Kinetics of the reaction of vinyl radicals with NO: Ab initio theory, master equation predictions, and laser absorption measurements

Striebel, Frank; Jusinski, Leonard E.; Fahr, Askar; Halpern, Joshua B.; Klippenstein, Stephen J.; Taatjes, Craig A.

doi:10.1039/b401163e

Cited by 23 publications

(35 citation statements)

References 39 publications

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“…The key reactions involving NO are C 2 H 3 + NO (R7) and CHCHOH + NO (R8), both forming HCN. Reaction R7 was studied experimentally and theoretically by Stribel et al [35] ; the rate constant for CHCHOH + NO (R8) is assumed to be similar to k 7 .…”

Section: Detailed Kinetic Modelmentioning

confidence: 99%

The C2H2 + NO2 reaction: Implications for high pressure oxidation of C2H2/NOx mixtures

Marshall,

Leung,

Gimenez-Lopez

et al. 2019

Proceedings of the Combustion Institute

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The reaction of C 2 H 2 with NO 2 has been studied theoretically. It is a complex overall reaction with multiple wells and multiple product channels. The calculated rate constant for the preferred channel, formation of a CHOCHON adduct, is compatible with the only experimental determination. The CHOCHON adduct is assumed to dissociate rapidly to form the triplet carbene CHCHO and NO. An experimental and kinetic modeling study of the interaction between C 2 H 2 , O 2 and NO x was performed under flow reactor conditions in the intermediate temperature range (600-900 K), high pressure (50-60 bar), and for stoichiometries ranging from reducing to strongly oxidizing. The results show that presence of NO x serves both to sensitize and inhibit oxidation of C 2 H 2. Calculations with a detailed chemical kinetic model, partly established in the present work, confirm that C 2 H 2 + NO 2 is the major initiation step, as well as the major sensitizing reaction. This reaction converts NO 2 to NO, which is then partly converted to HCN by reaction with C 2 H 3 and CHCHOH. The latter reactions are both chain terminating and serve as the major inhibiting steps.

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Section: Detailed Kinetic Modelmentioning

confidence: 99%

The C2H2 + NO2 reaction: Implications for high pressure oxidation of C2H2/NOx mixtures

Marshall,

Leung,

Gimenez-Lopez

et al. 2019

Proceedings of the Combustion Institute

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“…The barrier to form HCN + CH 2 O is about 37 kcal/mol [25], 15 kcal/mol less than the barrier to C 2 H 3 + NO. In the present work we have assumed that HCN + CH 2 O is the sole product of the C 2 H 3 + NO reaction, adopting the estimated high pressure limit at 700 K from Striebel et al [17]. Studies of the C 2 H 3 +NO 2 reaction are scarce in literature.…”

Section: Chemical Kinetic Modelmentioning

confidence: 99%

“…However, our calculated heat of The subset involving reactions between the vinyl radical and nitrogen oxides warrants particular attention in the present work. There are a number of studies on the C 2 H 3 + NO reaction [17,[25][26][27][28][29]; several of them focusing on the inhibiting role of NO in the pyrolysis of acetylene [26][27][28]. Recent experimental and theoretical results [17,25] indicate that HCN + CH 2 O (R4) is the only significant product channel near room temperature and at low pressure.…”

Section: Chemical Kinetic Modelmentioning

confidence: 99%

High pressure oxidation of C2H4/NO mixtures

Giménez-López

Alzueta

Rasmussen

et al. 2011

Proceedings of the Combustion Institute

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An experimental and kinetic modeling study of the interaction between C 2 H 4 and NO has been performed under flow reactor conditions in the intermediate temperature range (600-900 K), high pressure (60 bar), and for stoichiometries ranging from reducing to oxidizing conditions. The main reaction pathways of the C 2 H 4 /O 2 /NO x conversion, the capacity of C 2 H 4 to remove NO, and the influence of the presence of NO x on the C 2 H 4 oxidation are analyzed. Compared to the C 2 H 4 /O 2 system, the presence of NO x shifts the onset of reaction 75-150 K to lower temperatures. The mechanism of sensitization involves the reaction HOCH 2 CH 2 OO + NO → CH 2 OH + CH 2 O + NO 2 , which pushes a complex system of partial equilibria towards products. This is a confirmation of the findings of Doughty et al. [Proc. Combust. Inst. 26 (1996) 589-596] for a similar system at atmospheric pressure. Under reducing conditions and temperatures above 700 K, a significant fraction of the NO x is removed. This removal is partly explained by the reaction C 2 H 3 + NO → HCN + CH 2 O. However, a second removal mechanism is active in the 700-850 K range, which is not captured by the chemical kinetic model. With the present thermochemistry and kinetics, neither formation of nitro-hydrocarbons

