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The atmospheric chemistry of sulphuryl fluoride, SO2F2

Item

Title (Dublin Core)

The atmospheric chemistry of sulphuryl fluoride, SO2F2

Description (Dublin Core)

The atmospheric chemistry of sulphuryl fluoride, SO<sub>2</sub>F<sub>2</sub>, was investigated in a series of laboratory studies. A competitive rate method, using pulsed laser photolysis (PLP) to generate O(<sup>1</sup>D) coupled to detection of OH by laser induced fluorescence (LIF), was used to determine the overall rate coefficient for the reaction O(<sup>1</sup>D) + SO<sub>2</sub>F<sub>2</sub> &rarr; products (R1) of <i>k</i><sub>1</sub> (220&ndash;300 K) = (1.3 &plusmn; 0.2) &times; 10<sup>&minus;10</sup> cm<sup>3</sup> molecule<sup>&minus;1</sup> s<sup>&minus;1</sup>. Monitoring the O(<sup>3</sup>P) product (R1a) enabled the contribution (α) of the physical quenching process (in which SO<sub>2</sub>F<sub>2</sub> is not consumed) to be determined as α (225&ndash;296 K)=(0.55 &plusmn; 0.04). Separate, relative rate measurements at 298 K provided a rate coefficient for reactive loss of O(<sup>1</sup>D), <i>k</i><sub>1b</sub>, of (5.8 &plusmn; 0.8) &times; 10<sup>&minus;11</sup> cm<sup>3</sup> molecule<sup>&minus;1</sup> s<sup>&minus;1</sup> in good agreement with the value calculated from (1&minus;&alpha;) &times; <i>k</i><sub>1</sub>=(5.9 &plusmn; 1.0) &times; 10<sup>&minus;11</sup> cm<sup>3</sup> molecule<sup>&minus;1</sup> s<sup>&minus;1</sup>. Upper limits for the rate coefficients for reaction of SO<sub>2</sub>F<sub>2</sub> with OH (R2, using PLP-LIF), and with O<sub>3</sub> (R3, static reactor) were determined as <i>k</i><sub>2</sub> (294 K)&lt;1 &times; 10<sup>&minus;15</sup> cm<sup>3</sup> molecule<sup>&minus;1</sup> s<sup>&minus;1</sup> and <i>k</i><sub>3</sub> (294 K)&lt;1 &times; 10<sup>&minus;23</sup> cm<sup>3</sup> molecule<sup>&minus;1</sup> s<sup>&minus;1</sup>. In experiments using the wetted-wall flow tube technique, no loss of SO<sub>2</sub>F<sub>2</sub> onto aqueous surfaces was observed, allowing an upper limit for the uptake coefficient of γ(pH 2&ndash;12)&lt;1 &times; 10<sup>&minus;7</sup> to be determined. These results indicate that SO<sub>2</sub>F<sub>2</sub> has no significant loss processes in the troposphere, and a very long stratospheric lifetime. Integrated band intensities for SO<sub>2</sub>F<sub>2</sub> 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(<sup>1</sup>D) with several important atmospheric species were determined. The results (in units of 10<sup>&minus;10</sup> cm<sup>3</sup> molecule<sup>&minus;1</sup> s<sup>&minus;1</sup>, <i>k</i><sub>(O<sup>1</sup>D + N<sub>2</sub>)</sub>=(0.33 &plusmn; 0.06); <i>k</i><sub>(O<sup>1</sup>D + N<sub>2</sub>O)</sub>=(1.47 &plusmn; 0.2) and <i>k</i><sub>(O<sup>1</sup>D + H<sub>2</sub>O)</sub>=(1.94 &plusmn; 0.5) were in good agreement with other recent determinations.

Creator (Dublin Core)

Dillon, T. J.
Horowitz, A.
Crowley, J. N.

Date (Dublin Core)

2018-01-15

Type (Dublin Core)

Text

Format (Dublin Core)

application/pdf

Identifier (Dublin Core)

10.5194/acp-8-1547-2008
https://acp.copernicus.org/articles/8/1547/2008/

Source (Dublin Core)

eISSN: 1680-7324

Language (Dublin Core)

eng
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