An Ab Initio RRKM-Based Master Equation Study for Kinetics of OH-Initiated Oxidation of 2-Methyltetrahydrofuran and Its Implications in Kinetic Modeling

Tam V.-T. Mai, Thanh Q. Bui, Nguyen Thi Ai Nhung (), Phan Tu Quy, Krishna Prasad Shrestha, Fabian Mauss, Binod Raj Giri () and Lam K. Huynh ()
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Tam V.-T. Mai: Institute of Fundamental and Applied Sciences, Duy Tan University, 06 Tran Nhat Duat, Tan Dinh Ward, District 1, Ho Chi Minh City 700000, Vietnam
Thanh Q. Bui: Department of Chemistry, University of Sciences, Hue University, Hue City 530000, Vietnam
Nguyen Thi Ai Nhung: Department of Chemistry, University of Sciences, Hue University, Hue City 530000, Vietnam
Phan Tu Quy: Department of Natural Sciences & Technology, Tay Nguyen University, Buon Ma Thuot City 630000, Vietnam
Krishna Prasad Shrestha: Thermodynamics and Thermal Process Engineering, Brandenburg University of Technology, Siemens-Halske-Ring 8, 03046 Cottbus, Germany
Fabian Mauss: Thermodynamics and Thermal Process Engineering, Brandenburg University of Technology, Siemens-Halske-Ring 8, 03046 Cottbus, Germany
Binod Raj Giri: Physical Science and Engineering Division, Clean Combustion Research Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
Lam K. Huynh: School of Chemical and Environmental Engineering, International University, Quarter 6, Linh Trung Ward, Thu Duc City, Ho Chi Minh City 700000, Vietnam

Energies, 2023, vol. 16, issue 9, 1-25

Abstract: Cyclic ethers (CEs) can be promising future biofuel candidates. Most CEs possess physico-chemical and combustion indicators comparable to conventional fuels, making them suitable for internal combustion engines. This work computationally investigates the kinetic behaviors of hydrogen abstraction from 2-methyl tetrahydrofuran (2MTHF), one of the promising CEs, by hydroxyl radicals under combustion and atmospheric relevant conditions. The various reaction pathways were explored using the CCSD(T)/cc-pVTZ//M06-2X/aug-cc-pVTZ level of theory. The Rice–Ramsperger–Kassel–Marcus-based master equation (RRKM-ME) rate model, including treatments for hindered internal rotation and tunneling, was employed to describe time-dependent species profiles and pressure and temperature-dependent rate coefficients. Our kinetic model revealed that the H-abstraction proceeds via an addition-elimination mechanism forming reaction complexes at both the entrance and exit channels. Eight different reaction channels yielding five radical products were located. The reaction exhibited complex kinetics yielding a U-shaped Arrhenius behavior. An unusual occurrence of negative temperature dependence was observed at low temperatures, owing to the negative barrier height for the hydrogen abstraction reaction from the C-H bond at the vicinity of the O-atom. A shift in the reaction mechanism was observed with the dominance of the abstraction at C α -H of 2MTHF ring (causing negative- T dependence) and at CH 3 (positive- T dependence) at low and high temperatures, respectively. Interestingly, the pressure effect was observed at low temperatures, revealing the kinetic significance of the pre-reaction complex. Under atmospheric pressure, our theoretical rate coefficients showed excellent agreement with the available literature data. Our model nicely captured the negative temperature-dependent behaviors at low temperatures. Our predicted global rate coefficients can be expressed as k ( T , 760 Torr) = 3.55 × 10 1 × T −4.72 × exp [−340.0 K/ T ] + 8.21 × 10 −23 × T 3.49 × exp [918.8 K/ T ] (cm 3 /molecule/s). Our work provides a detailed kinetic picture of the OH-initiated oxidation kinetics of 2MTHF. Hence, this information is useful for building a kinetic me chanism for methylated cyclic ethers.

Keywords: ab initio; RRKM-ME calculations; 2-methyl tetrahydrofuran; OH radicals; kinetic modeling (search for similar items in EconPapers)
JEL-codes: Q Q0 Q4 Q40 Q41 Q42 Q43 Q47 Q48 Q49 (search for similar items in EconPapers)
Date: 2023
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