Detailed Modeling of the Reaction of C2H5 + O2

Carstensen, Hans-Heinrich; Naik, Chitralkumar V.; Dean, Anthony M.

doi:10.1021/jp0451142

Cited by 69 publications

(110 citation statements)

References 59 publications

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“…These reaction pathways continue to be the focus of intense scrutiny and theoretical attention; for example, recent studies have shown [34][35][36] The MCH radical isomers are denoted by a number for a radical site on the ring or "X" for a radical site on the CH 3 group. Fig.…”

Section: Discussionmentioning

confidence: 99%

Modeling and experimental investigation of methylcyclohexane ignition in a rapid compression machine

Pitz¹,

Naik²,

Mhaoldúin³

et al. 2007

Proceedings of the Combustion Institute

175

234

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A new chemical kinetic reaction mechanism has been developed for the oxidation of methylcyclohexane (MCH), combining a new low-temperature mechanism with a recently developed high temperature mechanism. Predictions from this kinetic model are compared with experimentally measured ignition delay times from a rapid compression machine. Computed results were found to be particularly sensitive to isomerization rates of methylcyclohexylperoxy radicals. Three different methods were used to estimate rate constants for these isomerization reactions. Rate constants based on comparable alkylperoxy radical isomerizations corrected for the differences in the structure of MCH and the respective alkane, predicted ignition delay times in very poor agreement with the experimental results. The most significant drawback was the complete absence of a region of negative temperature coefficient (NTC) in the model results using this method, although a prominent NTC region was observed experimentally. Alternative estimates of the isomerization reaction rate constants, based on the results from previous experimental studies of low temperature cyclohexane oxidation, provided much better agreement with the present experiments, including the pronounced NTC behavior. The most important feature of the resulting methylcyclohexylperoxy radical isomerization reaction analysis was found to be the relative rates of isomerizations that proceed through 5-, 6-, 7-and 8--3-membered transition state ring structures and their different impacts on the chainbranching behavior of the overall mechanism. Theoretical implications of these results are discussed, with particular attention on how intramolecular H atom transfer reactions are influenced by the differences between linear alkane and cycloalkane structures.

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Section: Discussionmentioning

confidence: 99%

Modeling and experimental investigation of methylcyclohexane ignition in a rapid compression machine

Pitz¹,

Naik²,

Mhaoldúin³

et al. 2007

Proceedings of the Combustion Institute

175

234

View full text Add to dashboard Cite

show abstract

“…Typically, they have the structure of a methyl ester group attached to a long hydrocarbon chain of about [16][17][18][19] carbon atoms (C [16][17][18][19] H x -C(=O)O-CH 3 ). Due to their large size and their chemical/physical complexity (e.g., the introduction of the heterogeneous O atom compared to hydrocarbon fuels), detailed kinetic study on these biodiesel molecules is challenging both experimentally and theoretically.…”

Section: Introductionmentioning

confidence: 99%

Mechanism and kinetics of low-temperature oxidation of a biodiesel surrogate−methyl acetate radicals with molecular oxygen

V.‐T.

Huynh

2014

Struct Chem

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Accurate description of reactions between methyl acetate (MA) radicals and molecular oxygen is an essential prerequisite for understanding as well as modeling low-temperature oxidation and/or ignition of MA, a small biodiesel surrogate, because their multiple reaction pathways either accelerate the oxidation process via chain branching or inhibit it by forming relatively stable products. The accurate composite CBS-QB3 level of theory was used to explore potential energy surfaces for MA radicals ? O 2 system. Using the electronic structure calculation results under the framework of canonical statistical mechanics and transition state theory, thermodynamic properties of all species as well as high-pressure rate constants of all reaction channels were derived with explicit corrections for tunneling and hindered internal rotations. Our calculated results are in good agreement with a limited number of scattered data in the literature. Furthermore, pressure-and temperature-dependent rate constants were then computed using the Quantum RiceRamsperger-Kassel and the modified strong collision theories. This procedure resulted in a thermodynamically consistent detailed kinetic mechanism for low-temperature oxidation of the title fuel. We also demonstrated that even the detailed mechanism consists of several reactions of different reaction types, only the addition of the reactants and the re-dissociation of the initially formed adducts are important for low-temperature combustion at engine-liked conditions.

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“…Recent studies, including that of Carstensen et al 41 on n-alkanes such as ethane and propane have highlighted the importance of the direct elimination of olefin and a hydroperoxyl from RO 2 .…”

mentioning

confidence: 99%

Detailed Chemical Kinetic Modeling of Cyclohexane Oxidation†

et al. 2007

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A detailed chemical kinetic mechanism has been developed and used to study the oxidation of cyclohexane at both low and high temperatures. Reaction rate constant rules are developed for the low temperature combustion of cyclohexane. These rules can be used for in chemical kinetic mechanisms for other cycloalkanes. Since cyclohexane produces only one type of cyclohexyl radical, much of the low temperature chemistry of cyclohexane is described in terms of one potential energy diagram showing the reaction of cyclohexyl radical + O 2 through 2 five, six and seven membered ring transition states. The direct elimination of cyclohexene and HO 2 from RO 2 is included in the treatment using a modified rate constant of Cavallotti et al.Published and unpublished data from the Lille rapid compression machine, as well as jet-stirred reactor data are used to validate the mechanism. The effect of heat loss is included in the simulations, an improvement on previous studies on cyclohexane. Calculations indicated that the production of 1,2-epoxycyclohexane observed in the experiments can not be simulated based on the current understanding of low temperature chemistry. Possible 'alternative' H-atom isomerisations leading to different products from the parent O 2 QOOH radical were included in the low temperature chemical kinetic mechanism and were found to play a significant role.

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Detailed Modeling of the Reaction of C₂H₅ + O₂

Cited by 69 publications

References 59 publications

Modeling and experimental investigation of methylcyclohexane ignition in a rapid compression machine

Modeling and experimental investigation of methylcyclohexane ignition in a rapid compression machine

Mechanism and kinetics of low-temperature oxidation of a biodiesel surrogate−methyl acetate radicals with molecular oxygen

Detailed Chemical Kinetic Modeling of Cyclohexane Oxidation†

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