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

• Main Authors: Bui, T.Q (Author), Giri, B.R (Author), Huynh, L.K (Author), Mai, T.V.T (Author), Mauss, F. (Author), Nhung, N.T.A (Author), Quy, P.T (Author), Shrestha, K.P (Author)
• Format: Article
• Language: English
• Published: MDPI 2023
• Subjects: 2-methyl tetrahydrofuran; 2-methyltetrahydrofuran; ab initio; Ab initio; Abstracting; Atmospheric chemistry; Atmospheric pressure; Atmospheric temperature; Combustion; Cyclic ether; Free radicals; Hydrogen; Indicators (chemical); kinetic modeling; Kinetic models; Kinetic theory; Kinetics; Lows-temperatures; Master equations; Nitrogen oxides; OH -; OH radical; OH radicals; Pressure effects; Reaction kinetics; Rice–ramsperge–kassel–marcu-based master equation calculation; Rice-ramsperger-kassel-marcus; RRKM-ME calculations; Temperature distribution
• Online Access: View Fulltext in Publisher

 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. © 2023 by the authors.