Energy transfer in thermal methyl isocyanide isomerization. Comprehensive investigation

Chan, Siu C.; Rabinovitch, B. S.; Bryant, James T.; Spicer, Leonard D.; Fujimoto, Takehiko; Lin, Yueh Neu; Pavlou, Stavros

doi:10.1021/j100711a002

Cited by 138 publications

(59 citation statements)

References 6 publications

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“…Hence, we can take 0.3 as a conservative estimate of a,. This is in reasonable agreement with energy transfer efficiencies in unimolecular reactions (Chan et al, 1970). From Table 3 we see that this, together with the assumption a, > a,, implies that i< 0.5 pm, in agreement with most of the experimental results.…”

Section: Theory Of Aerosol Growthsupporting

confidence: 89%

Aerosol Growth and the Condensation Coefficient for Water: A Review

Mozurkewich

1986

Aerosol Science and Technology

139

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The transfer of gas phase species to aerosols depends a somewhat modified form is presented. Experimental critically on the condensation (or sticking) coefficient. measurements of aerosol growth are consistent with a Reported values for water on water vary from 0.03 to 1. condensation coefficient of unity but indicate that the Theoretical arguments indicate that the condensation thermal accommodation coefficient may be somewhat coefficient should be near unity for polar species on an smaller. Aerosols grown on natural condensation nuclei aqueous surface. As long as heat transfer is properly may have smaller condensation coefficients owing to the accounted for, measurements on bulk water support this presence of organic films. conclusion. The theory of aerosol growth is reviewed and NOMENCLATURE a drop radius C, concentration of the drop a, thdrmal accommodation coefficient, Eq. (11) A effective mean free path, Eqs. (1) and (12) C, concentration of vapor in equilibrium with the drop

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Section: Theory Of Aerosol Growthsupporting

confidence: 89%

Aerosol Growth and the Condensation Coefficient for Water: A Review

Mozurkewich

1986

Aerosol Science and Technology

139

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“…Considerable work has been directed toward determining relative collision diameters of molecules in chemical activation [27] and thermal unimolecular reaction systems [28]. The conclusion appears to be that for large molecules (several atoms) relative collision diameters in these systems seem to follow gas viscosity based values fairly well.…”

Section: Discussionmentioning

confidence: 99%

Chemically activated methylcyclobutane exothermicity of singlet methylene reactions and the heat of formation of singlet methylene

Simons

Hase

Phillips

et al. 1975

Int J of Chemical Kinetics

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The specific decomposition rates of chemically activated methylcyclobutane produced from CH#Al) reaction with cyclobutane $ave been determined. CHz(lAl)was produced from ketene photolyses at 3340 and 3130 A and from diazomethane photolyses at 4358 and 3660 A. Comparisons of the excitation energies of the methylcyclobutane, determined by RRKM theory calculations, and the experimental results for the ketene systems, with thermochemically predicted maximum excitation energies, favor an Arrhenius A factor in the range of 5 X IOl5 to 1 X 10l6 sec-' for methylcyclobutane. This result is consistent with ( I ) the comparison of RRKM theory calculations and the experimental unimolecular falloff for methylcyclobutane, (2) the comparison of experimental A factors for cyclobutane and other alkylcyclobutane decompositions, and (3) two out of three reported experimental A factors for methylcyclobutane. An analysis of these and previous results leads to a value of the CHz(lA1) H C H Z (~B J energy splitting of 9 f 3 kcal/mole.

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“…We have already mentioned incubation times and "lowpressure turn-up", and should also include in this context the inefficiency of gas-gas collisions relative to gas-wall collisions found in many thermal reactions (33-37); likewise, neither measurement of relative collision efficiencies in the fall-off region (38)(39)(40) nor of absolute collision efficiencies, viz. X = p/Z[M] (7), provides us with any discriminating power.…”

Section: Discussionmentioning

confidence: 99%

Internal energy randomisation in weak-collision unimolecular reaction systems

Pritchard¹,

Vatsya²

1981

Can. J. Chem.

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H. 0. PRITCHARD and S. R. VATSYA. Can. J. Chem. 59, 2575 (1981). We examine the conjecture that the principal difference between weak-collision and strong-collision behaviour in thermal unimolecular reaction systems arises from a difference in internal energy randomisation rates. To do this, we solve analytically the strong-collision master equation for a thermal unimolecular reaction including explicit allowance for the randomisation processes, and we show that all weak-collision effects so far observed in thermal systems can be accommodated within this framework.In an appendix, we give the extension of this analytic solution for reactions yielding two (or more) distinct sets of products. Nous examinons I'hypothese relative au fait que la difference principale de comportement entre une collision faible et collision forte, dans les systkmes de reactions thermique unimolCculaire, provient de la difference entre les vitesses de distribution au hasard de I'energie interne. Pour ce faire nous rCsolvons analytiquement I'tquation principale de collision forte pour une reaction thermique unimolCculaire incluant une correction explicite pour le processus de distribution au hasard, et nous montrons que tous les effets de collision faible observes dans les systkmes thermiques peuvent s'integrer dans ce cadre.En appendice nous donnons le dkveloppement de cette solution analytique pour les reactions conduisant a deux (ou plus) ensembles distincts de produits.[Traduit par le journal]

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Energy transfer in thermal methyl isocyanide isomerization. Comprehensive investigation

Cited by 138 publications

References 6 publications

Aerosol Growth and the Condensation Coefficient for Water: A Review

Aerosol Growth and the Condensation Coefficient for Water: A Review

Chemically activated methylcyclobutane exothermicity of singlet methylene reactions and the heat of formation of singlet methylene

Internal energy randomisation in weak-collision unimolecular reaction systems

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