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Kinetic measurements of the ClO + O 3 → ClOO + O 2 reaction
Author(s) -
Stevens Philip S.,
Anderson James G.
Publication year - 1990
Publication title -
geophysical research letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.007
H-Index - 273
eISSN - 1944-8007
pISSN - 0094-8276
DOI - 10.1029/gl017i009p01287
Subject(s) - ozone , reaction rate constant , analytical chemistry (journal) , kinetic energy , chemistry , chemical reaction , molecule , thermal decomposition , spectroscopy , decomposition , torr , photodissociation , kinetics , thermodynamics , photochemistry , physics , environmental chemistry , biochemistry , organic chemistry , quantum mechanics
Upper limits for the bimolecular rate constant for the reaction ClO + O 3 → ClOO + O 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 3 ) was detected using Laser Magnetic Resonance spectroscopy, and distinguished from the reactant ClO through isotopic oxygen labelling. At 298 and 233 K, k 1 was found to be less than 1.4 × 10 −17 cm 3 molecule −1 s −1 . At 413 K1 k 1 = (4.0 ±2.0) × 10 −16 cm 3 molecule −1 s −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.