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A flash photolysis–resonance fluorescence kinetics study of ground‐state sulfur atoms. II. Rate parameters for reaction of S( 3 P ) with C 2 H 4
Author(s) -
Davis D. D.,
Klemm R. B.,
Braun W.,
Pilling M.
Publication year - 1972
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550040403
Subject(s) - chemistry , arrhenius equation , reaction rate constant , flash photolysis , ethylene , analytical chemistry (journal) , torr , atmospheric temperature range , resonance fluorescence , kinetics , chemical kinetics , kinetic energy , photodissociation , fluorescence , activation energy , photochemistry , thermodynamics , organic chemistry , catalysis , physics , quantum mechanics
Absolute rate constants for the reaction of S( 3 P ) with ethylene were measured over an ethylene concentration range of 7, a total pressure of 50 to 400 torr, and a flash intensity range of 10. At 298°K, the bimolecular rate constant was found to be invariant over this range of variables and had a measured value of 4.96 × 10 −13 cm 3 molec −1 s −1 . Over the temperature range of 218° to 442°K, the rate data could be fit to a simple Arrhenius equation of the form\documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = (7.13 \pm 0.74) \times 10^{ - 12} {\rm exp}\left({\frac{{{\rm - 1}{\rm .58} \pm {\rm 0}{\rm .08 kcal/mole}}}{{RT}}} \right)$$\end{document} Units are cm 3 molec −1 s −1 . The dependence of the measured value of k 1 on the concentration of the reaction product ethylene episulfide is discussed.