Atmospheric chemistry of perfluorobutenes (CF3CFCFCF3 and CF3CF2CFCF2): Kinetics and mechanisms of reactions with OH radicals and chlorine atoms,IR spectra,global warming potentials,and oxidation to perfluorocarboxylic acids |
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| Authors: | Cora J. Young Michael D. Hurley Timothy J. Wallington Scott A. Mabury |
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| Affiliation: | 1. Department of Chemistry, University of Toronto, 80 St George Street, Toronto, ON, Canada M5S 3H6;2. Ford Motor Company, Mail Drop SRL-3083, Dearborn, MI 48121, USA;1. Department of Chemistry, University of Zanjan, Zanjan 38791-45371, Iran;2. Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran;1. Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Republic of Korea;2. Department of Chemistry, Gangneung-Wonju National University, Gangneung, Gangwon-do 210-702, Republic of Korea;1. State Key Laboratory of Pollution Control and Resources Reuse, School of the Environment, Nanjing University, Nanjing 210023, China;2. College of Chemistry and Chemical Engineering, Xinyang Normal University, Henan, Xinyang 464000, China;1. Department of Civil and Environmental Engineering, Carleton University, Ottawa, Ontario, Canada;2. Department of Chemistry and Biochemistry, California State University at Long Beach, Long Beach, CA, USA;3. Geosyntec Consultants Inc., Guelph and Waterloo Offices, Ontario, Canada;4. Department of Civil and Environmental Engineering, University of Waterloo, Waterloo, Ontario, Canada;1. School of Chemistry & Chemical Engineering, Beijing Institute of Technology, 5 South Zhongguancun Street, Haidian District, Beijing 100081, PR China;2. National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan |
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| Abstract: | Relative rate techniques were used to determine k(Cl + CF3CF CFCF3) = (7.27 ± 0.88) × 10?12, k(Cl + CF3CF2CFCF2) = (1.79 ± 0.41) × 10?11, k(OH + CF3CFCFCF3) = (4.82 ± 1.15) × 10?13, and k(OH + CF3CF2CFCF2) = (1.94 ± 0.27) × 10?12 cm3 molecule?1 s?1 in 700 Torr of air or N2 diluent at 296 K. The chlorine atom- and OH radical-initiated oxidation of CF3CFCFCF3 in 700 Torr of air gives CF3C(O)F in molar yields of 196 ± 11 and 218 ± 20%, respectively. Chlorine atom-initiated oxidation of CF3CF2CFCF2 gives molar yields of 97 ± 9% CF3CF2C(O)F and 97 ± 9% COF2. OH radical-initiated oxidation of CF3CF2CFCF2 gives molar yields of 110 ± 15% CF3CF2C(O)F and 99 ± 8% COF2. The atmospheric fate of CF3CF2C(O)F and CF3C(O)F is hydrolysis to give CF3CF2C(O)OH and CF3C(O)OH. The atmospheric lifetimes of CF3CFCFCF3 and CF3CF2CFCF2 are determined by reaction with OH radicals and are approximately 24 and 6 days, respectively. The contribution of CF3CFCFCF3 and CF3CF2CFCF2 to radiative forcing of climate change will be negligible. |
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