A model of tetrahydrofuran low-temperature oxidation based on theoretically calculated rate constants

Abstract

, et al.. A model of tetrahydrofuran low-temperature oxidation based on theoretically calculated rate constants. Combustion and Flame, Elsevier, 2018, 191, pp.252-269. <10.1016/j.combustflame.2018 Published in Combustion and Flame (2018), 191, 252-269 AbstractThe first detailed kinetic model of the low-temperature oxidation of tetrahydrofuran has been developed. Thermochemical and kinetic data related to the most important elementary reactions have been derived from ab initio calculations at the CBS-QB3 level of theory. A comparison of the rate constants at 600 K, obtained from these calculations with values estimated using recently published rate rules for alkanes, sometimes show differences of several orders of magnitude for alkylperoxy radical isomerizations, HO2-eliminations, and oxirane formations. The new model satisfactorily reproduces previously published ignition delay times obtained in a rapid-compression machine and in a shock tube, as well as numerous product mole fractions measured in a jet-stirred reactor at low to intermediate temperatures and in a low-pressure laminar premixed flame. To highlight the most significant reaction pathways, flow-rate and sensitivity analyses have been performed with this new model.

vdW‐TSSCDS—An automated and global procedure for the computation of stationary points on intermolecular potential energy surfaces

“…With the combination of LL and HL calculations, the TSSCDS method serves as a powerful tool to obtain accurate information about reactivity and topography of the PES for a given system at low computational cost. The method has been successfully employed in a number of different applications ranging from combustion chemistry, through photolysis and mass spectrometry to organometallic catalysis …”

A Trajectory-Based Method to Explore Reaction Mechanisms

“…of 21 The method has been successfully employed to study reactions involved in combustion [66,67], photolysis [68][69][70], mass spectrometry [71] and organometallic catalysis [43]. The aim of this review is to go over several examples where tsscds is employed to either discover new mechanisms and/or to explain the experiments.…”

A Trajectory-Based Method to Explore Reaction Mechanisms

“…The source code can be downloaded from: http://forge.cesga.es/wiki/g/tsscds/HomePage. The method has been successfully employed to study reactions involved in combustion [66,67], photolysis [68][69][70], mass spectrometry [71] and organometallic catalysis [43]. The aim of this review is to go over several examples where tsscds is employed to either discover new mechanisms and/or to explain the experiments.…”

“…The solid and dashed lines correspond to the MP and 1W results, respectively. Very recently, Fenard et al developed a detailed kinetic model of the low-temperature oxidation of tetrahydrofuran (THF) based on theoretically-calculated rate constants[67]. The reaction pathways involved in these processes were probed with our automated software tsscds[67] using CBS-QB3 as the choice for the high-level of electronic structure.…”

“…Very recently, Fenard et al developed a detailed kinetic model of the low-temperature oxidation of tetrahydrofuran (THF) based on theoretically-calculated rate constants[67]. The reaction pathways involved in these processes were probed with our automated software tsscds[67] using CBS-QB3 as the choice for the high-level of electronic structure. The rate constants were determined using TST with a tunneling correction using an Eckart potential.The predictions from the model developed by Fenard et al are overall in good agreement with the different experimental measurements.…”