Chlorine‐photosensitized reactions in the Cl2+ O2+ 1,1,1,2‐C2H2Cl4system
作者:
D. Gillotay,
J. Olbregts,
期刊:
International Journal of Chemical Kinetics
(WILEY Available online 1976)
卷期:
Volume 8,
issue 1
页码: 11-22
ISSN:0538-8066
年代: 1976
DOI:10.1002/kin.550080103
出版商: John Wiley&Sons, Inc.
数据来源: WILEY
摘要:
AbstractThe gas‐phase photochlorination (λ = 436 nm) of the 1,1,1,2‐C2H2Cl4has been studied in the absence and the presence of oxygen at temperatures between 360 and 420°K. Activation energies have been estimated for the following reaction steps:\documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm CCl}_3 {\rm CHCl}^{\rm .} + {\rm Cl}_2 \to {\rm CCl}_3 {\rm CHCl}_{\rm 2} + {\rm Cl}^{\rm .}} & {E_3 = (4.6 \pm 0.4){\rm kcal/mole}} \\ \end{array}$$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm CCl}_3 {\rm CHCl}^{\rm .} \to {\rm CCl}_2 {\rm CHCl} + {\rm Cl}^{\rm .}} & {E_4 = (20.6 \pm 1.4){\rm kcal/mole}} \\ \end{array}$$\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$$\begin{array}{*{20}c} {{\rm CCl}_3 {\rm CHClO}_{\rm 2} {\rm CHClCCl}_3 \to 2{\rm CCl}_3 {\rm CHClO}^{\rm .}} & {E_{15} = (33.5 \pm 3.0){\rm kcal/mole}} \\ \end{array}$$\end{document}The dissociation energyD(CCl3CHClO2) ± (24.8 ± 1.5) kcal/mole has also been estimated from the difference in activation energy of the direct and reverse reactionsThe mechanism is discussed and the rate parameters are compared to those obtained for a series of other chlorinate
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