ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The kinetics of the gamma-radiation-induced free radical chain reaction in solutions of C2Cl3F in cyclohexane (RH) was investigated over a temperature range of 87.5-200°C. The following rate constants and rate constant ratios were determined for the reactions: \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (2a)}} & {{\rm R} + {\rm C}_{\rm 2} {\rm Cl}_{\rm 3} {\rm F} \to {\rm RCClFCCl}_{\rm 2}} \\ \end{array}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {(2{\rm b})} & \to \\ \end{array}{\rm RCCl}_{\rm 2} {\rm CClF}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c}{{\rm (3a)}} & {{\rm RCClFCCl}_{\rm 2} \to {\rm RCF}}\\ \end{array}{\raise1pt\hbox{$\Relbar \kern-4pt{\Relbar}$}}{\rm CCl}_{\rm 2} + {\rm Cl}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (4a)}} & {{\rm RCClFCCl}_{\rm 2} + {\rm RH} \to {\rm RCClFCCl}_{\rm 2} {\rm H} + {\rm R}} \\ \end{array}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_{2a} ({\rm mole}^{{\rm - 1}} 1.\,{\rm sec}^{{\rm - 1}}) = (8.64 \pm 0.35) - (6.38 \pm 0.41)/\theta ^1$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_{{\rm 2b}} /k_{{\rm 2a}} = (- 0.03 \pm 0.15) - (2.39 \pm 0.28)/\theta$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm (}k_{3{\rm a}} /k_{4{\rm a}})({\rm mole}\,1.^{{\rm - 1}}) = (6.17 \pm 0.10) - (10.14 \pm 0.18)/\theta$$\end{document} In competitive experiments in ternary solutions of C2Cl4 and C2Cl3F in cyclohexane the rate constant ratio k2c/k2a was determined \documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm (2c)}} & {{\rm R} + {\rm C}_{\rm 2} {\rm Cl}_{\rm 4} \to {\rm RC}_{\rm 2} {\rm Cl}_{\rm 4}} \\ \end{array}$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$\log {\rm }k_{{\rm 2c}} /k_{{\rm 2a}} = (0.13 \pm 0.06) - (1.20 \pm 0.12)/\theta$$\end{document} By comparing with previous data for the addition of cyclohexyl radicals to other chloroethylenes it is shown that in certain cases the trends in activation energies for cyclohexyl radical addition can be correlated with the C—Cl bond dissociation energies in the adduct radicals.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550060206
