Photochemical Oxidation of Carbonyl Sulfide and Carbon Disulfide in Solid O2 at 15 K and the Molecular Complexes of the Photoproducts

Article abstract of DOI:10.1021/j150657a022

The photooxidation of OCS and CS2 in solid O2 at 15 K by UV light (λ < 300 nm) has been studied by matrix FTIR spectroscopy.The OSC/O2 system gives CO and SO2 as major products and O3, SO3, and CO2 as minor products.The product distribution is mostly the result of an S atom reaction with O2 to give SO2.The SC2/O2 system gives OCS, SO2, and O3 as major products and SO3, CO, and CO2 as minor products.The distribution of the major product is probably the result of the reactive intermediate formation of CS.More O3 is formed from CS2 than OCS.The secondary photolysis of OCS upon prolonged photolysis of the CS2/O2 system gives a more complex product distribution.Probable precursor mechanisms are examined.The IR spectra of SO2, SO3, OCS, and CO molecular complexes are identified, and some of their structural features are examined.The photooxidation is not driven to completion to the thermochemically most stable set of products.