Abstract
The oxidation of carbon disulphide has been studied under conditions which are likely to pertain in the atmosphere. The quantum yield for direct photo-oxidation of CS2 in air at 1 atm pressure, using near UV radiation was 0.012, with OCS as a major product. The rate coefficient (k 1) for the reaction of OH with CS2, was determined from measurements of OCS formation in the near UV photolysis of HONO−CS2−O2−N2 mixtures. k 1 was dependent on oxygen concentration rising from ≤4×10-14 cm3 molecule-1 s-1 at O2≤15 Torr to (2.0±1.0)×10-12 cm3 molecule-1 s-1 at 1 atm air and 300 K. Equimolar amounts of carbonyl sulphide and sulphur dioxide were the major reaction products.
The concentration of carbon disulphide in the ambient atmosphere was measured and the concentration to be expected in the background atmosphere was estimated. Rate and concentration data were used to show that carbon disulphide oxidation represents a major source for atmospheric carbonyl sulphide. It can also serve as an alternate source for atmospheric sulphur dioxide in addition to that produced from hydrogen sulphide and dimethyl sulphide.
A consideration of atmospheric concentrations and rate data for these trace sulphur gases suggests that the natural sulphur budget is much smaller than the yearly amounts of sulphur dioxide emitted from anthropogenic sources.
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Jones, B.M.R., Cox, R.A. & Penkett, S.A. Atmospheric chemistry of carbon disulphide. J Atmos Chem 1, 65–86 (1983). https://doi.org/10.1007/BF00113980
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DOI: https://doi.org/10.1007/BF00113980