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Competitive chlorination–dehydrochlorination of 1,1,1,2‐C 2 H 2 Cl 4
Author(s) -
Olbregts J.
Publication year - 1979
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550110203
Subject(s) - chemistry , trichloroethylene , chlorine , chlorine atom , selectivity , carbon atom , carbon fibers , atom (system on chip) , atmospheric temperature range , photochemistry , organic chemistry , medicinal chemistry , catalysis , thermodynamics , alkyl , materials science , physics , composite number , computer science , composite material , embedded system
The competitive photochlorination and chlorine photosensitized dehydrochlorination of 1,1,1,2‐C 2 H 2 Cl 4 have been studied over the temperature range of 349.4–404.5 K after less than 1% conversion. The results are discussed and a value of\documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_{4A} (\sec ^{ - 1}) = (11.6\pm 0.6) - (16,400\pm 1000)/4.58T $$\end{document}is proposed for the reaction\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CCl}_{\rm 3} {\rm CHCl}\mathop \to \limits^{(4{\rm A)}} {\rm CCl}_{\rm 2} {\rm CHCl + Cl} $$\end{document}This result, combined with existing thermochemical data, indicates that there is no evidence of an activation energy for the addition of a Cl atom on the most chlorinated carbon in trichloroethylene: in that case the selectivity of the addition of Cl on the less chlorinated carbon should not depend on temperature.