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The atmospheric chemistry of sulphuryl fluoride, SO2F2
Max Planck Institute for Chemistry, Mainz, Germany
Abstract. The atmospheric chemistry of sulphuryl fluoride, SO2F2, was investigated in a series of laboratory studies. A competitive rate method, using pulsed laser photolysis (PLP) to generate O(1D) coupled to detection of OH by laser induced fluorescence (LIF), was used to determine the overall rate coefficient for the reaction O(1D)+SO2F2 → products (R1) of k1 (220–300 K)=(1.3±0.2)×10−10 cm³ molecule−1 s−1. Monitoring the O(³P) product (R1a) enabled the contribution (α) of the physical quenching process (in which SO2F2 is not consumed) to be determined as α1 (225–296 K)=(0.55±0.04). Separate, relative rate measurements at 298 K provided a rate coefficient for reactive loss of O(1D), k1b, of (5.8±0.8)×10−11 cm³ molecule−1 s−1 in good agreement with the value calculated from (1−α)×k1=(5.9±1.0)×10−11 cm³ molecule−1 s−1. Upper limits for the rate coefficients for reaction of SO2F2 with OH (R2, using PLP-LIF), and with O3 (R3, static reactor) were determined as k2 (294 K)<1×10−15 cm³ molecule−1 s−1 and k3 (294 K)<1×10−23 cm³ molecule−1 s−1. In experiments using the wetted-wall flow tube technique, no loss of SO2F2 onto aqueous surfaces was observed, allowing an upper limit for the uptake coefficient of γ(pH 2–12)<1×10−7 to be determined. These results indicate that SO2F2 has no significant loss processes in the troposphere, and a very long stratospheric lifetime. Integrated band intensities for SO2F2 infrared absorption features between 6 and 19 μm were obtained, and indicate a significant global warming potential for this molecule. In the course of this work, ambient temperature rate coefficients for the reactions O(1D) with several important atmospheric species were determined. The results (in units of 10−10 cm³ molecule−1 s−1), k(O1D+N2)=(0.33±0.06); k(O1D+N2O)=(1.47±0.2) and k(O1D+H2O)=(1.94±0.5) were in good agreement with other recent determinations.
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Citation: Dillon, T. J., Horowitz, A., and Crowley, J. N.: The atmospheric chemistry of sulphuryl fluoride, SO2F2, Atmos. Chem. Phys. Discuss., 7, 15213-15249, 2007. Bibtex EndNote Reference Manager
