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Absolute rate constants for the reactions O( 3 P ) atoms with HCl and HBr
Author(s) -
Brown Raymond D. H.,
Smith Ian W. M.
Publication year - 1975
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.550070211
Subject(s) - chemistry , afterglow , halide , arrhenius equation , reaction rate constant , hydrogen , analytical chemistry (journal) , nitrogen , hydrogen halide , oxygen , reaction rate , inorganic chemistry , kinetics , halogen , organic chemistry , catalysis , activation energy , physics , alkyl , gamma ray burst , quantum mechanics , astronomy
A flow tube method has been used to determine rate constants for the elementary reactions:Oxygen atoms were produced by adding a small excess of NO to a stream of partially dissociated nitrogen, and their reaction with hydrogen halide was monitored by observing the intensity of the NO + O afterglow. Experiments were carried out at temperatures from 293 to 440°K with HCl, and from 267 to 430°K with HBr. The role of secondary reactions was minimised and the residual effects were allowed for. The rate constants for the primary reactions could be matched by Arrhenius expressions:\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1a} = 2.5\left({_ - ^ + } \right.\left. {{}_{0.8}^{1.2} } \right) \times 10^{ - 12} \,{\rm exp}\frac{{{\rm ( - 5}{\rm .9} \pm {\rm 0}{\rm .3}\,{\rm kcal/mole)}}}{{RT}} $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ k_{1b} = 4.0( \pm 0.7) \times 10^{ - 12} \,{\rm exp}\frac{{{\rm ( - 2}{\rm .7} \pm {\rm 0}{\rm .1}\,{\rm kcal/mole)}}}{{RT}} $$\end{document} where the units are cm 3 /molec·sec and the errors correspond to a standard deviation.