The atmospheric chemistry of dimethylsulfoxide (DMSO) kinetics and mechanism of the OH+DMSO reaction |
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| Authors: | A. J. Hynes P. H. Wine |
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| Affiliation: | (1) Division of Marine and Atmospheric Chemistry, Rosenstiel School of Marine and Atmospheric Science, University of Miami, 4600 Rickenbacker Causeway, 33149 Miami, FL, U.S.A.;(2) School of Chemistry and Biochemistry, Georgia Institute of Technology, 30332 Atlanta, GA, U.S.A.;(3) School of Earth and Atmospheric Sciences, Georgia Institute of Technology, 30332 Atlanta, GA, U.S.A.;(4) Georgia Technical Research Institute, Georgia Institute of Technology, 30332 Atlanta, GA, U.S.A. |
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| Abstract: | We have employed a pulsed laser photolysis-pulsed laser induced fluorescence technique to study the kinetics and mechanism of the reaction of OH with dimethylsulfoxide and its deuterated analogue. A rate coefficient of (1.0±0.3)×10-10 cm3 molecule-1 s-1 was obtained ar room temperature. The rate coefficient was independent of pressure over the range 25–700 Torr, showed no dependence on the nature of the buffer gas and showed no kinetic isotope effect. A limited study of the temperature dependence indicated that the reaction displays a negative activation energy. The gas phase ultraviolet absorption spectrum was obtained at room temperature and showed a strong absorption feature in the far ultraviolet. The absolute absorption cross-section at 205 nm, the absorption peak, is (1.0±0.3)×10-17 cm2, where the large uncertainty results from experimental difficulties associated with the low vapor pressure and  stickiness of DMSO. |
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| Keywords: | hydroxyl radical dimethylsulfoxide kinetics sulfur cycle |
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