Reaction mechanism, rate constants, and product yields for unimolecular and H-assisted decomposition of 2,4-cyclopentadienone and oxidation of cyclopentadienyl with atomic oxygen

Ghildina, A. R.; Олейников, А. Д.; Azyazov, Valeriy N.; Mebel, Alexander M.

doi:10.1016/j.combustflame.2017.05.015

Cited by 36 publications

(32 citation statements)

References 58 publications

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“…and Yang et al 41 . Submechanisms for the oxidation and pyrolysis of cyclopentene and cyclopentadiene were taken from our previous works 20,42 and updated using the works by Zhong and Bozzelli, 43,44 Wang et al, 45 Oleinikov et al, 46 Ghildina et al, 47 and Vermeire et al 48 on 1,5‐hexadiene.…”

Section: Methodsmentioning

confidence: 99%

“…Finally, the methylcyclopentadiene submechanism was mostly taken from Herbinet et al 38 with the decomposition yielding methyl and cyclopentadienyl radicals coming from Sharma and Green 39 at atmospheric pressure. Fulvene formation was also considered following the work by Jin et al 40 and Yang et al 41 Submechanisms for the oxidation and pyrolysis of cyclopentene and cyclopentadiene were taken from our previous works 20,42 and updated using the works by Zhong and Bozzelli, 43,44 Wang et al, 45 Oleinikov et al, 46 Ghildina et al, 47 and Vermeire et al 48 on 1,5-hexadiene.…”

Section: Kinetic Modelingmentioning

confidence: 99%

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Experimental and kinetic modeling study of the oxidation of cyclopentane and methylcyclopentane at atmospheric pressure

Dayma

Thion

Serinyel

et al. 2020

Int J of Chemical Kinetics

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Cyclopentane and methylcyclopentane oxidation was investigated in a jet-stirred reactor at atmospheric pressure, over temperatures ranging from 900 to 1250 K, for fuel-lean, stoichiometric, and fuel-rich mixtures at a constant residence time of 70 ms. The initial mole fraction of both fuels was kept constant at 1000 ppm. The reactants were highly diluted by a flow of nitrogen to ensure thermal homogeneity. Samples of the reacting mixture were analyzed online and off-line by Fourier transform infrared spectroscopy and gas chromatography. A detailed kinetic mechanism consisting of 590 species involved in 3469 reactions was developed, and simulation results were compared to these new experimental data and previously reported ignition delays. Reaction pathways analysis as well as sensitivity analyses were performed to get insights into the differences observed during the oxidation process of cyclopentane and methylcyclopentane.

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Section: Methodsmentioning

confidence: 99%

Section: Kinetic Modelingmentioning

confidence: 99%

Experimental and kinetic modeling study of the oxidation of cyclopentane and methylcyclopentane at atmospheric pressure

Dayma

Thion

Serinyel

et al. 2020

Int J of Chemical Kinetics

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“…The importance of 1,3-cyclopentadiene (C5H6) and cyclopentadienyl radical (C5H5) chemistry toward the toluene reactivity is highlighted by Yuan et al [17]. Therefore, C5H6 sub-mechanism was updated according to recent data [18][19][20].…”

Section: Kinetic Modelingmentioning

confidence: 99%

Exploring and Modeling the Chemical Effect of a Cetane Booster Additive in a Low-Octane Gasoline Fuel

Matrat

Amara

et al. 2019

SAE Technical Paper Series

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Recent internal combustion (IC) engine developments focus on gasoline fuel. This requires a better understanding of fuel reactivity at different thermodynamic conditions. Gasoline fuel reactivity control by additives is an efficient method to get better IC engine performances. 2-Ethylhexyl nitrate (EHN) promoting effect (0.1-1% mol.) on combustion has been investigated experimentally and numerically. Rapid compression machine (RCM) experiments were carried out at equivalence ratio 0.5 at 10 bar, from 675 to 995 K. The targeted surrogate fuel is a mixture of toluene and n-heptane in order to capture the additive effect on both cool flame and main ignition. A kinetic model was developed from literature data assembly and validated upon a large set of variations including species profiles and ignition delays of pure compounds as well as mixtures. At the experimental conditions, it was found that the EHN reduces the ignition delay time (IDT) of the surrogate fuel in the whole temperature range. EHN effectiveness tends to be minimum around 705 K and increases with temperature. The results also indicate that EHN effect increases nonlinearly with EHN doping levels. Numerical analyses revealed that the EHN effect is linked to NO2-NO loops, which enhances fuel reactivity. The methodology proposed here enable to simulate the EHN effect with simple compounds rather than the full EHN chemistry set. This strategy could simplify the consideration of additive effect when computational fluid dynamics (CFD) simulations are performed on engine. Finally, the study also highlights the EHN effectiveness on several thermodynamic conditions as well as equivalence ratios. The objective is to assess its performance upon large operating conditions which appears to be of interest with novel combustion systems targeting low temperature as well as lean combustion.

