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

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).