ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The thermal dehydrochlorination CF2ClCH3 → CF2 = CH2 + HCl has been studied in a static system between 637 and 758 K. It is a homogeneous, molecular first-order reaction and its rate constant is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{{\rm 10}} {\rm }(k,{\rm s}^{ - {\rm 1}}) = - (53,400 \pm 100)/4.576{\rm T + (12}{\rm .21} \pm {\rm 0}{\rm .03)} $$\end{document} This reaction has also been studied in the presence of CCl4 and mixtures of CCl4 and HCl between 585 and 662 K. It is then accelerated and the initial rate increase is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ v = d[{\rm CF}_{\rm 2} {\rm = CH}_{\rm 2} ]/dt = k' \left( {1 + k'' {\textstyle{{{\rm [HCl]}} \over {{\rm [CF}_{\rm 2} {\rm ClCH}_{\rm 3} {\rm ]}}}}} \right)^{{\raise0.5ex\hbox{$\scriptstyle 1$}\kern-0.1em/\kern-0.15em\lower0.25ex\hbox{$\scriptstyle 2$}}} [{\rm CF}_2 {\rm ClCH}_3 ]^{{\raise0.5ex\hbox{$\scriptstyle 3$}\kern-0.1em/\kern-0.15em\lower0.25ex\hbox{$\scriptstyle 2$}}} $$\end{document} with log10 (k′, L½ /mol½ · s) = -(41,650 ± 180)/4.576T + (10.84 ± 0.06) and log10 k″ = (7900 ± 180)/4.576T - (0.59 ± 0.06). A radical chain mechanism is shown to be consistent with these latter results.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550170204