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“…The obtained results testified that in the presence of a six-membered ring, the five-membered moiety is commonly harder to oxidize because the six-membered ring stabilizes the molecule against the destruction processes . In the previous studies, we explored the class of reactions involving the oxidation of a single five-membered ring in the cyclopentadienyl radical with O, O 2 , and OH and the reaction of 2,4-cyclopentadienone C 5 H 4 O with H ,, and then focused on two-ring PAH radicalsreactions of indenyl radical C 9 H 7 with atomic and molecular oxygen and the reaction of the most probable product of the C 9 H 7 + O 2 interaction, 1-H-inden-1-one C 9 H 6 O, with the H atom abundant in the combustion environment. , These reactions were examined by means of ab initio/Rice–Ramsperger–Kassel–Marcus Master equation (RRKM-ME) − calculations. For example, the results for the C 5 H 4 O + H reaction and its analogous reaction C 9 H 6 O + H have shown that under typical combustion conditions, the rate constant for C 9 H 6 O + H → C 8 H 7 + CO is about a factor of 4 lower than that for C 5 H 4 O + H → C 4 H 5 + CO, due to higher barriers for the C–C cleavages (β-scissions) in the five-membered ring when it is attached to a six-membered ring.…”

Section: Introductionmentioning

confidence: 99%

“…In the previous studies, we explored the class of reactions involving the oxidation of a single five-membered ring in the cyclopentadienyl radical with O, O 2 , and OH and the reaction of 2,4-cyclopentadienone C 5 H 4 O with H ,, and then focused on two-ring PAH radicalsreactions of indenyl radical C 9 H 7 with atomic and molecular oxygen and the reaction of the most probable product of the C 9 H 7 + O 2 interaction, 1-H-inden-1-one C 9 H 6 O, with the H atom abundant in the combustion environment. , These reactions were examined by means of ab initio/Rice–Ramsperger–Kassel–Marcus Master equation (RRKM-ME) − calculations. For example, the results for the C 5 H 4 O + H reaction and its analogous reaction C 9 H 6 O + H have shown that under typical combustion conditions, the rate constant for C 9 H 6 O + H → C 8 H 7 + CO is about a factor of 4 lower than that for C 5 H 4 O + H → C 4 H 5 + CO, due to higher barriers for the C–C cleavages (β-scissions) in the five-membered ring when it is attached to a six-membered ring. The entrance barriers for C 9 H 6 O + H → C 8 H 7 + CO are only slightly higher than those for C 5 H 4 O + H, and the lower rate constants for the former reaction are also due to the subsequent pathways on the C 9 H 7 O PES and higher energy of the C 9 H 7 O intermediates involved, in comparison with the C 5 H 5 O isomers. , …”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Mechanism and Kinetics of the Oxidation of Cyclopenta[a]Naphthalenyl Radical C₁₃H₉ with Molecular Oxygen

et al. 2021

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Electronic structure/Rice−Ramsperger−Kassel−Marcus Master equation calculations were applied to unravel the oxidation mechanism and kinetics of the cyclopenta[a]naphthalenyl radical with molecular oxygen. The reaction has been shown to proceed through the addition of O 2 in the orthoposition in the five-membered ring of C 13 H 9 . At low temperatures, the reaction yields a collisionally stabilized C 13 H 9 O 2 complex, which rapidly decomposes back to the reactants. In the high-temperature regime, above 800, 900, 1125, and 1375 K at pressures of 0.03, 1, 10, and 100 atm, respectively, the reaction forms bimolecular products including 3H-/1Hcyclopenta[a]naphthalen-3-one + OH as the prevailing product together with 1-ethanol-substituted 2-naphthyl radical + CO and 3H-benzo[f ]chromen-3-one + H as minor ones, with the branching ratio of the OH elimination channel growing with temperature and the rate constants for the individual bimolecular channels being independent of pressure. The calculated rate constants and product branching for cyclopenta[a]naphthalenyl + O 2 closely agree with those reported earlier for the indenyl + O 2 reaction and are recommended for the combustion kinetic models for the oxidation reactions of five-membered rings on free edges of larger polycyclic aromatic hydrocarbon molecules. The results also confirm that the oxidation of a π radical located on a five-membered ring with molecular oxygen is very slow.

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Reaction mechanism, rate constants, and product yields for unimolecular and H-assisted decomposition of 2,4-cyclopentadienone and oxidation of cyclopentadienyl with atomic oxygen

Cited by 36 publications

References 58 publications

Experimental and kinetic modeling study of the oxidation of cyclopentane and methylcyclopentane at atmospheric pressure

Experimental and kinetic modeling study of the oxidation of cyclopentane and methylcyclopentane at atmospheric pressure

Exploring and Modeling the Chemical Effect of a Cetane Booster Additive in a Low-Octane Gasoline Fuel

Theoretical Study of the Mechanism and Kinetics of the Oxidation of Cyclopenta[a]Naphthalenyl Radical C₁₃H₉ with Molecular Oxygen

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Reaction mechanism, rate constants, and product yields for unimolecular and H-assisted decomposition of 2,4-cyclopentadienone and oxidation of cyclopentadienyl with atomic oxygen

Cited by 36 publications

References 58 publications

Experimental and kinetic modeling study of the oxidation of cyclopentane and methylcyclopentane at atmospheric pressure

Experimental and kinetic modeling study of the oxidation of cyclopentane and methylcyclopentane at atmospheric pressure

Exploring and Modeling the Chemical Effect of a Cetane Booster Additive in a Low-Octane Gasoline Fuel

Theoretical Study of the Mechanism and Kinetics of the Oxidation of Cyclopenta[a]Naphthalenyl Radical C13H9 with Molecular Oxygen

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Theoretical Study of the Mechanism and Kinetics of the Oxidation of Cyclopenta[a]Naphthalenyl Radical C₁₃H₉ with Molecular Oxygen