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Long path-FTIR studies of some atmospheric reactions involving CF3OO and CF3O radicals

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Abstract

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 → CF2 O + 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.

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References

  1. R. Atkinson, R. Cox, R. Lesclaux, H. Niki, and R. Zellner. An Assessment of Potential Degradation Products in the Gas-Phase Reactions of the Alternative Fluorocarbons in the Troposphere. in: World Meteorological Organization, Global Ozone Research and Monitoring Project, AFEAS Report 20.Vol. II, (1991).

  2. J. Chen, V. Young, T. Zhu, and H. Niki, J. Phys. Chem. 97, 11696 (1993).

    Article  CAS  Google Scholar 

  3. J. Chen, T. Zhu, and H. Niki, J. Phys. Chem. 96, 6115 (1992).

    Article  CAS  Google Scholar 

  4. J. Chen, T. Zhu, H. Niki, and G.J. Mains, Geophys. Res. Lett. 19, 2215 (1992).

    Article  CAS  Google Scholar 

  5. J. Chen, T. Zhu, V. Young, and H. Niki, J. Phys. Chem. 97, 7174 (1993).

    Article  CAS  Google Scholar 

  6. J. Mason, J. Chem. Soc. 4537 (1963).

  7. T.D. Allston, M.L. Fedyk, and G.A. Takacs, Chem. Phys. Lett. 60, 97 (1978).

    Article  CAS  Google Scholar 

  8. F. Caralp, R. Lesclaux, and A.M. Dognon, Chem. Phys. Lett. 129, 433 (1986).

    Article  CAS  Google Scholar 

  9. P. Felder, T.K. Ha, A.M. Dwivedi, and H.H. Gunthard, Spectrochim. Acta. 37A, 337 (1981).

    CAS  Google Scholar 

  10. H. Niki, P.D. Maker, C.M. Savage, and L.P. Breitenbach, Chem. Phys. Lett. 61, 100 (1979).

    Article  CAS  Google Scholar 

  11. A.H. Nielson, T.G. Burke, P.J.H. Woltz, and E.A. Jones, J. Chem. Phys. 20, 596 (1952).

    Article  Google Scholar 

  12. L.H. Jones, L.B. Asprey, and R.R. Ryan, J. Chem. Phys. 47, 3371 (1967).

    Article  CAS  Google Scholar 

  13. H. Niki, P.D. Maker, C.M. Savage, and L.P. Breitenbach, J. Mol. Struct. 59, 1 (1980).

    Article  CAS  Google Scholar 

  14. Z. Li and J.S. Francisco, J. Am. Chem. Soc. 111, 5660 (1989).

    Article  CAS  Google Scholar 

  15. J.S. Francisco and I.H. Williams, Int. J. Chem. Kinet. 20, 455 (1988).

    Article  CAS  Google Scholar 

  16. Z. Li and J.S. Francisco, Chem. Phys. Lett. 186, 336 (1991).

    Article  CAS  Google Scholar 

  17. K. Sugawara, T. Nakanaga, H. Takeo, and C. Matsumura, J. Phys. Chem. 93, 1894 (1989).

    Article  CAS  Google Scholar 

  18. P. Pagsberg, E. Ratajczak, and A. Sillesen, Chem. Phys. Lett. 141, 88 (1987).

    Article  CAS  Google Scholar 

  19. R. Atkinson, D.L. Baulch, R.A. Cox, R.F. Hampson, J.A. Kerr, and J. Troe, J. Phys. Chem. Ref. Data 18, 1072 (1989).

    Google Scholar 

  20. W.B. DeMore, S.P. Sander, D.M. Golden, R.F. Hampson, M.J. Kurylo, C.J. Howard, A.R. Ravishankara, C.E. Kolb, and M.J. Molina. Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling, NASA Report, JPL Publication, 92–20, Aug. 15, (1992).

