Premium
Kinetics of the metathetical reaction between carbon tetrachloride and toluene
Author(s) -
Shoulders Diana Curcio,
Hardwick T. J.,
Ketter Donald C.,
Pukanic George W.
Publication year - 1972
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.550040405
Subject(s) - chemistry , toluene , hydrogen chloride , carbon tetrachloride , bibenzyl , chloroform , benzyl chloride , dehydrohalogenation , chlorine , chloride , hydrogen , photochemistry , olefin fiber , medicinal chemistry , organic chemistry , inorganic chemistry , catalysis
A metathetical reaction between carbon tetrachloride and toluene to give benzyl chloride and chloroform occurs at temperatures above 200° C ( k = 4.8 × 10 10 e −32,900/ RT cc mole −1 sec −1 ). The reaction does not involve free radicals, as is shown by the kinetic behavior of the system, by the lack of effect of added free‐radical chain inhibitors, and by the absence of the expected chain termination product, hexachloroethane. The reaction is one of a general type between carbon tetrachloride and alkanes or alkylaromatics, but at the temperatures required it is often obscured by dehydrohalogenation of the product to the highly reactive olefin. At high temperatures, benzyl chloride reacts with toluene to give bibenzyl and hydrogen chloride, apparently also by a metathetical reaction. The transition state is postulated to be four‐center, in which the carbon‐chlorine and carbon–hydrogen bonds are broken and reformed: The experimental preexponential factor is in good agreement with that calculated from transition‐state theory.