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Tests of stratospheric models: The reactions of atomic chlorine with O sub 3 and CH sub 4 at low temperature

Journal Article · · Journal of Geophysical Research; (United States)
DOI:https://doi.org/10.1029/90JD02737· OSTI ID:5398182
 [1]
  1. California Inst. of Tech., Pasadena (USA)

The reactions of atomic chlorine with O{sub 3} and CH{sub 4} are very important in stratospheric ozone photochemistry. The relative rates of these reactions strongly influence the ClO/HCl ration. However, there remains considerable uncertainty in the absolute rate constants for the two reactions at stratospheric temperatures. Since only the relative rate is of primary importance in the stratosphere, experiments on the competitive chlorination of O{sub 3}/CH{sub 4} mixtures have been carried out at 197-217 K, with the objective of directly measuring the rate constant ratio in this temperature range. The results with the objective of directly measuring the rate constant ratio in this temperature range. The results show that the absolute rate constants recommended by the NASA Panel for Data Evaluation (DeMore et al., 1990) are accurate on a relative basis to within 15% at stratospheric temperatures. The following rate constant upper limits are also established for temperatures near 200 K: ClO + CH{sub 3}O{sub 2} {yields} ClOO + CH{sub 3}O, k < 4 {times} 10{sup {minus}12}; ClO + CH{sub 3}O{sub 2} {yields} OClO + CH{sub 3}O, k < 1 {times} 10{sup {minus}15} cm{sup 3} molec{sup {minus}1}s{sup {minus}1}.

OSTI ID:
5398182
Journal Information:
Journal of Geophysical Research; (United States), Journal Name: Journal of Geophysical Research; (United States) Vol. 96:D3; ISSN 0148-0227; ISSN JGREA
Country of Publication:
United States
Language:
English