Some Reactions of Ground-State (3P) and Electronically Excited (1D) Sulfur Atoms

Reactions of $\mathrm{S}{(}^3\mathrm{P)}$ and $\mathrm{S}{(}^1\mathrm{D)}$ have been studied by utilizing carbonyl sulfide photolysis as a source of both species. It has been shown that 46% ± 4% of the sulfur atoms generated in the photolysis of OCS in the 2250–2650‐Å spectral region can react as $\mathrm{S}{(}^3\mathrm{P)}$ , but that substantial portion of the $\mathrm{S}{(}^3\mathrm{P)}$ is likely produced by deactivating collisions of OCS molecules with $\mathrm{S}{(}^1\mathrm{D)}$ . Both $\mathrm{S}{(}^1\mathrm{D)}$ and $\mathrm{S}{(}^3\mathrm{P)}$ react with CS₂. The rate constant ratios for these reactions relative to the reactions with OCS have been determined as ∼ 1.9 and ∼ 2.4 × 10², respectively. Efficient isotopic exchange of $\mathrm{S}{(}^3\mathrm{P)}$ with CS₂ is proposed to occur by means of CS₃ formation in a reaction independent of pressure above 50 torr. The reaction of $\mathrm{S}{(}^1\mathrm{D)}$ with N₂O yields N₂, but kinetic complexities suggest the intermediate formation of a species such as N₂OS. Measurement of the quenching of the N₂ yield has led to the determination of the relative rates of collisional deactivation of $\mathrm{S}{(}^1\mathrm{D)}$ for several gases.