Ozone kinetics of dimethyl sulfide in the presence of water vapor

Abstract

The outdoor smog chamber was used to thorough investigate the rate constants of gas-phase reaction between dimethyl sulfide (DMS) and ozone (O₃) under conditions of relative humidity 55.0%–67.8% at (296±2)K for the first time. The rate constants were measured, at a total pressure of 1 atm, to be (10.4±0.2) × 10^-19 cm³·molecule^-1·s^-1 at relative humidity of 67.5%±0.3% at 298K, (10.1±0.1) × 10^-19 cm³·molecule^-1·s^-1 at relative humidity of 66.5%±0.5% at 296K, (7.75±0.39) × 10^-19 cm³·molecule^-1·s^-1at relative humidity of 64.8%±0.1% at 294K and (3.42±0.21) × 10^-19 cm³·molecule^-1·s^-1at relative humidity of 55.8%±0.8% at 295K. Base on these results, it is possible to see the reaction of O₃/DMS in the presence of water vapor as an important sink for DMS in the earth atmosphere.

Keywords

rate constants / ozone (O₃) / dimethyl sulfide (DMS) / water vapor

References

[1] Fairall C W, Yang M, Bariteau L, Edson J B, Helmig D, McGillis W, Pezoa S, Hare J E, Huebert B, Blomquist B., Implementation of the coupled ocean-atmosphere response experiment flux algorithm with CO₂, dimethyl sulfide, and O₃. Journal of Geophysical Research, 2011, 116(C00F09): doi: 10.1029/2010JC006884

[2] Bates T S, Lamb B K, Guenther A, Dignon J, Stoiber R E. Sulfur emissions to the atmsphere for natural sources. Journal of Atmospheric Chemistry, 1992, 14(1–4): 315–337

[3] Winer A M, Atkinson R, Pitts J N. Gaseous nitrate radical: possible nighttime atmospheric sink for biogenic organic compounds. Scince, 1984, 224(4645): 156–159

[4] Stickel R E, Nicovich J M, Wang S, Zhao Z, Wine P H. Kinetic and mechanistic study of the reaction of atomic chlorine with dimethyl sulfide. Journal of Physical Chemistry, 1992, 96(24): 9875–9883

[5] Wang H T, Zhang Y J, Mu Y J. Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide. Journal of Environmental Sciences-China, 2007, 19(6): 641–643

[6] Lee Y, Zhou X. Aqueous reaction kinetics of ozone and dimethylsulfide and its atmospheric implications. Journal of Geophysical Research, 1994, 99(D2): 3597–3605

[7] Barcellos Da Rosa M, Behnke W, Zetzsch C. Study of the heterogeneous reaction of O₃ with CH₃SCH₃ using the wetted-wall flowtube technique. Atmospheric Chemistry and Physics, 2003, 3(5): 1965–1673

[8] Du L, Xu Y, Ge M, Jia L, Yao L, Wang W. Rate constant of gas-phase of reaction of dimethyl sulfide (CH₃SCH₃) with ozone. Chemical Physics Letters, 2007, 436(1–3): 36–40

[9] Hatakeyama S, Leu M T. Rate constants for reactions between atmospheric reservoir species.2.water. Journal of Physical Chemistry, 1989, 93(15): 5784–5789

[10] Arin L M, Warneck P. Reaction of ozone with carbon monoxide. Journal of Physical Chemistry, 1972, 76(11): 1514–1516

[11] Kosak-Channing L F, Helz G R. Solubility of ozone in aqueous solutions of 0-0.6 M ionic strength at 5°C–30°C. Environmental Science & Technology, 1983, 17(3): 145–149

[12] Eberhard R, Hendrik S, Adrian S. Ozone solubilities in water and aqueous salt solutions. Journal of Chemical & Engineering Data, 2000, 45(2): 338–340

[13] Martinez R I, Herron J T. Stopped-flow study of the gas-phase reaction of ozone with organic sulfides: dimethyl sulfide. International Journal of Chemical Kinetics, 1978, 10(5): 433–452

[14] Gershenzon M, Davidovits P, Jaync J T, Kolb C E, Worsnop D R. Simultaneous uptake of DMS and ozone on water. Journal of Physical Chemistry A, 2001, 105(29): 7031–7036

[15] Stotelo J L, Beltran F J, Benitez F J, Beltran-Heredia J. Henry’s law constant for the ozone-water system. Water Research, 1989, 23(10): 1239–1246

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Grant No. 21177158).

RIGHTS & PERMISSIONS

2014 Higher Education Press and Springer-Verlag Berlin Heidelberg