BSBL‐Rechnungen zu Wasserstoffabspaltungsreaktionen (durch Alkenylradikale; Vinylradikale

Scherzer, K.; Löser, Uwe; Stiller, W.

doi:10.1002/zfch.19870270815

Cited by 12 publications

(5 citation statements)

References 8 publications

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“…In addition, rate constants of the C 2 H 3 + C 2 H 6 →C 2 H 4 + C 2 H 5 reaction were derived from fitting to a complex mechanism. Stiller et al estimated this rate with BEBO method for temperatures 480, 500, and 520 K. Rate constants suggested from a review by Tsang and Hampson, in the high temperature regime ( T > 1000 K), agree well with the most recent theoretical calculations presented by Liu et al These authors calculated thermal rate constants using the canonical variational TS theory (CVT) and the small-curvature tunneling correction (SCT). The energetic data were obtained at the G2 level of theory together with the gradient and Hessian information at QCISD(T)/6-31+G(d).…”

Section: Resultsmentioning

confidence: 57%

“…The literature data available come from either BEBO calculations or extensive literature review . Figure a,b shows the predicted rate constant of reactions R 2 and R 3 using the RC-TST method and from literature data. , In this figure, the “RC-TST LER” notation means that the reaction class factors were calculated with the approximate expressions listed in Table . Because there are not big differences between the results obtained from either using the BH&HLYP/cc-pVDZ or AM1 reaction energies, only rate constants from BH&HLYP are presented here.…”

Section: Resultsmentioning

confidence: 99%

“…It is noted that there is no direct experimental data available for these reactions. The literature data available come from either BEBO calculations or extensive literature review . Figure a,b shows the predicted rate constant of reactions R 2 and R 3 using the RC-TST method and from literature data. , In this figure, the “RC-TST LER” notation means that the reaction class factors were calculated with the approximate expressions listed in Table .…”

Section: Resultsmentioning

confidence: 99%

“…It is noted that there is no direct experimental data available for these reactions. The literature data available come from either BEBO calculations 25 or extensive literature review. 26 Figure 7a,b shows the predicted rate constant of reactions R 2 and R 3 using the RC-TST method and from literature data.…”

Section: Prediction Of Ratementioning

confidence: 99%

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Kinetics of the Hydrogen Abstraction C₂H₃^• + Alkane → C₂H₄ + Alkyl Radical Reaction Class

et al. 2009

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This paper presents an application of the reaction class transition state theory (RC-TST) to predict thermal rate constants for hydrogen abstraction reactions of the type C(2)H(3) + alkane --> C(2)H(4) + alkyl radical. The linear energy relationship (LER) was proven to hold for both noncyclic and cyclic hydrocarbons. We have derived all parameters for the RC-TST method from rate constants of 19 representative reactions, coupling with LER and the barrier height grouping (BHG) approach. Both the RC-TST/LER, where only reaction energy is needed, and the RC-TST/BHG, where no other information is needed, can predict rate constants for any reaction in this reaction class with satisfactory accuracy for combustion modeling. Our analysis indicates that less than 90% systematic errors on the average exist in the predicted rate constants using the RC-TST/LER or RC-TST/BHG method, while in comparison to explicit rate calculations, the differences are within a factor of 2 on the average.

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Section: Resultsmentioning

confidence: 57%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Prediction Of Ratementioning

confidence: 99%

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Kinetics of the Hydrogen Abstraction C₂H₃^• + Alkane → C₂H₄ + Alkyl Radical Reaction Class

et al. 2009

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“…Rate constants for H-atom abstraction from cyclohexane by R = H, • CH 3 , • C 2 H 3 , • C 3 H 5 , and • C 2 H 5 radicals: (i) R = H, present work; (ii) R = • CH 3 , estimated; (vi) R = • C 2 H 3 , estimated; (vii) R = • C 2 H 5 , estimated; (viii) R = • C 3 H 5 , estimated …”