  21. G. Kloeter and K. Seppelt, J. Am. Chem. Soc. 102, 347 (1979).

    Article  Google Scholar 

  22. H. Niki, P.D. Maker, C.M. Savage, and L.P. Breitenbach, J. Phys. Chem. 86, 3825 (1982).

    Article  CAS  Google Scholar 

  23. H. Niki and P.D. Maker, Advances in Photochemistry 15, 69 (1990).

    Article  CAS  Google Scholar 

  24. P.A. Bernstein, F.A. Hohorst, and D.D. DesMarteau, J. Am. Chem. Soc. 93, 3882 (1971).

    Article  Google Scholar 

  25. T.J. Bevilacqua, D.R. Hanson, and C.J. Howard, J. Phys. Chem. 97, 3750 (1993).

    Article  CAS  Google Scholar 

  26. W. Tsang and R.F. Hampson, J. Phys. Chem. Ref. Data. 15, 1087 (1986).

    Article  CAS  Google Scholar 

  27. J.A. Logan, J. Geophys. Res. 88, 10785 (1983).

    Article  CAS  Google Scholar 

  28. M.J. Bollinger, C.J. Hahn, D.D. Parrish, P.C. Murphy, D.L. Albritton, and F.C. Fehsenfeld, J. Geophys. Res. 89, 9623 (1984).

    Article  CAS  Google Scholar 

  29. H.B. Singh and P.B. Zimmerman in J.O. Nriagu (Ed.), Gaseous Pollutions: Characterization and Cycling, Wiley, 1992, pp. 177–235.

  30. R. Atkinson, Chem. Rev. 86, 69 (1986).

    Article  CAS  Google Scholar 

  31. K.S. Chen and J.K. Kochi, J. Am. Chem. Soc. 96, 1383 (1974).

    Article  CAS  Google Scholar 

  32. H. Niki, P.D. Maker, C.M. Savage, and L.P. Breitenbach, J. Phys. Chem. 82, 135 (1978).

    Article  CAS  Google Scholar 

  33. J. Nakanaga, J. Chem. Phys. 74, 5384 (1981).

    Article  CAS  Google Scholar 

  34. M.C. Tobin, Spectrochim. Acta. 16A, 1108 (1960).

    Article  Google Scholar 

  35. J.R. Durig, A.B. Nease, and J.J. Rizzolo, J. Mol. Struct. 95, 59 (1982).

    Article  CAS  Google Scholar 

  36. R. Atkinson, Atoms. Environ. 24A, 1 (1990).

    CAS  Google Scholar 

  37. T.Jobson, Z. Wu, H. Niki, and L.A. Barrie, J. Geophys. Res. (1993), in press.

  38. H. Niki, P.D. Maker, C.M. Savage, and L.P. Breitenbach, Chem. Phys. Lett. 55, 289 (1978).

    Article  CAS  Google Scholar 

  39. F.A. Hohorst and D.D. DesMarteau, Inorg. Chem. 13, 715 (1974).

    Article  CAS  Google Scholar 

  40. D. Koeppenkastrop and F. Zabel, Int. J. Chem. Kinet. 23, 1 (1991).

    Article  CAS  Google Scholar 

  41. D.L. Bemitt, R.H. Miller, and I.C. Hisatsune, Spectro-Chimera. Acta. 23A, 237 (1967).

    Google Scholar 

  42. T. Shimanouchi, J. Phys. Chem. Ref. Data 2, 238 (1973).

    Google Scholar 

  43. T.J. Lee and J.E. Rice, J. Chem. Phys. 97, 4223 (1992).

    Article  CAS  Google Scholar 

  44. J. Sehested and T.J. Wallington, Environ. Sci. Technol. 27, 146 (1993).

    Article  CAS  Google Scholar 

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  1. Centre for Atmospheric Chemistry and Department of Chemistry, York University, 4700 Keele Street, M3J1P3, North York, Ontario, Canada

    H. Niki, J. Chen & V. Young

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  1. H. Niki
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  2. J. Chen
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Niki, H., Chen, J. & Young, V. Long path-FTIR studies of some atmospheric reactions involving CF3OO and CF3O radicals. Res Chem Intermed 20, 277–301 (1994). https://doi.org/10.1163/156856794X00342

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