Computed Rate Coefficients and Product Yields for c-C5H5 + CH3 → Products

Sharma, Sandeep; Green, William

doi:10.1021/jp900679t

Cited by 76 publications

(82 citation statements)

References 48 publications

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“…Reaction rate coefficients for hydrogen abstraction by oxygen atoms, hydroxyl radicals (reactions 32-41) were deduced from Evans-Polanyi correlations proposed by Dean and Bozelli [31], analogous to recently developed tetrahydrofuran and tetrahydropyran kinetic models [10,34]. Kinetics for hydrogen abstraction from MTHF by hydroperoxy radicals (reactions [42][43][44][45][46] were taken from the theoretical calculations by Chakravarty et al [15]. Hydrogen abstraction reactions by carbon centered radicals, such as ethyl and allyl, were estimated from hydrogen abstraction by methyl but taking into consideration the effect of resonance stabilization [35,36].…”

Section: Hydrogen Abstraction From Mthfmentioning

confidence: 99%

Experimental and modeling study of the pyrolysis and combustion of 2-methyl-tetrahydrofuran

Bruycker

Tran

Carstensen

et al. 2017

Combustion and Flame

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Saturated cyclic ethers are being proposed as next-generation bio-derived fuels. However, their pyrolysis and combustion chemistry has not been well established. In this work, the pyrolysis and combustion chemistry of 2-methyl-tetrahydrofuran (MTHF) was investigated through experiments and detailed kinetic modeling. Pyrolysis experiments were performed in a dedicated plug flow reactor at 170 kPa, temperatures between 900 and 1100K and a N 2 (diluent) to MTHF molar ratio of 10. The combustion chemistry of MTHF was investigated by measuring mole fraction profiles of stable species in premixed flat flames at 6.7 kPa and equivalence ratios 0.7, 1.0 and 1.3 and by determining laminar burning velocities of MTHF/air flat flames with unburned gas temperatures of 298, 358 and 398K and equivalence ratios between 0.6 and 1.6. Furthermore, a kinetic model for pyrolysis and combustion of MTHF was developed, which contains a detailed description of the reactions of MTHF and its derived radicals with the aid of new high-level theoretical calculations. Model calculated mole fraction profiles and laminar burning velocities are in relatively good agreement with the obtained experimental data. At the applied pyrolysis conditions, unimolecular decomposition of MTHF by scission of the methyl group and concerted ring opening to 4-penten-1-ol dominates over scission of the ring bonds; the latter reactions were significant in tetrahydrofuran pyrolysis. MTHF is mainly consumed by hydrogen abstraction reactions. Subsequent decomposition of the resulting radicals by β-scission results in the observed product spectrum including small alkenes, formaldehyde, acetaldehyde and ketene. In the studied flames, unimolecular ring opening of MTHF is insignificant and consumption of MTHF through radical chemistry dominates. Recombination of 2-oxo-ethyl and 2-oxo-propyl, primary radicals in MTHF decomposition, with hydrogen atoms and carboncentered radicals results in a wide range of oxygenated molecules.

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Section: Hydrogen Abstraction From Mthfmentioning

confidence: 99%

Experimental and modeling study of the pyrolysis and combustion of 2-methyl-tetrahydrofuran

Bruycker

Tran

Carstensen

et al. 2017

Combustion and Flame

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“…The kinetics and thermochemistry for these reactions and species were taken from Sharma and Green. 30 Another important aspect of the kinetic model at high exo-TCD conversion is the secondary conversion of ethenylcyclopentenes. The latter produce fulvene and represents an important pathway to α-H-fulvenyl, cf.…”

Section: Secondary Chemistry and Aromatics Formationmentioning

confidence: 99%

Kinetic Modeling of Jet Propellant-10 Pyrolysis

et al. 2014

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A detailed kinetic model for the thermal decomposition of the advanced fuel Jet-Propellant 10 (JP-10) was constructed using a combination of automated mechanism generation techniques and ab initio calculations. Rate coefficients for important unimolecular initiation routes of exo-TCD were calculated using the multireference method CAS-PT2, while rate coefficients for the various primary decompositions of the exo-TCD-derived monoradicals were obtained using CBS-QB3. Rateof-production analysis showed the importance of four dominating JP-10 decomposition channels. The model predictions agree well with five independent experimental data sets for JP-10 pyrolysis that cover a wide range of operating conditions (T = 300− 1500 K, P = 300 Pa−1.7 × 10 5 Pa, dilution = 0.7−100 mol% JP-10, conversion = 0−100%) without any adjustment of the model parameters. A significant part of the model comprises secondary conversion routes to aromatic and polyaromatic hydrocarbons and could thus be used to assess the tendency for deposit formation in fuel-rich zones of endothermic fuel applications.

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“…Refs. [10,11] show that the final products of this reaction are fulvene and benzene. Melius et al [12] theoretically studied the isomerisation of fulvene using the method BAC-MP4.…”

Section: Introductionmentioning

confidence: 94%

Reaction of cyclopentadienyl and methyl radicals

Krasnoukhov

Mebel

Zavershinskiy

et al. 2017

JBPE

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Geometries and potential energies of reagents, products, and intermediate states for the reaction between cyclopentadienyl (C5H5) and methyl (CH3) radicals are found by means of ab initio quantum mechanical methods CCSD(T)/cc-pVTZ-f12, B2PLYPD3/AUG-CC-PVDZ and B3LYP/6-311G. Basing on the analysis of the found energy, structural and kinetic characteristics of the compounds involved, the reaction paths leading to the formation of fulvene and benzene, the simplest aromatic compound, are determined. The reaction path begins from the formation of the intermediate compound, methylcyclopentadiene, followed by tearing-off a hydrogen atom from it: C5H5 + CH3 → C5H5CH3 → C5H4CH3 + H. The subsequent monomolecular transformations of C5H4CH3 are closed by the formation of either fulvene (via the loss of one hydrogen atom from the methyl group) or benzene (via the stages of transforming the pentamerous ring into a hexamerous one and tearing-off a hydrogen atom). The rate constants found in the paper using the software package MESS show that the rate of benzene formation is always higher than that for fulvene within the temperature interval 500-2250 K. Since fulvene can also isomerize into benzene, the reaction C5H5 + CH3 is an important supplier of the initial bricks for building polycyclic aromatic hydrocarbons dangerous for living systems.

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Computed Rate Coefficients and Product Yields for c-C₅H₅ + CH₃ → Products

Cited by 76 publications

References 48 publications

Experimental and modeling study of the pyrolysis and combustion of 2-methyl-tetrahydrofuran

Experimental and modeling study of the pyrolysis and combustion of 2-methyl-tetrahydrofuran

Kinetic Modeling of Jet Propellant-10 Pyrolysis

Reaction of cyclopentadienyl and methyl radicals

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