We have investigated production of carbon- and sulfur-containing end products of the OH-initiated oxidation of CS2 in the presence of O2, an important atmospheric chemical reaction which is known to proceed via the following three elementary steps: OH + CS2 + M ↔ CS2OH + M; CS2OH + O2 → products. Two different experimental approaches were employed. In one set of experiments (CP-FTIR studies) continuous photolysis of CH3ONO/NO/CS2/Air mixtures at 298 K and 700-Torr total pressure was combined with product detection by Fourier transform infrared spectroscopy; these studies measured moles of products formed per mole of CS2 consumed. In a second set of experiments (LFP-TDLAS studies) 248-nm laser flash photolysis of H2O2/ CS2/N2O/He/O2 mixtures at 298 K and 25-100-Torr total pressure was combined with product detection by time-resolved tunable diode laser absorption spectroscopy; in this case, the quantity measured was moles of product formed per mole of OH consumed. In both studies OCS and CO are observed as carbon-containing products with yields of 0.83 ± 0.08 and 0.16 ± 0.03, respectively; uncertainties represent estimates of absolute accuracy at the 95% confidence level. The LFP-TDLAS experiments demonstrate that the above yields represent "prompt" product formation; i.e., OCS and CO are formed either as primary products of the CS2OH + O2 reaction or as products of a fast (k > 10-15 cm3 molecule-1 s-1) secondary reaction of a primary product with O2. The CP-FTIR experiments show that, under atmospheric conditions, SO2 is produced with a yield of 1.15 ± 0.10; in this case, the LFP-TDLAS results strongly suggest that only about three-fourths of the SO2 is formed as a prompt product, with the remainder generated via slow reaction of SO (generated as a prompt product of the CS2OH + O2 reaction) with O2. The implications of our results for understanding the detailed mechanism of the very complex CS2OH + O2 reaction are discussed, as are their implications for understanding the atmospheric cycles of CS2 and OCS.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry