Dielectric studies. Part XXV. Methoxy group rotation in anisole and three para-substituted anisoles

Abstract

The dielectric absorption at several microwave frequencies of anisole, p-methylanisole, and p-bromoanisole in the solvent p-xylene, and p-dimethoxybenzene in the solvent cyclohexane has been investigated at 4 to 6 temperatures. Anisole, p-methylanisole, and p-dimethoxybenzene were all found to relax mainly by methoxy group rotation, whereas the relaxation process in p-bromoanisole was very largely molecular relaxation. In the literature, considerable divergence exists for the analyses of the dielectric data of anisole and substituted anisoles into contributions from two relaxation times and the magnitude of the weight factors governing each relaxation process. Such divergencies have been explored and justifiable analyses established for these systems where the weight factors governing the relaxation processes are shown to be roughly of the same order as those estimated from group moment data. The weight factor for molecular relaxation in the pure liquid appears considerably greater than that for a dilute solution of it in a non-polar solvent.