Pressure and temperature dependence of reactions proceeding via a bound complex. 2. Application to 2CH3 → C2H5 + H

Stewart, Paul H.; Larson, C. W.; Golden, David M.

doi:10.1016/0010-2180(89)90084-9

Cited by 118 publications

(68 citation statements)

References 23 publications

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“…These values are in good agreement with the results of Zaslonko et al [26]. However, no fall-off parameters were reported by Glänzer and Troe; their work on the CH 3 NO 2 (ϩ M) reaction was prior to the methodologies developed by Troe and others [39,40] that describe more accurately the fall-off behavior of a pressure-dependent reaction using a center broadening parameter. Zaslonko et al [26] describe the pressure dependency in terms of the Kassel integral, but do not provide an expression for the center broadening.…”

Section: Reaction Setsupporting

confidence: 86%

Nitromethane dissociation: Implications for the CH3 + NO2 reaction

Glarborg¹,

Bendtsen²,

Miller³

1999

Int. J. Chem. Kinet.

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The thermal decomposition of nitromethane under highly diluted conditions in shock tubes has been analyzed in terms of a detailed chemical kinetic model. The experimental data were adopted from Glä nzer and Troe, Hsu and Lin, and Zhang and Bauer, respectively; they cover the temperature range and pressures from 0.5 to 6.0 bar. Based on 1000-1400 K these results, rate constants for the reactions (R1) andThe high and low pressure limits for reaction (R1) determined by Glä nzer and Troe have been shown to be consistent with more recent shock tube data, provided a center broadening parameter is introduced to describe the fall-off behavior. Our reinterpretation of the shock tube results of Glä nzer and Troe together with room temperature measurements indicate that the rate constant for (R14) decreases slightly with temperature, as cm mol s . order of magnitude faster than recombination of CH 3 and NO 2 to form nitromethane. Based on the available data for the forward and reverse rate of reaction (R1) a value of 66.7 Ϯ 2.0 cal/(mol K) for the entropy S 0,298 of CH 3 NO 2 is estimated.

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Section: Reaction Setsupporting

confidence: 86%

Nitromethane dissociation: Implications for the CH3 + NO2 reaction

Glarborg¹,

Bendtsen²,

Miller³

1999

Int. J. Chem. Kinet.

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“…An alternative representation of F (T) was introduced by Stewart et al (1989) F = [aexp(-blT) +exp(-Tlc)t…”

Section: Combustion Chemistry Of Nitrogen 131mentioning

confidence: 99%

Combustion Chemistry of Nitrogen

Dean

Bozzelli

2000

Gas-Phase Combustion Chemistry

231

317

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“…The approach taken at the Stanford Research Institute (SRI) by Stewart et al (1989) is in many ways similar to that taken by Troe, but the blending function F is approximated differently. Here, F is given by…”

Section: Appendix C: Pressure-dependent Reactionsmentioning

confidence: 99%

“…-the Lindemann et al (1922) formulation, illustrated by reaction (1) in Table C.1; -the Troe (1983) formulation, see for example reaction (2) in Table C.1; -the SRI formulation proposed by Stewart et al (1989), illustrated by reaction (3) in Table C.1.…”

Section: Appendix C: Pressure-dependent Reactionsmentioning

confidence: 99%

A chemical model for the atmosphere of hot Jupiters

Venot

Hébrard

Agúndez

et al. 2012

A&A

228

560

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Context. The atmosphere of hot Jupiters can be probed by primary transit and secondary eclipse spectroscopy. Owing to the intense UV irradiation, mixing, and circulation, their chemical composition is maintained out of equilibrium and must be modeled with kinetic models. Aims. Our purpose is to release a chemical network and the associated rate coefficients, developed for the temperature and pressure range relevant to hot Jupiters atmospheres. Using this network, we study the vertical atmospheric composition of the two hot Jupiters (HD 209458b and HD 189733b) with a model that includes photolyses and vertical mixing, and we produce synthetic spectra. Methods. The chemical scheme has been derived from applied combustion models that were methodically validated over a range of temperatures and pressures typical of the atmospheric layers influencing the observations of hot Jupiters. We compared the predictions obtained from this scheme with equilibrium calculations, with different schemes available in the literature that contain N-bearing species, and with previously published photochemical models. Results. Compared to other chemical schemes that were not subjected to the same systematic validation, we find significant differences whenever nonequilibrium processes take place (photodissociations or vertical mixing). The deviations from the equilibrium, hence the sensitivity to the network, are larger for HD 189733b, since we assume a cooler atmosphere than for HD 209458b. We found that the abundances of NH 3 and HCN can vary by two orders of magnitude depending on the network, demonstrating the importance of comprehensive experimental validation. A spectral feature of NH 3 at 10.5 μm is sensitive to these abundance variations and thus to the chemical scheme.Conclusions. Due to the influence of the kinetics, we recommend using a validated scheme to model the chemistry of exoplanet atmospheres. The network we release is robust for temperatures within 300-2500 K and pressures from 10 mbar up to a few hundred bars, for species made of C, H, O, and N. It is validated for species up to 2 carbon atoms and for the main nitrogen species (NH 3 , HCN, N 2 , NO x ). Although the influence of the kinetic scheme on the hot Jupiters spectra remains within the current observational error bars (with the exception of NH 3 ), it will become more important for atmospheres that are cooler or subjected to higher UV fluxes, because they depart more from equilibrium.

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Pressure and temperature dependence of reactions proceeding via a bound complex. 2. Application to 2CH3 → C2H5 + H

Cited by 118 publications

References 23 publications

Nitromethane dissociation: Implications for the CH3 + NO2 reaction

Nitromethane dissociation: Implications for the CH3 + NO2 reaction

Combustion Chemistry of Nitrogen

A chemical model for the atmosphere of hot Jupiters

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