LAPSE:2023.35667
Published Article
LAPSE:2023.35667
An Ab Initio RRKM-Based Master Equation Study for Kinetics of OH-Initiated Oxidation of 2-Methyltetrahydrofuran and Its Implications in Kinetic Modeling
May 23, 2023
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 Cα-H of 2MTHF ring (causing negative-T dependence) and at CH3 (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 × 101 × T−4.72 × exp [−340.0 K/T] + 8.21 × 10−23 × T3.49 × exp [918.8 K/T] (cm3/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.
Record ID
Keywords
2-methyl tetrahydrofuran, ab initio, kinetic modeling, OH radicals, RRKM-ME calculations
Subject
Suggested Citation
Mai TVT, Bui TQ, Nhung NTA, Quy PT, Shrestha KP, Mauss F, Giri BR, Huynh LK. An Ab Initio RRKM-Based Master Equation Study for Kinetics of OH-Initiated Oxidation of 2-Methyltetrahydrofuran and Its Implications in Kinetic Modeling. (2023). LAPSE:2023.35667
Author Affiliations
Mai TVT: Institute of Fundamental and Applied Sciences, Duy Tan University, 06 Tran Nhat Duat, Tan Dinh Ward, District 1, Ho Chi Minh City 700000, Vietnam; Faculty of Natural Sciences, Duy Tan University, Da Nang City 550000, Vietnam [ORCID]
Bui TQ: Department of Chemistry, University of Sciences, Hue University, Hue City 530000, Vietnam [ORCID]
Nhung NTA: Department of Chemistry, University of Sciences, Hue University, Hue City 530000, Vietnam [ORCID]
Quy PT: Department of Natural Sciences & Technology, Tay Nguyen University, Buon Ma Thuot City 630000, Vietnam
Shrestha KP: Thermodynamics and Thermal Process Engineering, Brandenburg University of Technology, Siemens-Halske-Ring 8, 03046 Cottbus, Germany
Mauss F: Thermodynamics and Thermal Process Engineering, Brandenburg University of Technology, Siemens-Halske-Ring 8, 03046 Cottbus, Germany
Giri BR: Physical Science and Engineering Division, Clean Combustion Research Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
Huynh LK: School of Chemical and Environmental Engineering, International University, Quarter 6, Linh Trung Ward, Thu Duc City, Ho Chi Minh City 700000, Vietnam; Vietnam National University, Ho Chi Minh City 700000, Vietnam [ORCID]
Bui TQ: Department of Chemistry, University of Sciences, Hue University, Hue City 530000, Vietnam [ORCID]
Nhung NTA: Department of Chemistry, University of Sciences, Hue University, Hue City 530000, Vietnam [ORCID]
Quy PT: Department of Natural Sciences & Technology, Tay Nguyen University, Buon Ma Thuot City 630000, Vietnam
Shrestha KP: Thermodynamics and Thermal Process Engineering, Brandenburg University of Technology, Siemens-Halske-Ring 8, 03046 Cottbus, Germany
Mauss F: Thermodynamics and Thermal Process Engineering, Brandenburg University of Technology, Siemens-Halske-Ring 8, 03046 Cottbus, Germany
Giri BR: Physical Science and Engineering Division, Clean Combustion Research Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia
Huynh LK: School of Chemical and Environmental Engineering, International University, Quarter 6, Linh Trung Ward, Thu Duc City, Ho Chi Minh City 700000, Vietnam; Vietnam National University, Ho Chi Minh City 700000, Vietnam [ORCID]
Journal Name
Energies
Volume
16
Issue
9
First Page
3730
Year
2023
Publication Date
2023-04-27
Published Version
ISSN
1996-1073
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Original Submission
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PII: en16093730, Publication Type: Journal Article
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LAPSE:2023.35667
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doi:10.3390/en16093730
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[v1] (Original Submission)
May 23, 2023
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May 23, 2023
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Original Submitter
Calvin Tsay
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