Kinetics of the Reaction of OH Radicals with CH<sub>2</sub>CO

Oehlers, C.; Temps, F.; Wagner, H. Gg.; Wolf, Maarten G.

doi:10.1002/bbpc.19920960211

Cited by 31 publications

(20 citation statements)

References 14 publications

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“…The reactions with other radicals have been investigated to a lesser extent. For the hydroxyl radical, OH, some of the experimental results do not fully agree with the theoretical study as discussed recently . Similarly, limited experimental data and theoretical calculations are available for the reactions with oxygen atom O.…”

Section: Introductionmentioning

confidence: 79%

Mechanism and Rate Constants of the CH₃+ CH₂CO Reaction: A Theoretical Study

Semenikhin

Shubina

Savchenkova

et al. 2018

Int J of Chemical Kinetics

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The mechanism of the reaction of ketene with methyl radical has been studied by ab initio CCSD(T)‐F12/cc‐pVQZ‐f12//B2PLYPD3/6‐311G** calculations of the potential energy surface. Temperature‐ and pressure‐dependent reaction rate constants have been computed using the Rice–Ramsperger–Kassel–Marcus (RRKM)–Master Equation and transition state theory methods. Three main channels have been shown to dominate the reaction; the formation of the collisionally stabilized CH3COCH2 radical and the production of the C2H5 + CO and HCCO + CH4 bimolecular products. Relative contributions of the CH3COCH2, C2H5 + CO, and HCCO + CH4 channels strongly depend on the reaction conditions; the formation of thermalized CH3COCH2 is favored at low temperatures and high pressures, HCCO + CH4 is dominant at high temperatures, whereas the yield of C2H5 + CO peaks at intermediate temperatures around 1000 K. The C2H5 + CO channel is favored by a decrease in pressure but remains the second most important reaction pathway after HCCO + CH4 under typical flame conditions. The calculated rate constants at different pressures are proposed for kinetic modeling of ketene reactions in combustion in the form of modified Arrhenius expressions. Only rate constant to form CH3COCH2 depends on pressure, whereas those to produce C2H5 + CO and HCCO + CH4 appeared to be pressure independent.

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Section: Introductionmentioning

confidence: 79%

Mechanism and Rate Constants of the CH₃+ CH₂CO Reaction: A Theoretical Study

Semenikhin

Shubina

Savchenkova

et al. 2018

Int J of Chemical Kinetics

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“…In the atmosphere, the photodegradation of ketenes and the reaction of active radicals are significant homogeneous degradation processes. Recently, the simplest ketene (CH 2 CO) with CH 2, [ 1 ] NCO, [ 2 ] NCS, [ 2 ] O, [ 3–5 ] Cl, [ 6–9 ] F, [ 10,11 ] H, [ 12–14 ] O 3, [ 15 ] OH, [ 10,16,17 ] CH 3 , [ 18 ] and CN [ 19 ] has been widespread investigated. However, the experimental research of the CH 3 CHCO and (CH 3 ) 2 CCO with H reactions are extremely rare.…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigations on mechanisms and kinetics of methylketene with H reaction in the atmosphere

Sun

et al. 2021

J of Physical Organic Chem

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Detailed oxidation course of H‐initiated degradation of CH3CHCO has been researched taking advantage of quantum chemical methods. Geometrical optimizations of reactants, intermediates, transition states, and products were operated at the B3LYP/6‐31++G(d,p) level. Single‐point energy computations were implemented at the CCSD(T)/cc‐pVTZ//B3LYP/6‐311++G(d,p) level. The results state clearly that the H association was more energetically beneficial than the abstraction of H, and the dominant pathway is generation of P1 (CH3CH2 + CO). Rate constants of H association reactions are computed by making use of Rice–Ramsperger–Kassel–Marcus (RRKM) program at 200–3000 K. Specifically, the total rate constant of H association reactions is 6.47 × 10−13 cm3 molecule−1 s−1 at 298 K, which is consistent with the experimental results (6.58 × 10−13 cm3 molecule−1 s−1). This research offers a thorough comprehending of the reaction mechanism involved in H‐initiated atmospheric degradation of CH3CHCO and might act as a relevant supplemental reference criteria for experimental research.

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“…Hence, methylketene is a major by-product in the procedure of hydrocarbon oxidation. Up to now, several experimental and theoretical information for ketene reaction with CH 2 [1], NCO [2], NCS [2], O [3][4][5], Cl [6][7][8][9], F [10,11], H [12][13][14], O3 [15], OH [10,16,17], CH 3 [18], and CN [19] has been researched widely. However, the reaction of methylketene is rare, and only one experiment has researched the ketene, methylketene, and dimethylketene with O( 3 P) atom reaction.…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigations on mechanisms and kinetics of methylketene with O(3P) reaction in the atmosphere

et al. 2021

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The O( 3 P)-initiated conversion mechanism and dynamics of CH 3 CHCO were researched in atmosphere by executing density functional theory (DFT) computations. Optimizations of all the species and single-point energy computations were implemented at the B3LYP/6-311++G(d,p) and CCSD(T)/cc-pVTZ level, respectively. The explicit oxidation mechanism was introduced and discussed. The results state clearly that the O( 3 P) association was more energetically beneficial than the abstraction of H. The rate coefficients over the probable temperature range of 200-3000 K were forecasted by implementing Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Specifically, the total rate coefficient of O( 3 P) association reactions is 1.19 × 10 −11 cm 3 molecule −1 s −1 at 298 K, which is consistent with the experimental results (1.16 × 10 −11 cm 3 molecule −1 s −1 ). The rate coefficients for the O( 3 P) with CH 2 CO, CH 3 CHCO, and (CH 3 ) 2 CCO suggest that rate coefficient of ketene derivatives increase with the increase of methylation degree.

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Kinetics of the Reaction of OH Radicals with CH₂CO

Cited by 31 publications

References 14 publications

Mechanism and Rate Constants of the CH₃+ CH₂CO Reaction: A Theoretical Study

Mechanism and Rate Constants of the CH₃+ CH₂CO Reaction: A Theoretical Study

Theoretical investigations on mechanisms and kinetics of methylketene with H reaction in the atmosphere

Theoretical investigations on mechanisms and kinetics of methylketene with O(3P) reaction in the atmosphere

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Kinetics of the Reaction of OH Radicals with CH2CO

Cited by 31 publications

References 14 publications

Mechanism and Rate Constants of the CH3+ CH2CO Reaction: A Theoretical Study

Mechanism and Rate Constants of the CH3+ CH2CO Reaction: A Theoretical Study

Theoretical investigations on mechanisms and kinetics of methylketene with H reaction in the atmosphere

Theoretical investigations on mechanisms and kinetics of methylketene with O(3P) reaction in the atmosphere

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Kinetics of the Reaction of OH Radicals with CH₂CO

Mechanism and Rate Constants of the CH₃+ CH₂CO Reaction: A Theoretical Study

Mechanism and Rate Constants of the CH₃+ CH₂CO Reaction: A Theoretical Study