Pressure dependence of the reaction of chlorine atoms with ethene and acetylene in air at 295 K

T. J. Wallington, Jean M. Andino, I. M. Lorkovic, E. W. Kaiser, G. Marston

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Abstract

The relative rate technique has been used to determine rate constants for the reaction of chlorine atoms with ethene and acetylene over the pressure ranges 10-3000 and 10-5800 Torr, respectively, of synthetic air at 295 K. The decays of the reactants were measured relative to that of either ethane or chloroethane or both. Using a pressure-independent value of 5.7 × 10-11 cm3 molecule-1 s-1 for the reaction of Cl with ethane, the relative data were placed on an absolute basis and fit to the Troe expression with the broadening factor, F, fixed at 0.6. Values of the best-fit low-pressure termolecular rate constant k0, and high-pressure limiting bimolecular rate constant, k∞, for the reaction of Cl atoms with ethene were k01, = 1.6-0.3+1 × 10-29 cm6 molecule-2 s-1 and k∞1 = 3.05-0.4+2 × 10-10 cm3 molecule-1 s-1, and those for the reaction of Cl atoms with acetylene were k02 = (5.2 ± 0.7) × 10-30 cm6 molecule-2 s-1 and k∞2 = (2.3 ± 0.7) × 10-10 cm3 molecule-1 s-1. Quoted uncertainties reflect statistical (95% confidence) errors and uncertainty in the value of F. The results are discussed with respect to the previous literature data for these reactions and to the chemistry of the upper atmosphere.

Original languageEnglish
Pages (from-to)3644-3648
Number of pages5
JournalJournal of Physical Chemistry
Volume94
Issue number9
Publication statusPublished - 1990

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Acetylene
Chlorine
acetylene
pressure dependence
chlorine
Atoms
Molecules
air
Air
Rate constants
Ethane
atoms
molecules
ethane
Ethyl Chloride
Upper atmosphere
upper atmosphere
confidence
low pressure
ethylene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Wallington, T. J., Andino, J. M., Lorkovic, I. M., Kaiser, E. W., & Marston, G. (1990). Pressure dependence of the reaction of chlorine atoms with ethene and acetylene in air at 295 K. Journal of Physical Chemistry, 94(9), 3644-3648.

Pressure dependence of the reaction of chlorine atoms with ethene and acetylene in air at 295 K. / Wallington, T. J.; Andino, Jean M.; Lorkovic, I. M.; Kaiser, E. W.; Marston, G.

In: Journal of Physical Chemistry, Vol. 94, No. 9, 1990, p. 3644-3648.

Research output: Contribution to journalArticle

Wallington, TJ, Andino, JM, Lorkovic, IM, Kaiser, EW & Marston, G 1990, 'Pressure dependence of the reaction of chlorine atoms with ethene and acetylene in air at 295 K', Journal of Physical Chemistry, vol. 94, no. 9, pp. 3644-3648.
Wallington, T. J. ; Andino, Jean M. ; Lorkovic, I. M. ; Kaiser, E. W. ; Marston, G. / Pressure dependence of the reaction of chlorine atoms with ethene and acetylene in air at 295 K. In: Journal of Physical Chemistry. 1990 ; Vol. 94, No. 9. pp. 3644-3648.
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abstract = "The relative rate technique has been used to determine rate constants for the reaction of chlorine atoms with ethene and acetylene over the pressure ranges 10-3000 and 10-5800 Torr, respectively, of synthetic air at 295 K. The decays of the reactants were measured relative to that of either ethane or chloroethane or both. Using a pressure-independent value of 5.7 × 10-11 cm3 molecule-1 s-1 for the reaction of Cl with ethane, the relative data were placed on an absolute basis and fit to the Troe expression with the broadening factor, F, fixed at 0.6. Values of the best-fit low-pressure termolecular rate constant k0, and high-pressure limiting bimolecular rate constant, k∞, for the reaction of Cl atoms with ethene were k01, = 1.6-0.3+1 × 10-29 cm6 molecule-2 s-1 and k∞1 = 3.05-0.4+2 × 10-10 cm3 molecule-1 s-1, and those for the reaction of Cl atoms with acetylene were k02 = (5.2 ± 0.7) × 10-30 cm6 molecule-2 s-1 and k∞2 = (2.3 ± 0.7) × 10-10 cm3 molecule-1 s-1. Quoted uncertainties reflect statistical (95{\%} confidence) errors and uncertainty in the value of F. The results are discussed with respect to the previous literature data for these reactions and to the chemistry of the upper atmosphere.",
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N2 - The relative rate technique has been used to determine rate constants for the reaction of chlorine atoms with ethene and acetylene over the pressure ranges 10-3000 and 10-5800 Torr, respectively, of synthetic air at 295 K. The decays of the reactants were measured relative to that of either ethane or chloroethane or both. Using a pressure-independent value of 5.7 × 10-11 cm3 molecule-1 s-1 for the reaction of Cl with ethane, the relative data were placed on an absolute basis and fit to the Troe expression with the broadening factor, F, fixed at 0.6. Values of the best-fit low-pressure termolecular rate constant k0, and high-pressure limiting bimolecular rate constant, k∞, for the reaction of Cl atoms with ethene were k01, = 1.6-0.3+1 × 10-29 cm6 molecule-2 s-1 and k∞1 = 3.05-0.4+2 × 10-10 cm3 molecule-1 s-1, and those for the reaction of Cl atoms with acetylene were k02 = (5.2 ± 0.7) × 10-30 cm6 molecule-2 s-1 and k∞2 = (2.3 ± 0.7) × 10-10 cm3 molecule-1 s-1. Quoted uncertainties reflect statistical (95% confidence) errors and uncertainty in the value of F. The results are discussed with respect to the previous literature data for these reactions and to the chemistry of the upper atmosphere.

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