to the main furylCH2 radical from the methyl dehydrogenation in 2-MF forms three peroxide radicals PO1, PO2, and PO3 with the energy barriers of 15.1, 19.3, and 20.6 kcal mol-1 and the reaction ΔG of -8.2, 5.7, and -0.1 kcal mol-1 (298 K and 1 atm), respectively. Through hydrogen transfer followed by dehydroxylation, these nascent products evolve into stable aldehydes and cyclic ketones, which may further decompose into smaller species under the action of OH. Calculations and simulations show that the product P1 from the dehydroxylation of PO1 has a dominant population (higher than 96%) among the final products, although the temperature and pressure may influence the species profiles and rate constants to some extent. Based on the G4-calibrated thermodynamic parameters, the temperature and pressure dependence of the rate constants and the two- and three-parameter Arrhenius coefficients for all reactions considered here have been determined by using the transition state theory (TST) and Rice-Ramsperger-Kassel-Marcus (RRKM) methods. The present results provide a comprehensive understanding of the mechanisms and kinetics of the LTO process of the 2-MF biofuel. SN - 1463-9084 UR - https://www.unboundmedicine.com/medline/citation/31970347/Mechanisms_and_kinetics_of_the_low-temperature_oxidation_of_2-methylfuran:_insight_from_DFT_calculations_and_kinetic_simulations L2 - https://doi.org/10.1039/c9cp05937g DB - PRIME DP - Unbound Medicine ER -
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