Kinetics of the reaction between vinyl radical and ethylene

Shestov, Alexander A.; Попов, К. В.; Slagle, Irene R.; Knyazev, Vadim D.

doi:10.1016/j.cplett.2005.04.057

Cited by 12 publications

(29 citation statements)

References 20 publications

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“…Comparison between theoretical and experimental rate coefficients for C 2 H 4 + Ċ 2 H 3 → products. (Theoretical study in literature: Huang et al; Experiments: black ■ and red ● Ismail et al, blue ▲ Shestov et al, magenta ▼ Fahr et al)…”

Section: Resultsmentioning

confidence: 99%

“…Shestov et al investigated the bimolecular reaction C 2 H 4 + Ċ 2 H 3 using the laser photolysis/photoionization mass spectrometry technique in the temperature range of 625–950 K and bath gas (helium) densities of (6–12) × 10 16 atom cm –3 . C 4 H 6 and Ċ 4 H 7 were detected as the primary products, and the thermal stability of the Ċ 4 H 7 radical at 950 K indicated that it is a delocalized radical.…”

Section: Introductionmentioning

confidence: 99%

“…Their calculations indicate that the transformation from i-C ̇4H 7 to the straight-chain C ̇4H 7 radical is kinetically unfavorable due to the high strain energy of the three-membered ring structure in the transition state. Shestov et al 12 investigated the bimolecular reaction C 2 H 4 + C ̇2H 3 using the laser photolysis/photoionization mass spectrometry technique in the temperature range of 625−950 K and bath gas (helium) densities of (6−12) × 10 16 atom cm −3 . C 4 H 6 and C ̇4H 7 were detected as the primary products, and the thermal stability of the C ̇4H 7 radical at 950 K indicated that it is a delocalized radical.…”

Section: Introductionmentioning

confidence: 99%

“…Comparison between theoretical and experimental rate coefficients for C2H4 + Ċ2H3 → products. (Experiments: Fahr et al63 , Shestov et al12 , Ismail et al13 )…”

mentioning

confidence: 99%

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Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ₄H₇ Potential Energy Surface

Klippenstein

Zhou

et al. 2017

J. Phys. Chem. A

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The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of polyunsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution toward soot formation. On the basis of our previous work on propene and the butene isomers (1-, 2-, and isobutene), it was found that the reaction kinetics of Ḣ-atom addition to the C═C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations, and flame speed measurements. In this study, the rate constants and thermodynamic properties for Ḣ-atom addition to 1,3-butadiene and related reactions on the ĊH potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero-point energies, single-point energies, rate constants, barrier heights, and thermochemistry are systematically compared among the two quantum chemical methods. 1-Methylallyl (ĊH1-3) and 3-buten-1-yl (ĊH1-4) radicals and CH + ĊH are found to be the most important channels and reactivity-promoting products, respectively. We calculated that terminal addition is dominant (>80%) compared to internal Ḣ-atom addition at all temperatures in the range 298-2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction CH + Ḣ → products and CH + ĊH → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C species, the calculated thermochemical values are also in good agreement with literature data. In addition, the rate constants for H atom abstraction by Ḣ atoms have also been calculated, and it is found that abstraction from the central carbon atoms is the dominant channel (>70%) at temperatures in the range of 298-2000 K. Finally, by incorporating our calculated rate constants for both Ḣ atom addition and abstraction into our recently developed 1,3-butadiene model, we show that laminar flame speed predictions are significantly improved, emphasizing the value of this study.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Comparison between theoretical and experimental rate coefficients for C2H4 + Ċ2H3 → products. (Experiments: Fahr et al63 , Shestov et al12 , Ismail et al13 )…”

mentioning

confidence: 99%

See 2 more Smart Citations

Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ₄H₇ Potential Energy Surface

Klippenstein

Zhou

et al. 2017

J. Phys. Chem. A

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“…While a number of these parameters have been derived from experiment, [20][21][22][23] supplementation with ab initio studies has also proven invaluable. [24][25][26][27] Given the fundamental similarities between silicate and hydrocarbon polymerization, aspects of the methodology employed by the combustion community may potentially be applied to silicate systems.…”

Section: Introductionmentioning

confidence: 99%

A theoretical kinetic model of the temperature and pH dependent dimerization of orthosilicic acid in aqueous solution

McIntosh

2012

Phys. Chem. Chem. Phys.

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The first steps in a pH- and temperature-dependent theoretical kinetic model of silicate polymerization and dissolution are examined in this work with a combined ab initio and transition state theory based study of the dimerization of H(4)SiO(4). The role of solvation has been of primary concern in this work, and its influence on theoretical activation energies and pre-exponential factors has been thoroughly benchmarked. Relatively inexpensive MP2/6-31+G(d)//HF/6-31+G(d) calculations of octahydrate clusters, with conductor-like polarizable continuum model corrections obtained in the MP2-level single-point calculations, have been shown to lead to a good description of the limited experimentally determined energetics of dimerization for most elementary reactions. Pre-exponential factors computed from this level of theory are found to be relatively insensitive to the level of theory utilized for geometry optimizations, the number of explicit waters, hindered rotor corrections, and variational effects arising from the minimization of rate constants. Within this framework, a kinetic model of the chemistry of H(4)SiO(4) and H(3)SiO(4)(-), forming H(6)Si(2)O(7) and H(5)Si(2)O(7)(-), has been compiled. Numerical simulations over pH = 3-12 show that a number of pH- and temperature dependent trends in reaction rates and positions of equilibrium are well described with this simple dimerization model. More specifically to the dimerization process, we obtain dimerization constants, log K(dim), of 1.85 and -7.15 for the formation of H(6)Si(2)O(7) and H(5)Si(2)O(7)(-) respectively, which compare well with experimentally determined values of 1.2 and -8.5, respectively.

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Chemical mechanism for high temperature combustion of engine relevant fuels with emphasis on soot precursors

Blanquart

Pepiot-Desjardins

Pitsch

2009

Combustion and Flame

430

306

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Kinetics of the reaction between vinyl radical and ethylene

Cited by 12 publications

References 20 publications

Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ₄H₇ Potential Energy Surface

Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ₄H₇ Potential Energy Surface

A theoretical kinetic model of the temperature and pH dependent dimerization of orthosilicic acid in aqueous solution

Chemical mechanism for high temperature combustion of engine relevant fuels with emphasis on soot precursors

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Kinetics of the reaction between vinyl radical and ethylene

Cited by 12 publications

References 20 publications

Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ4H7 Potential Energy Surface

Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ4H7 Potential Energy Surface

A theoretical kinetic model of the temperature and pH dependent dimerization of orthosilicic acid in aqueous solution

Chemical mechanism for high temperature combustion of engine relevant fuels with emphasis on soot precursors

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Product

Resources

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Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ₄H₇ Potential Energy Surface

Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ₄H₇ Potential Energy Surface