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“…been performed in a variety of light-and heavy-duty vehicles and engines [6][7][8][9]. The vinyl radical (C 2 H 3 ) is a key intermediate in the combustion reactions of large hydrocarbon molecules and can react with atoms, radicals, and molecules such as H 2 , C 2 H 2 , CH 3 ,CO, O 2 , NO, O, HCHO, and so forth [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25]. In the diesel engines with diesel/methanol dual fuel [26,27], methanol is injected into the intake manifold to form homogeneous mixture with air in the cylinder, whereas diesel is directly injected into the cylinder.…”

Section: Introductionmentioning

confidence: 99%

“…Detailed and skeletal reaction mechanisms for methanol conversion have been proposed based on flow reactor and shock tube data , and different experimental studies concerning methanol/hydrocarbon blends have been performed in a variety of light‐ and heavy‐duty vehicles and engines . The vinyl radical (C 2 H 3 ) is a key intermediate in the combustion reactions of large hydrocarbon molecules and can react with atoms, radicals, and molecules such as H 2 , C 2 H 2 , CH 3 ,CO, O 2 , NO, O, HCHO, and so forth . In the diesel engines with diesel/methanol dual fuel , methanol is injected into the intake manifold to form homogeneous mixture with air in the cylinder, whereas diesel is directly injected into the cylinder.…”

Section: Introductionmentioning

confidence: 99%

A Computational Study of the Kinetics and Mechanism for the C₂H₃+ CH₃OH Reaction

Chen

Song

Chen

et al. 2015

Int. J. Chem. Kinet.

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The mechanism for the C 2 H 3 + CH 3 OH reaction has been investigated by the Gaussian-4 (G4) method based on the geometric parameters of the stationary points optimized at the B3LYP/6-31G(2df, p) level of theory. Four transition states have been identified for the production of C 2 H 4 + CH 3 O (TSR/P1), C 2 H 4 + CH 2 OH (TSR/P2), C 2 H 3 OH + CH 3 (TSR/P3), and C 2 H 3 OCH 3 + H (TSR/P4) with the corresponding barriers 8.48, 9.25, 37.62, and 34.95 kcal/mol at the G4 level of theory, respectively. The rate constants and branching ratios for the two lower energy H-abstraction reactions were calculated using canonical variational transition state theory with the Eckart tunneling correction at the temperature range 300-2500 K. The predicted rate constants have been compared with existing literature data, and the uncertainty has been discussed. The branching ratio calculation suggests that the channel producing CH 3 O is dominant up to about 1070 K, above which the channel producing CH 2 OH becomes very competitive. C 2015 Wiley Periodicals, Inc. Int J Chem Kinet 47: [764][765][766][767][768][769][770][771][772] 2015

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Kinetics of the reaction of vinyl radicals with NO: Ab initio theory, master equation predictions, and laser absorption measurements

Cited by 23 publications

References 39 publications

The C2H2 + NO2 reaction: Implications for high pressure oxidation of C2H2/NOx mixtures

The C2H2 + NO2 reaction: Implications for high pressure oxidation of C2H2/NOx mixtures

High pressure oxidation of C2H4/NO mixtures

A Computational Study of the Kinetics and Mechanism for the C₂H₃+ CH₃OH Reaction

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Kinetics of the reaction of vinyl radicals with NO: Ab initio theory, master equation predictions, and laser absorption measurements

Cited by 23 publications

References 39 publications

The C2H2 + NO2 reaction: Implications for high pressure oxidation of C2H2/NOx mixtures

The C2H2 + NO2 reaction: Implications for high pressure oxidation of C2H2/NOx mixtures

High pressure oxidation of C2H4/NO mixtures

A Computational Study of the Kinetics and Mechanism for the C2H3+ CH3OH Reaction

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A Computational Study of the Kinetics and Mechanism for the C₂H₃+ CH₃OH Reaction