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Kinetic study of gas‐phase reactions with CF 2 Cl 2 and CFCl 3 . Analysis using the transition state theory (TST) of the chlorine atom transfer reactions by CF 3 and CH 3 radicals from halomethanes
Author(s) -
Taccone R. A.,
Salinovich O.,
Staricco E. H.
Publication year - 1987
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.550190705
Subject(s) - chemistry , radical , arrhenius equation , chlorine , transition state theory , chlorine atom , gas phase , atmospheric temperature range , kinetic energy , atom (system on chip) , reaction rate constant , analytical chemistry (journal) , thermodynamics , kinetics , activation energy , medicinal chemistry , organic chemistry , physics , quantum mechanics , computer science , embedded system
The following gas‐phase reactions:were studied by the competitive method with CF 3 I as the source of radicals. The kinetic parameters obtained in the temperature range 533–613 K and 503–613 K respectively for chlorine atom transfer reactions are given by:\documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_1 /k_c ^{1/2} ({\rm cm}^{\rm 3}\, {\rm mol}^{{\rm - 1/2}} s^{ - 1/2}) = (6.19 \pm 0.10) - (16900 \pm 100)/\theta $$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_2 /k_c ^{1/2} ({\rm cm}^{\rm 3}\, {\rm mol}^{{\rm - 1/2}} s^{ - 1/2}) = (6.52 \pm 0.10) - (14890 \pm 100)/\theta $$\end{document}where θ = 2.303 RT (cal mol −1 ). The Arrhenius A values were calculated for seven chlorine atom transfer reactions (CF 2 Cl 2 , CFCl 3 , CCl 4 with CF 3 radicals; CF 3 Cl, CF 2 Cl 2 , CFCl 3 and CCl 4 with CH 3 radicals) by using the thermochemical kinetic version of the Transition State Theory (TST).