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Absolute rate constants for the reactions of O( 3 P ) atoms and OH radicals with SiH 4 over the temperature range of 297–438°K
Author(s) -
Atkinson R.,
Pitts J. N.
Publication year - 1978
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.550101105
Subject(s) - chemistry , radical , arrhenius equation , flash photolysis , reaction rate constant , atmospheric temperature range , photodissociation , resonance fluorescence , photochemistry , activation energy , analytical chemistry (journal) , fluorescence , kinetics , thermodynamics , organic chemistry , physics , quantum mechanics
Absolute rate constants for the reaction of SiH 4 with O( 3 P ) atoms and OH radicals have been determined over the temperature range 297°–438°K using flash photolysis–NO 2 chemiluminescence and flash photolysis–resonance fluorescence techniques, respectively. The Arrhenius expressions obtained are\documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 ^{{\rm O}(3{\rm P})} = 6.84 \times 10^{- 12} {\rm e}^{{\rm - (1580} \pm {\rm 300)/RT}} {\rm cm}^{\rm 3} {\rm molecule}^{{\rm - 1}} {\rm sec}^{{\rm - 1}} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 ^{{\rm OH}} = 1.44 \times 10^{- 11} {\rm e}^{{\rm - (95} \pm 4{\rm 00)/RT}} \,{\rm cm}^{\rm 3} \,{\rm molecule}^{{\rm - 1}} \,{\rm sec}^{{\rm - 1}} $$\end{document}where the error limits in the Arrhenius activation energies are the estimated overall error limits. Rate data for the reactions of SiH 4 , CH 4 , and H 2 S with O( 3 P ), H, and F atoms and with OH, CH 3 , and CF 3 radicals are compared, showing that H 2 S and SiH 4 , which have similar bond energies, have reasonably similar reactivities toward these atoms and radicals.