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Long Path-Ftir Studies of Some Atmospheric Reactions Involving Cf3Oo and Cf3o rAdicals

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In attempts to obtain kinetic and mechanistic data required for an assessment of atmospheric fate of alternative halocarbons containing a CF3 group, reactions of the key free radical intermediates CF3OO and CF3O with several atmospheric compounds (i.e., NO, NO2, alkanes and alkenes) have been studied at 297 ± 2 K in 700 torr of air. Experiments employed the long path-FTIR spectroscopic method for product analysis and the visible (400 nm) photolysis of CF3NO → CF3 + NO as a source for the precursor radical CF3. Numerous labile and stable F-containing molecular products have been characterized based on kinetic and spectroscopic data obtained at sufficiently short photolysis time (1 min) to minimize heterogeneous decay on the reactor walls. Major new findings have been made for the reactions involving CF3O radicals. The behavior of CF3O radicals has been shown to be markedly different from that of CH3O radicals, i.e., (1) O2-reaction: no evidence for the F-atom transfer reaction CF3O + O2 → CF2O + FOO; (2) NO-reaction: addition reaction CH3O + NO (+M) → CH3ONO (+M), but F-transfer reaction CF3O +NO → CF2O + FNO; (3) NO2-reaction: addition reaction for both radicals, but F-transfer reaction CF3 + NO2 → CF2O + FNO2 to a minor extent; (4) alkane-reaction: much faster H-abstraction by CF3O, comparable to HO; (5) alkene-reaction: much faster addition reaction of CF3O, comparable to HO. These results are summarized in this paper.

Affiliations: 1: Centre for Atmospheric Chemistry and Department of Chemistry, York University, 4700 Keele Street, North York, Ontario, Canada M3J 1P3


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