Atmospheric Chemistry of CH_3O(CF_2CF_2O)_nCH_3 (n = 1-3): Kinetics and Mechanism of Oxidation Initiated by Cl Atoms and OH Radicals, IR Spectra, and Global Warming Potentials

M. P. Sulbaek Andersen; M. D. Hurley; T. J. WallingtonF. BlandiniN. R. JensenV. LibrandoJ. HjorthG. MarchionniM. AvataneoM. Visca

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Atmospheric Chemistry of CH_3O(CF_2CF_2O)_nCH_3 (n = 1-3): Kinetics and Mechanism of Oxidation Initiated by Cl Atoms and OH Radicals, IR Spectra, and Global Warming Potentials

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Smog chambers equipped with FTIR spectrometers were used to study the Cl atom and OH radical initiated oxidation of CH_3O(CF_2CF_2O)_nCH_3 (n = 1-3) in 720 ± 20 Torr of air at 296 ± 3 K. Relative rate techniques were used to measure k(Cl + CH_3O(CF_2CF_2O)_nCH_3) = (3.7 ± 0.7) * 10~(-13) and k(OH + CH_3O(CF_2CF_2O)_nCH_3) = (2.9 ± 0.5) * 10~(-14) cm~3 molecule-1 s~(-1) leading to an estimated atmospheric lifetime of 2 years for CH_3O(CF_2CF_2O)_nCH_3. The Cl initiated oxidation of CH_3O(CF_2CF_2O)_nCH_3 in air diluent gives CH_3O(CF_2CF_2O)_nC(O)H in a yield which is indistinguishable from 100. Further oxidation leads to the diformate, H(O)CO(CF_2CF_2O)_nC(O)H. A rate constant of k(Cl + CH_3O(CF_2CF_2O)_nCHO) = (1.81 ± 0.36) * 10~(-13) cm~3 molecule-1 s-1 was determined. Quantitative infrared spectra for CH_3O(CF_2CF_2O)_nCH_3 (n = 1-3) were recorded and used to estimate halocarbon global warming potentials of 0.051, 0.058, and 0.055 (100 year time horizon, relative to CFC-11) for CH_3OCF_2CF_2OCH_3, CH_3O(CF_2CF_2O)_2CH_3, and CH_3O(CF_2CF_2O)_3CH_3, respectively. Results are discussed with respect to the atmospheric chemistry of hydrofluoropolyethers (HFPEs).

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2004年第11期|1964-1972|共9页
作者
M. P. Sulbaek Andersen; M. D. Hurley; T. J. WallingtonF. BlandiniN. R. JensenV. LibrandoJ. HjorthG. MarchionniM. AvataneoM. Visca;
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Ford Research and Advanced Engineering, SRL-3083, Ford Motor Company, Dearborn, P.O. Box 2053, Michigan 48121-2053;

EC-Joint Research Centre, Institute for Environment and Sustainability, TP 290, I-21020 Ispra (VA), Italy;

Chemistry Department, University of Catania, Viale Doria 6, I-95127 Catania, ItalySolvay Solexis, Via S. Pietro 50, I-20021 Bollate (MI), Italy;

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正文语种英语
中图分类物理化学（理论化学）、化学物理学;
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Atmospheric Chemistry of CH_3O(CF_2CF_2O)_nCH_3 (n = 1-3): Kinetics and Mechanism of Oxidation Initiated by Cl Atoms and OH Radicals, IR Spectra, and Global Warming Potentials

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