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A Computational Kinetics Study on the Intramolecular Hydrogen Shift Reactions of Alkylperoxy Radicals in 2‐Methyltetrahydrofuran Oxidation
Author(s) -
Parab Prajakta R.,
Sakade Naoki,
Sakai Yasuyuki,
Fernandes Ravi,
Heufer K. Alexander
Publication year - 2017
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21087
Subject(s) - chemistry , intramolecular force , isomerization , transition state theory , kinetics , radical , reaction rate constant , ring (chemistry) , photochemistry , hydrogen atom abstraction , chemical kinetics , combustion , medicinal chemistry , computational chemistry , catalysis , stereochemistry , organic chemistry , physics , quantum mechanics
2‐Methyltetrahydrofuran (2‐MTHF) is one of the potential fuel components based on its combustion behavior, engine efficiency, and emission performance as proposed by the Cluster of Excellence “Tailor Made Fuels from Biomass (TMFB)” at RWTH Aachen University, Germany. Reaction kinetics of intramolecular hydrogen shift (ROO to QOOH) reactions in 2‐MTHF is theoretically investigated in this work. High‐pressure limit rate constants (500–2000 K) are determined from the transition state theory by employing the CBS‐QB3 composite method. Carbon sites neighboring a ring oxygen atom are favorable abstraction sites in 2‐MTHF due to its weak C─H bond strengths. The size of the transition state ring (six‐ and five‐membered) also plays an important role in the isomerization reaction kinetics. Further, effects of ring oxygen and methyl group position in 2‐MTHF are investigated. At 500 K, total rate constants for the isomerization reactions in ROO2 and ROO5t are 51 and 67 times faster in 2‐MTHF than in methylcyclopentane.