Microcanonical Correlation Analysis of Collisional Energy Transfer Efficiencies in Unimolecular Reactions

The recombination of c-C 5 H 5 with H-atoms has been studied behind reflected shock waves. The obtained rate coefficients are almost independent of temperature and were found to be k rec = 2.6 × 10 14 cm 3 mol −1 s −1 for pressures around 2 bar in the temperature range between 1150 and 1500 K. Together with rate coefficients for the dissociation, obtained in an earlier work (Roy et al., Proc Combust Inst 1998, 27, 329-336) at pressures and temperatures close to those applied in the present work, we calculated equilibrium constants K c (T) for C 5 H 6 c-C 5 H 5 + H. A "third law" analysis was performed. Data for the enthalpy of formation of cyclopentadienyl DH f,0 = 65.4 ± 1 kcal mol −1 and DH f,298 = 62.5 ± 1 kcal mol −1 were derived, respectively. The analysis was based upon new results on the entropy of cyclopentadienyl, recently calculated by Kiefer et al. (J phy chem, in press). Finally, our measured data were subjected to a fall-off analysis. The simulation turned out very satisfactorily.

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Section: Modeling Of the Fall-offmentioning

confidence: 99%

Kinetics of the cyclopentadiene decay and the recombination of cyclopentadienyl radicals with H‐atoms: Enthalpy of formation of the cyclopentadienyl radical

Roy¹,

Braun‐Unkhoff²,

Frank³

et al. 2001

Int J of Chemical Kinetics

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“…For noble gases as main collision partners, numbers for large molecules are reported to lie in the range between 50 and 200 cm −1 (see e.g. [38,42]). We tried to find a set of numbers for k ∞ rec and − E (0) all , which could be used to reproduce the results of both groups.…”

Section: Modeling Of the Fall-offmentioning

confidence: 99%

Erratum: “Kinetics of the cyclopentadiene decay and the recombination of cyclopentadienyl radicals with H‐atoms: Enthalpy of formation of the cyclopentadienyl radical”, Int J Chem Kinet 2001, 33, 821

Roy¹,

Braun‐Unkhoff²,

Frank³

et al. 2002

Int J of Chemical Kinetics

View full text Add to dashboard Cite

The recombination of c-C 5 H 5 with H-atoms has been studied behind reflected shock waves. The obtained rate coefficients are almost independent of temperature and were found to be k rec = 2.6 × 10 14 cm 3 mol −1 s −1 for pressures around 2 bar in the temperature range between 1150 and 1500 K. Together with rate coefficients for the dissociation, obtained in an earlier work (Roy et al., Proc Combust Inst 1998, 27, 329-336) at pressures and temperatures close to those applied in the present work, we calculated equilibrium constants K c (T) for C 5 H 6 c-C 5 H 5 + H. A "third law" analysis was performed. Data for the enthalpy of formation of cyclopentadienyl DH f,0 = 65.4 ± 1 kcal mol −1 and DH f,298 = 62.5 ± 1 kcal mol −1 were derived, respectively. The analysis was based upon new results on the entropy of cyclopentadienyl, recently calculated by Kiefer et al. (Phys Chem, in press). Finally, our measured data were subjected to a fall-off analysis. The simulation turned out very satisfactorily.

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“…In RRKM calculations, a step size of 0.4 kJ mol −1 (ΔE + ) was used to calculate the available energy for the activated complexes, and the external rotations were treated as adiabatic. N 2 was chosen as bath gas with a value of 0.5 for the collision [99]. To calculate the sums and densities of states, the semiclassical technique of Tardy, Whitten, and Rabinovitch [100], as implemented in the RRKM program, was used, in which the effective number of oscillators was adjusted as a function of the internal energy at each point along the reaction coordinate.…”

Section: Rrkm-ssa Methodsmentioning

confidence: 99%

The kinetics and dynamics of the multichannel multiwell reaction of CO(1Σ+) with OH(2Π): theoretical investigation

Masoumpour

Daryanavard

2020

SN Appl. Sci.

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The kinetics and mechanism of the gas-phase reaction between carbon monoxide and hydroxyl radical have been theoretically investigated on the lowest potential energy surface. The dynamics of the reaction of CO(1 Σ +) with OH(2 Π) is studied by stochastic one-dimensional chemical master equation (CEM) simulation method. The role of the energized intermediates on the kinetics of the reaction was investigated by determination the fraction of different intermediates and products at the early stages of the reaction. The temperature dependence of the rate constants of the each individual channels of the reaction over a wide range of temperature (200-2000 K) was studied. The calculated rate constants from the CEM simulation were compared with those obtained from the RRKM-SSA [Rice-Ramsperger-Kassel-Marcus (RRKM) theory and Steady State Approximation (SSA)] method based on strong collision assumption. At lower temperatures, the calculated RRKM-SSA rate constant was found to be twice of the calculated by CEM, although the results are in good agreement with experimental values.

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Microcanonical Correlation Analysis of Collisional Energy Transfer Efficiencies in Unimolecular Reactions

Cited by 33 publications

References 6 publications

Kinetics of the cyclopentadiene decay and the recombination of cyclopentadienyl radicals with H‐atoms: Enthalpy of formation of the cyclopentadienyl radical

Kinetics of the cyclopentadiene decay and the recombination of cyclopentadienyl radicals with H‐atoms: Enthalpy of formation of the cyclopentadienyl radical

Erratum: “Kinetics of the cyclopentadiene decay and the recombination of cyclopentadienyl radicals with H‐atoms: Enthalpy of formation of the cyclopentadienyl radical”, Int J Chem Kinet 2001, 33, 821

The kinetics and dynamics of the multichannel multiwell reaction of CO(1Σ+) with OH(2Π): theoretical investigation

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