Some catalysed halogen addition reactions in carbon tetrachloride

Abstract

The study of the kinetics of halogen addition to ethylenic bonds began some forty years ago with the work of Bauer (1) who was the first to observe the effect of substituent groups upon the rate of addition of bromine. Hertz and Mylius (2), Bauer and Moser (3), noted that the rate of addition varied with the solvent employed and that iodine has a considerable catalytic effect in carbon tetrachloride and carbon bisulphide. These workers and others (4,5,6), stated that the reactions were bimolecular. Most of this early work was carried out in non-dissociating solvents, and the results obtained varied widely, although a similar technique was employed in all cases. According to Sudborough & Thomas (6):.... "The values of K for any given compound are not very concordant. Other authorities have noticed this fact (compare Hertz & Mylius, Hofmann & Kirmreuther, loc. cit.) The only reason that we can offer is that a trace of some impurity has a considerable effect upon the velocity of the reaction."