A flash photolysis–resonance fluorescence kinetics study of ground‐state sulfur atoms. IV. Rate parameters for reaction of S( 3 P ) with propene and 1‐butene

Using the technique of flash photolysis‐resonance fluorescence, absolute rate constants have been measured for the reaction of S( 3 P ) with propene and 1‐butene. Variations in experimental conditions included the following: temperature (215–500° K ); total pressure a factor of 10; olefin concentration, a factor of 6; flash intensity (S atom concentration), a factor of 10. It was found that over these variations in the experimental conditions only the temperature had a measureable effect on the bimolecular rate constant. The derived Arrhenius rate expressions for the reactions (2) and (3) were as follows:\documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = \left( {6.03 \pm 0.72} \right) \times 10^{ - 12} \exp \left( {\frac{{ - 0.38 \pm 0.09kcal/mol}}{{RT}}} \right) $$\end{document}temperature range 214–500°K\documentclass{article}\pagestyle{empty}\begin{document}$$ k_3 = \left( {7.41 \pm 1.15} \right) \times 10^{ - 12} \exp \left( {\frac{{ - 0.36 \pm 0.09kcal/mol}}{{RT}}} \right) $$\end{document}Units are cm 3 molec −1 s −1 .