Section: Resultsmentioning

confidence: 92%

Shock Tube and Theory Investigation of Cyclohexane and 1-Hexene Decomposition

et al. 2009

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The decomposition of cyclohexane (c-C(6)H(12)) was studied in a shock tube using the laser-schlieren technique over the temperature range 1300-2000 K and for 25-200 Torr in mixtures of 2%, 4%, 10%, and 20% cyclohexane in Kr. Vibrational relaxation of the cyclohexane was also examined in 10 experiments covering 1100-1600 K for pressures below 20 Torr, and relaxation was found to be too fast to allow resolution of incubation times. The dissociation of 1-hexene (1- C(6)H(12)), apparently the sole initial product of cyclohexane decomposition, was also studied over 1220-1700 K for 50 and 200 Torr using 2% and 3% 1-hexene in Kr. On heating, cyclohexane simply isomerizes to 1-hexene, and this then dissociates almost entirely by a more rapid C-C scission to allyl and n-propyl radicals. This two-step reaction results in an initial small density gradient from the slight endothermicity of the isomerization. The gradient then rises strongly as the product 1-hexene dissociates. For the lower temperatures, this behavior is fully resolved here. For the higher pressures, 1-hexene decomposition generates negative gradients (exothermic reaction) as the radicals formed begin to recombine. Cyclohexane also generates such gradients, but these are now much smaller because the radical pool is depleted by abstraction from the reactant. A complete mechanism for the 1-hexene decomposition and for that of cyclohexane involving 79 reactions and 30 species is used in the final modeling of the gradients. Rate constants and RRKM fit parameters for the initial reactions are provided for the entire range of conditions. The possibility of direct reaction to allyl and n-propyl radicals, without stabilization of the intermediate 1-hexene, is examined down to pressures as low as 25 Torr, without a clear resolution of the issue. High-pressure limit rate constants from RRKM extrapolation are k(infinity)(c-C(6)H(12) --> 1-C(6)H(12)) = (8.76 x 10(17)) exp((-91.94 kcal/mol)/RT) s(-1) (T = 1300-2000 K) and k(infinity)(1-C(6)H(12) --> (*)C(3)H(7) + (*)C(3)H(5)) = (1.46 x 10(16)) exp((-69.12 kcal/mol)/RT) s(-1) (T = 1200-1700 K). This high-pressure rate for cyclohexane is entirely consistent with the notion that the isomerization involves initial C-C fission to a diradical. These extrapolated high-pressure rates are in good agreement with much of the literature.

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Experimental and modeling study of the oxidation of 1‐butyne and 2‐butyne

Belmekki

Glaude

Costa

et al. 2002

Int J of Chemical Kinetics

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Ignition delays were measured behind shock waves in the cases of hydrocarbonoxygen-argon mixtures containing 1-butyne or 2-butyne (1 or 2% of hydrocarbons for equivalence ratios from 0.5 to 2). Reflected shock waves permitted to obtain temperatures from 1100 to 1600 K and pressures from 6.3 to 9.1 atm.A detailed mechanism of the reactions of 1-butyne and 2-butyne has been explained in the line of the mechanism developed previously for the reaction of C 3 -C 4 unsaturated hydrocarbons (propyne, allene, 1,3-butadiene) [Int J Chem Kin 1999, 31, 361]. It is based on the most recent kinetic data values published in the literature and is consistent with thermochemistry.This mechanism has been validated by comparing the results of our simulations to the experimental results obtained for ignition delays in our shock tube and to measurements of species obtained during thermal decomposition [Int

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BSBL‐Rechnungen zu Wasserstoffabspaltungsreaktionen (durch Alkenylradikale; Vinylradikale

Cited by 12 publications

References 8 publications

Kinetics of the Hydrogen Abstraction C₂H₃^• + Alkane → C₂H₄ + Alkyl Radical Reaction Class

Kinetics of the Hydrogen Abstraction C₂H₃^• + Alkane → C₂H₄ + Alkyl Radical Reaction Class

Shock Tube and Theory Investigation of Cyclohexane and 1-Hexene Decomposition

Experimental and modeling study of the oxidation of 1‐butyne and 2‐butyne

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BSBL‐Rechnungen zu Wasserstoffabspaltungsreaktionen (durch Alkenylradikale; Vinylradikale

Cited by 12 publications

References 8 publications

Kinetics of the Hydrogen Abstraction C2H3• + Alkane → C2H4 + Alkyl Radical Reaction Class

Kinetics of the Hydrogen Abstraction C2H3• + Alkane → C2H4 + Alkyl Radical Reaction Class

Shock Tube and Theory Investigation of Cyclohexane and 1-Hexene Decomposition

Experimental and modeling study of the oxidation of 1‐butyne and 2‐butyne

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Product

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Kinetics of the Hydrogen Abstraction C₂H₃^• + Alkane → C₂H₄ + Alkyl Radical Reaction Class

Kinetics of the Hydrogen Abstraction C₂H₃^• + Alkane → C₂H₄ + Alkyl Radical Reaction Class