Temperature Study of the Rates of the Reactions of Atomic Chlorine with H2S and C2H4S

Article abstract of DOI:10.1021/j100268a012

Absolute rate constants for the reaction of atomic chlorine with hydrogen sulfide, Cl + H2S -> HCl + HS (1) over the temperature range 211 to 353 K, and with episulfide, Cl + C2H4S -> C2H4 + SCl (3) over the temperature range 211 to 298 K, have been measured by the flash photolysis-resonance fluorescence technique.In both systems, the results were independent of substantial variation in reactant concentration, total pressure (Ar), and flash intensity (i.e., initial ).The rate constants were also shown to be invariant with temperature.The best representation of the reaction rate constant for the respective temperature range studied was found to be k₁ = (6.29 +/- 0.46) * 10^-11 cm³ molecule^-1 s^-1 and k₃ = (1.02 +/- 0.10) * 10^-10 cm³ molecule^-1 s^-1, respectively, where the errors are one standard deviation.An upper limit for the rate constant for the reaction Cl + OCS -> SCl + CO (2) was also obtained at 298 K.The results for reactions 1 and 2 are compared to previous studies and the potential importance of the rate constants for these reactions in the atmospheric chemistry of Earth and Venus is considered.