ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The thermal addition of CF3O3CF3(T) to CF2CCl2(E) has been investigated between 49.6 and 69.5°C. The initial pressure of CF3O3CF3 was varied between 7 and 240 torr and that of CF2CCl2 between 4 and 600 torr. Four products of formula CF3O(E)j OOCF3, where j = 1 → 4 are formed. The sum of the products Σi = 14 CF3O(E)jOOCF3 is equal to the amount of trioxide decomposed.The reaction is homogeneous. Its rate is not affected by the total pressure and the presence of inert gas. It is a free radical telomerization with four basic steps: thermal decomposition of CF3O3CF3 into CF3O. and CF3O2., chain initiation by addition of CF3O. to olefin incorporated in, and telomeric radicals termination.The consumption of alkene is well represented by the equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ - d[E]/dt = k_1 [T]\left\{ {1 + \sum\limits_{j = 1}^3 {\prod\limits_{i = 1}^j {[1 + (k_{t_1 } k_1^{1/2} /k_{gi} } k_t^{1/2})([T]^{1/2} /[E])]^{ - 1} } } \right\} $$\end{document} where (d[E]/d[T]) = \documentclass{article}\pagestyle{empty}\begin{document}$$ \bar n $$\end{document} is the mean chain length of telomerization. \documentclass{article}\pagestyle{empty}\begin{document}$$ \bar n $$\end{document} varies from 1.45 at 1.5 torr of E to 3.3 at 400 torr of E. Above this pressure E has no influence on \documentclass{article}\pagestyle{empty}\begin{document}$$ \bar n $$\end{document}.The estimated value of the constant for the addition of telomeric radicals to alkene is:\documentclass{article}\pagestyle{empty}\begin{document}$$ k_g \simeq 8.6 \pm 6.0 \times 10^4 \exp ( - 2300 \pm 200{\rm col mol}^{{\rm - 1}} /RT){\rm M}^{{\rm - 1}} {\rm s}^{{\rm - 1}} $$\end{document}
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550181204
