Location of Repository

A kinetics and mechanistic study of the atmospherically relevant reaction between molecular chlorine and dimethyl sulfide (DMS)

By John M. Dyke, M.V. Ghosh, David Kinnison, Giacomo Levita, Alan Morris and Dudley Shallcross

Abstract

A gas-phase kinetics study of the atmospherically important reaction between Cl2 and dimethyl sulfide (DMS)1Cl2+ CH3SCH3 productshas been made using a flow-tube interfaced to a photoelectron spectrometer. The rate constant for this reaction has been measured at 1.6 and 3.0 torr at T=(294 ± 2) K as (3.4 ± 0.7)× 10–14 cm3 molecule–1 s–1. Reaction (1) has been found to proceed via an intermediate, (CH3)2SCl2, to give CH3SCH2Cl and HCl as the products. The mechanism of this reaction and the structure of the intermediate were investigated using electronic structure calculations. A comparison of the mechanisms of the reactions between Cl atoms and DMS, and Cl2 and DMS has been made and the relevance of the results to atmospheric chemistry is discusse

Topics: QD
Year: 2005
OAI identifier: oai:eprints.soton.ac.uk:147211
Provided by: e-Prints Soton

Suggested articles

Preview

Citations

  1. (1994). (a) D.Wang and X.Qian J.Elect Spec Rel Phen 83, 1997, 41 (b) D.X.Wang, S.Li, D.Wang and Y.Li J.Elec Spec Rel Phen 70,
  2. (1970). A.D.Baker, and C.R.Brundle Molecular Photoelectron Spectroscopy Wiley-Interscience, doi
  3. (1992). A.Guenther, J.Dignon and R.E.Stoiber J.Atmos.Chem 14, doi
  4. (1982). A.Morris and N.Jonathan Int. Rev Phys Chem 2,
  5. (1997). Almeida J.Phys Chem A 101, doi
  6. (1995). and D.D.Davis in Composition, Chemistry and Climate of the Atmosphere van Nostrand Reinhold,
  7. Andreae and S.G. doi
  8. (2003). Atmos. doi
  9. (1998). B.J.Finlayson-Pitts, R.A.Platridge, J.M.Hubbe, D.J.Fast and C.M.Berkowitz Nature 394, doi
  10. (1999). C.Qiao and D.Wang Chem Phys Letts 299,
  11. (2001). E.Baboukas, and N.Mihalopoulos doi
  12. (1995). G.Poulet and G.LeBras J.Phys Chem 99, doi
  13. (1980). H.Rodhe and I.Isaksen J.Geophys. doi
  14. (1981). Handbook of He I photoelectron spectra Japan Scientific Societies Press,
  15. (2001). J.Hirokawa and H.Akimoto doi
  16. (2002). J.Phys Chem A 106, doi
  17. MOLPRO is a package of ab initio programs written by
  18. (2000). N.H.Savage, A.G.Allen, J.L.Grenfell, B.J.Allan, J.M.C.Plane, C.N.Hewitt, B.Davison, doi
  19. N.Jonathan and A.Morris Electron Spectroscopy Vol 3,1979, 189
  20. (1985). N.Jonathan and A.Morris J.C.S Faraday II 81, doi
  21. P.Kasibhatla, B.R.Bandy, D.C.Thornton, B.J.Huebert A.D.Clarke, and B.W.Blomquist, doi
  22. (2004). S.Hashimoto, M.Kawasaki, S.Aloisio and J.S.Francisco J.Phys Chem A 108, doi
  23. (2003). Vacuum Technology, Calculations in Chemistry, Royal Society of Chemistry, doi
  24. (1999). W.Koch, K.Miaskiewicz and I.A.Topol Chem. doi
  25. (1996). X.Qian and J.Peng Chem Phys Letts 258,

To submit an update or takedown request for this paper, please submit an Update/Correction/Removal Request.