Atmospheric chemistry of perfluorobutenes (CF 3CF CFCF 3 and CF 3CF 2CF CF 2): Kinetics and mechanisms of reactions with OH radicals and chlorine atoms, IR spectra, global warming potentials, and oxidation to perfluorocarboxylic acids

Relative rate techniques were used to determine k(Cl + CF 3CF CFCF 3) = (7.27 ± 0.88) × 10 −12, k(Cl + CF 3CF 2CF CF 2) = (1.79 ± 0.41) × 10 −11, k(OH + CF 3CF CFCF 3) = (4.82 ± 1.15) × 10 −13, and k(OH + CF 3CF 2CF CF 2) = (1.94 ± 0.27) × 10 −12 cm 3 molecule −1 s −1 in 700 Torr of air or N 2 dilue...

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Bibliographic Details
Published in:	Atmospheric environment (1994) Vol. 43; no. 24; pp. 3717 - 3724
Main Authors:	Young, Cora J., Hurley, Michael D., Wallington, Timothy J., Mabury, Scott A.
Format:	Journal Article
Language:	English
Published:	Kidlington Elsevier Ltd 01-08-2009 Elsevier
Subjects:	Applied sciences Atmospheric oxidation Atmospheric pollution Atmospherics Chemical composition and interactions. Ionic interactions and processes Chlorine Earth, ocean, space Exact sciences and technology External geophysics Fluorinated alkene Global warming Hydrolysis Meteorology Oxidation Perfluorocarboxylic acid Pollutants physicochemistry study: properties, effects, reactions, transport and distribution Pollution Radiative efficiency Radiative forcing Radicals Spectra Radiative efficiency Fluorinated alkene Perfluorocarboxylic acid Atmospheric oxidation Global warming potential Chlorine Hydrofluorocarbon fluid Reaction initiator Fluorocarbon Chemical reaction kinetics Ethylenic aliphatic compound Atmospheric chemistry Environment impact Organic fluorine compounds Reaction mechanism Hydroxyl radicals Air pollution Effect on climate Oxidation Substitute Organic compounds
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Summary:	Relative rate techniques were used to determine k(Cl + CF 3CF CFCF 3) = (7.27 ± 0.88) × 10 −12, k(Cl + CF 3CF 2CF CF 2) = (1.79 ± 0.41) × 10 −11, k(OH + CF 3CF CFCF 3) = (4.82 ± 1.15) × 10 −13, and k(OH + CF 3CF 2CF CF 2) = (1.94 ± 0.27) × 10 −12 cm 3 molecule −1 s −1 in 700 Torr of air or N 2 diluent at 296 K. The chlorine atom- and OH radical-initiated oxidation of CF 3CF CFCF 3 in 700 Torr of air gives CF 3C(O)F in molar yields of 196 ± 11 and 218 ± 20%, respectively. Chlorine atom-initiated oxidation of CF 3CF 2CF CF 2 gives molar yields of 97 ± 9% CF 3CF 2C(O)F and 97 ± 9% COF 2. OH radical-initiated oxidation of CF 3CF 2CF CF 2 gives molar yields of 110 ± 15% CF 3CF 2C(O)F and 99 ± 8% COF 2. The atmospheric fate of CF 3CF 2C(O)F and CF 3C(O)F is hydrolysis to give CF 3CF 2C(O)OH and CF 3C(O)OH. The atmospheric lifetimes of CF 3CF CFCF 3 and CF 3CF 2CF CF 2 are determined by reaction with OH radicals and are approximately 24 and 6 days, respectively. The contribution of CF 3CF CFCF 3 and CF 3CF 2CF CF 2 to radiative forcing of climate change will be negligible.
Bibliography:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23
ISSN:	1352-2310 1873-2844
DOI:	10.1016/j.atmosenv.2009.04.025