ISSN:
0538-8066
Schlagwort(e):
Chemistry
;
Physical Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Chloroethanes react with aqueous caustic to yield either elimination or substitution products. The reaction rates were measured for the dichloroethanes, trichloroethanes, tetrachloroethanes, and pentachloroethane between 283 and 353°K. The constants of HCl eleminations referring to the rate equation \documentclass{article}\pagestyle{empty}\begin{document}$$r = k[{\rm OH}^{\rm - }][{\rm dissolved \,substrate]}$$\end{document} are given by \documentclass{article}\pagestyle{empty}\begin{document}$${\rm 1,2 - C}_{\rm 2} {\rm H}_{\rm 4} {\rm Cl}_{\rm 2} {\rm }\,k = 10^{10.99 \pm 0.03} \exp (- 23,000 \pm 50RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm 1,1,2 - C}_{\rm 2} {\rm H}_{\rm 3} {\rm Cl}_{\rm 3} {\rm}\,k = 10^{13.99 \pm 0.03} \exp (- 22,400 \pm 50/RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm 1,1,1,2 - C}_{\rm 2} {\rm H}_{\rm 2} {\rm Cl}_{\rm 4} {\rm }\,k = 10^{15.45 \pm 0.14} \exp (- 25,800 \pm 210/RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm 1,1,2,2 - C}_{\rm 2} {\rm H}_{\rm 2} {\rm Cl}_{\rm 4} {\rm }\,k = 10^{16.40 \pm 0.05} \exp (- 22,550 \pm 70/RT)$$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$${\rm C}_{\rm 2} {\rm HCl}_{\rm 5} {\rm }\,k = 10^{12.50 \pm 0.08} \exp (- 15,200 \pm 110/RT)$$\end{document} all rate constants being in 1./mole·s and R in cal/mole· deg.With ethyl chloride, 1,1-dichloroethane, and 1,1,l-trichloroethane, the elimination is not observed and a slow substitution takes place. The influence of chlorine substituents on both sides of the molecule on mechanism and rate parameters is discussed.
Zusätzliches Material:
4 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/kin.550060602
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