ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The thermal decomposition of 1,1,1-trifluoro-2-chloroethane has been investigated in the single-pulse shock tube between 1120° and 1300deg;K at total reflected shock pressures from ∼2610 to 3350 torr. Under these conditions, the major reaction is the α,α-elimination of hydrogen chloride, \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CF}_{\rm 3} {\rm CH}_{\rm 2} {\rm Cl}\mathop {{\rm \rightarrow}}\limits^{k_1 } {\rm CF}_{\rm 2} {\rm CHF} + {\rm HCl}$$\end{document} with \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log(}k_1^\infty {\rm, sec}^{ - {\rm 1}} {\rm) = 13}{\rm .3} \pm {\rm 0}{\rm .4} - (65.5 \pm 2.2{\rm kcal})/2.303RT$$\end{document} The decomposition also involves the slower α,β-elimination of hydrogen fluoride, \documentclass{article}\pagestyle{empty}\begin{document}$${\rm CF}_{\rm 3} {\rm CH}_{\rm 2} {\rm Cl}\mathop {{\rm \rightarrow}}\limits^{k_2 } {\rm CF}_{\rm 2} {\rm CHCl} + {\rm HF}$$\end{document} with the first-order rate constant given by \documentclass{article}\pagestyle{empty}\begin{document}$${\rm log(}k_2^\infty {\rm, sec}^{ - {\rm 1}} {\rm) = 12}{\rm .7} \pm {\rm 0}{\rm .5} - (67.6 \pm 2.7{\rm kcal})/2.303RT$$\end{document} At temperatures above 1270°K, two additional minor products were observed. These were identified as CF2CFCl and CF3CHCl2 and suggest C—Cl rupture as a third reaction channel leading to complicated kinetics.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550040510
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