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The vapor phase reactions of perfluoropropene, CF(3)-CF = CF(2), and perfluorobuta-1.3-diene, CF(2) = CF-CF = CF(2), with OH, NO(3) and O(3) were studied at 298+/-K and 740+/-5 Torr using long-path FT-IR detection. The reactions with ozone are very slow, kCF(3)CFCF(2)+O(3) = (6.2+/-1.5)x1E-22 and kCF(2)CFCF(2)+O(3) = (6.5+/-0.2)x1E-21 cm{3} molecules {-1}s{-1}, and upper limits of 3x1E-15 cm{3} molecules {-1}s{-1} are reported for the NO(3) reaction rate coefficients. The OH reaction rate coefficient were determined as kCF(3)CFCF(2)+OH = (2.6+/-0.7)x1E-12 and kCF(2)CFCF(2)+OH = (1.1+/-0.3)x1E-11 cm{3} molecules {-1}s{-1}; perfluoropropene gave a nearly quantitative yield of CF(3)CFO and CF(2)O as organic products, while perfluorobuta-1.3-diene gave from 130% to 170% of CF(2)O.

A chemistry transport model was applied to calculate the atmospheric distributions and lifetimes of the perfluoroalkenes. The global and yearly averaged lifetimes were calculated as 1.9 day for C(2)F(4) and C(4)F(6) and 6 days for C(3)F(6).

Quantitative infrared cross-sections of perfluoroethene, perfluoropropene, and perfluorobuta-1.3-diene have been obtained at 298 K in the region 100-2600 cm{-1}. Radiative forcing calculations have been performed for these gases assuming either constant vertical profiles or the distribution derived from the chemistry transport model. The results show that the Global Warming Potentials are totally negligible for these compounds. ds.

Additional information

Authors: ACERBONI G, JRC, Environment Institute, Ispra (IT);JENSEN N R, JRC, Environment Institute, Ispra (IT);HJORTH J, JRC, Environment Institute, Ispra (IT);BEUKES J A, University of Oslo (NO);NIELSEN C J, University of Oslo (NO);MYHRE G, University of Oslo, Department of Geophysics (NO);SUNDET J K, University of Oslo, Department of Geophysics (NO)
Bibliographic Reference: An article published in: Atmospheric Environment, Vol.35 (2001), pp.4113-4123
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