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A flash photolysis–resonance fluorescence kinetics study of ground‐state sulfur atoms: I. Absolute rate parameters for reaction of S( 3 P ) with O 2 ( 3 Σ).
Author(s) -
Davis D. D.,
Klemm R. B.,
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.550040402
Subject(s) - chemistry , arrhenius equation , flash photolysis , resonance fluorescence , photodissociation , diluent , kinetics , fluorescence , sulfur , ground state , chemical kinetics , reaction rate constant , photochemistry , atmospheric temperature range , analytical chemistry (journal) , resonance (particle physics) , activation energy , atomic physics , thermodynamics , organic chemistry , physics , quantum mechanics
The flash photolysis–resonance fluorescence technique has been used to measure the reaction of ground‐state sulfur atoms with molecular oxygen as a function of both temperature and total pressure. The most suitable source of S( 3 P ) for this study was found to be COS in the presence of CO 2 , as a diluent gas and with the photolysis flash filtered so as to remove all radiation of wavelengths below 1650 Å. Under these conditions, it was found that over the temperature range of 252–423°K the rate data could be fit to a simple Arrhenius‐type equation of the form\documentclass{article}\pagestyle{empty}\begin{document}$$k_1 = (2.24 \pm 0.27) \times 10^{ - 12} {\rm exp}\left({\frac{{{\rm - 0}{\rm .00} \pm {\rm 0}{\rm .10 kcal/mole}}}{{RT}}} \right)$$\end{document} Units are cm 3 molec −1 s −1 . The small A ‐factor for this reaction, the lack of any pressure dependence, and the direct observation of the production of O( 3 P ) with increasing reaction time suggest that the S( 3 P ) atom attacks the O 2 ( 3 Σ) molecule end‐on forming SOO which rapidly falls apart to form SO ( 3 Σ) and O( 3 P ).