Pyrolysis of cyclopentadiene: Rates for initial C−H bond fission and the decomposition of c-C5H5

Kern, R. D.; Zhang, Q.; Yao, Jianxi; Jursic, Branko S.; Tranter, Robert S.; Greybill, M.A.; Kiefer, J. H.

doi:10.1016/s0082-0784(98)80399-8

Cited by 41 publications

(64 citation statements)

References 12 publications

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“…Our experimental conditions were such that the reaction proceeded rather close to the high pressure limit. This is in contrast to the measurements by Kern et al [11]. In those experiments the reaction was studied closer to the low pressure limit, in particular, if T exceeds 1500 K. Our experiments are more sensitive to the selected value for k ∞ rec , whereas Kern's and Kiefer's experiments depend stronger on E (0) all .…”

Section: Modeling Of the Fall-offcontrasting

confidence: 83%

“…In those experiments the reaction was studied closer to the low pressure limit, in particular, if T exceeds 1500 K. Our experiments are more sensitive to the selected value for k ∞ rec , whereas Kern's and Kiefer's experiments depend stronger on E (0) all . A simple direct comparison of the respective modeling of the two experimental data sets, the present work and that of Kern et al [11], is not easily possible. The latter group applied a RRKM analysis not taking into account effects of external rotation.…”

Section: Modeling Of the Fall-offmentioning

confidence: 76%

“…The entropy of cyclopentadienyl in the range from 300 to 2000 K is reproduced from this work in Table IV. We need for our modeling equilibrium coefficients in the temperature range from about 1000 K up to 2500 K. In particular, data at the highest temperature have to be used in order to compare the experimental data on the C 5 H 5 decay obtained by Kern et al [11] with our (2) 3091 (1) 3072 (2) 3075 (1) 1396 (2) 3043 (1) 1271 (1) 2900 (1) 1146 (2) 2886 (1) 1086 (1) 1580 (1) 990 (2) 1500 (1) 874 (2) 1378 (1) 874 (2) 1365 (1) 793 (2) 1292 (1) 746 (2) 1239 (1) 635 (1) 1100 (1) 505 (2) 1106 (1) 1090 (1) 994 (1) 959 (1) 941 (1) 925 (1) 915 (1) 891 (1) 805 (1) 802 (1) 700 (1) 664 (1) 516 (1) 350 (1) a Electronic degeneracies: g el = 2 (see text); Rotational constants (cm −1 ): A = 0.295; B = 0.295; C = 0.147; Symmetry factor = 10. Source: Kiefer et al [14].…”

Section: C-c 5 H 5 + H Recombination Reactionmentioning

confidence: 99%

“…8, which were taken from [11], represent the RRKM interpolation for 0.6 and 0.266 bar. Kern et al [11] give k(M) in units of cm 3 mol −1 s −1 . We have converted their data by multiplying them with M to obtain the ks in units of s −1 .…”

Section: Modeling Of the Fall-offmentioning

confidence: 99%

“…One observes even for T ≤ 1600 K a rather bad fit of the experimental data. Presently, we propose the optimized sets: k ∞ rec = 5.0 × 10 14 cm 3 mol −1 s −1 and − E (0) all between 20 and 25 cm −1 (for T ≤ 1600 K) by which the experiments given in [11] can be sufficiently well modeled. α(T ) for T ≤ 1600 K was taken from Eq.…”

Section: Modeling Of the Fall-offmentioning

confidence: 99%

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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

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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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Section: Modeling Of the Fall-offcontrasting

confidence: 83%

Section: Modeling Of the Fall-offmentioning

confidence: 76%

Section: C-c 5 H 5 + H Recombination Reactionmentioning

confidence: 99%

Section: Modeling Of the Fall-offmentioning

confidence: 99%

Section: Modeling Of the Fall-offmentioning

confidence: 99%

See 3 more Smart Citations

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

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Unimolecular isomerization/decomposition of cyclopentadienyl and related bimolecular reverse process:ab initio MO/statistical theory study

Moskaleva

Lin

2000

J. Comput. Chem.

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The cyclopentadienyl radical decomposition has been studied in detail by high-level correlation MO methods combined with multichannel RRKM rate constant calculations. The product channels of the reaction were examined by calculating their pressure-dependent branching rate constants. The overall reaction rate has been shown to be controlled by the first transition state corresponding to 1,2-hydrogen atom migration. Also, the reverse bimolecular reactions (C 3 H 3 + C 2 H 2 → products) have been included in the study. We provide a summary of pressure dependent rate constant expressions for the 1000-3000 K temperature range that may be useful for kinetic modeling of relevant combustion systems.

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Hydrogen Abstraction/Acetylene Addition Revealed

et al. 2014

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For almost half a century, polycyclic aromatic hydrocarbons (PAHs) have been proposed to play a key role in the astrochemical evolution of the interstellar medium (ISM) and in the chemistry of combustion systems. However, even the most fundamental reaction mechanism assumed to lead to the simplest PAH naphthalene—the hydrogen abstraction–acetylene addition (HACA) mechanism—has eluded experimental observation. Here, by probing the phenylacetylene (C8H6) intermediate together with naphthalene (C10H8) under combustion‐like conditions by photo‐ionization mass spectrometry, the very first direct experimental evidence for the validity of the HACA mechanism which so far had only been speculated theoretically is reported.

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Pyrolysis of cyclopentadiene: Rates for initial C−H bond fission and the decomposition of c-C5H5

Cited by 41 publications

References 12 publications

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

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

Unimolecular isomerization/decomposition of cyclopentadienyl and related bimolecular reverse process:ab initio MO/statistical theory study

Hydrogen Abstraction/Acetylene Addition Revealed

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