A Computational Kinetics Study on the Intramolecular Hydrogen Shift Reactions of Alkylperoxy Radicals in 2‐Methyltetrahydrofuran Oxidation

Parab, Prajakta Rajaram; Sakade, Naoki; Sakai, Yasuyuki; Fernandes, Ravi X.; Heufer, Karl Alexander

doi:10.1002/kin.21087

Cited by 8 publications

(8 citation statements)

References 38 publications

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“…The variations in the structure between THF and 2,5-DMTHF required modification of the activation energy of -2 kcal/mol in the case of a tertiary carbon and +2 kcal/mol for a primary carbon bonded to the eliminated H atom [8]. The reaction rate coefficients for isomerization reactions of RȮ 2 into Q OOH were taken from the work of Parab et al [38], calculated for 2-MTHF. Analogies with the reaction rate coefficients used for the model of THF [5] were adopted for the reactions of hydroperoxyl radical elimination from Q OOH, formation of a cyclic ether and ȮH radical, beta-scission of Q OOH radical, and molecular rearrangement forming a dioxene molecule and an ȮH radical.…”

Section: Low Temperature Model For 25-dmthfmentioning

confidence: 99%

2,5-Dimethyltetrahydrofuran combustion: Ignition delay times at high and low temperatures, speciation measurements and detailed kinetic modeling

Fenard

Song

Minwegen

et al. 2019

Combustion and Flame

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Ignition delays of stoichiometric mixture of 2,5-dimethyltetrahydrofuran/O 2 /inert mixtures were measured at temperatures ranging from 650 to 1300 K in a RCM and in a shock tube. Operating pressures ranged from 10 to 40 bar at higher temperature (ST) and 10 to 20 bar at lower temperatures (RCM). The ignition delay times exhibit a slight deviation from Arrhenius behaviour, and limited low-temperature reactivity. This behaviour is similar to other cyclic ethers studied in comparable conditions namely THF, 2-MTHF and 3-MTHF, where 2,5-dimethylterahydrofuran (2,5-DMTHF) is showing the lowest reactivity of this series of cyclic ethers.Detailed speciation and quantification of the intermediates formed by a stoichiometric 2,5-DMTHF/O 2 /N 2 mixture in the combustion chamber of the RCM was performed at different times between top dead center and the ignition event for T c = 712 K and p TDC = 10 bar. The major fuel specific species observed are 2,5-dimethylfuran, 2,6-dimethyl-1,3-diox-4-ene, hexa-2,5-dione, 1-(2methylcyclopropyl)ethanone, and hex-3-en-2-one.To provide further insight into the kinetics of the oxidation of 2,5-DMTHF, a comprehensive kinetic model was developed and validated upon the acquired experimental data. Reaction pathway analysis and sensitivity analysis give an overview of the oxidation process of 2,5-DMTHF and elucidates the formation of the experimentally observed fuel-specific intermediates.

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Section: Low Temperature Model For 25-dmthfmentioning

confidence: 99%

2,5-Dimethyltetrahydrofuran combustion: Ignition delay times at high and low temperatures, speciation measurements and detailed kinetic modeling

Fenard

Song

Minwegen

et al. 2019

Combustion and Flame

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“…• Reaction rate constants for the RȮ 2 to QOOH isomerization type of reactions (class 15) were adopted from the theoretical study of Parab et al [35]. These rate parameters were calculated for all sites of 2-MTHF at CBS-QB3 level of theory.…”

Section: General Model Featuresmentioning

confidence: 99%

Ignition characteristics of 2-methyltetrahydrofuran: An experimental and kinetic study

Tripathi

Lee

Fernandes

et al. 2017

Proceedings of the Combustion Institute

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The present paper elucidates oxidation behavior of 2-methyltetrahydrofuran (2-MTHF), a novel second-generation biofuel. New experimental data sets for 2-MTHF including ignition delay time measurements in two different combustion reactors, i.e. rapid compression machine and high-pressure shock tube, are presented. Measurements for 2-MTHF/oxidizer/diluent mixtures were performed in the temperature range of 639 − 1413 K, at pressures of 10, 20, and 40 bar, and at three different equivalence ratios of 0.5, 1.0, and 2.0. A detailed chemical kinetic model describing both low-and high-temperature chemistry of 2-MTHF was developed and validated against new ignition delay measurements and already existing flame species profiles and ignition delay measurements. The mechanism provides satisfactory agreement with the experimental data. For identifying key reactions at various combustion conditions and to attain a better understanding of the combustion behavior, reaction path and sensitivity analyses were performed.

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“…The study compared the rate constants of ROO isomers of 3-MTHF with their counterparts of methylcyclopentane, which revealed that faster kinetics in 3-MTHF can be attributed to the effect of ring O 2 on the intramolecular hydrogen shift reactions. A similar approach was employed by Parab et al [131], where the most important abstraction sites were found to be carbon sites neighboring a ring oxygen atom, which was linked to weak C-H bond. Furthermore, Sudholt et al [28] calculated the BDEs of a number of THFs and explored the initial reactions during the auto-ignition for these fuels.…”

Section: Quantum Chemical Kinetic Calculationsmentioning

confidence: 95%

“…Tetrahydrofurans were the focus of another group of computational chemical kinetic studies [26,28,[129][130][131][132]. For instance, the study by Simmie [26] presented calculations of the entropies, enthalpies of formation, enthalpy functions, specific heats (c p ) and all C-H and C-CH 3 BDEs for THF, 2-MTHF and 2,5-dimethyltetrahydrofuran (DMTHF).…”

Section: Quantum Chemical Kinetic Calculationsmentioning

confidence: 99%

Recent Trends in the Production, Combustion and Modeling of Furan-Based Fuels

Eldeeb

Akih-Kumgeh

2018

Energies

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Abstract:There is growing interest in the use of furans, a class of alternative fuels derived from biomass, as transportation fuels. This paper reviews recent progress in the characterization of its combustion properties. It reviews their production processes, theoretical kinetic explorations and fundamental combustion properties. The theoretical efforts are focused on the mechanistic pathways for furan decomposition and oxidation, as well as the development of detailed chemical kinetic models. The experiments reviewed are mostly concerned with the temporal evolutions of homogeneous reactors and the propagation of laminar flames. The main thrust in homogeneous reactors is to determine global chemical time scales such as ignition delay times. Some studies have adopted a comparative approach to bring out reactivity differences. Chemical kinetic models with varying degrees of predictive success have been established. Experiments have revealed the relative behavior of their combustion. The growing body of literature in this area of combustion chemistry of alternative fuels shows a great potential for these fuels in terms of sustainable production and engine performance. However, these studies raise further questions regarding the chemical interactions of furans with other hydrocarbons. There are also open questions about the toxicity of the byproducts of combustion.

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A Computational Kinetics Study on the Intramolecular Hydrogen Shift Reactions of Alkylperoxy Radicals in 2‐Methyltetrahydrofuran Oxidation

Cited by 8 publications

References 38 publications

2,5-Dimethyltetrahydrofuran combustion: Ignition delay times at high and low temperatures, speciation measurements and detailed kinetic modeling

2,5-Dimethyltetrahydrofuran combustion: Ignition delay times at high and low temperatures, speciation measurements and detailed kinetic modeling

Ignition characteristics of 2-methyltetrahydrofuran: An experimental and kinetic study

Recent Trends in the Production, Combustion and Modeling of Furan-Based Fuels

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