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Kinetic measurements of the ClO + O sub 3 yields ClOO + O sub 2 reaction

Journal Article · · Geophysical Research Letters (American Geophysical Union); (USA)
;  [1]
  1. Harvard Univ., Cambridge, MA (USA)

Upper limits for the bimolecular rate constant for the reaction ClO + O{sub 3} {yields} ClOO + O{sub 2} have been measured directly between 233 and 413 K using a discharge-flow system at 1-2 torr total pressure. Production of ClO (which occurs quickly after thermal decomposition of ClOO in the presence of O{sub 3}) was detected using Laser Magnetic Resonance spectroscopy, and distinguished from the reactant ClO through isotopic oxygen labeling. At 298 and 233 K, k{sub 1} was found to be less than 1.4 {times} 10{sup {minus}17} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. At 413 K, k{sub 1} = (4.0 {plus minus} 2.0) {times} 10{sup {minus}16} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. The experimental conditions were modelled using a kinetic simulation program to show that chemical and isotopic scrambling interferences were negligible. From these results, it is concluded that this bimolecular reaction does not contribute significantly to the observed ozone depletion within the antarctic vortex.

OSTI ID:
5991663
Journal Information:
Geophysical Research Letters (American Geophysical Union); (USA), Journal Name: Geophysical Research Letters (American Geophysical Union); (USA) Vol. 17:9; ISSN 0094-8276; ISSN GPRLA
Country of Publication:
United States
Language:
English