Dielectric Saturation and Hydrogen Bonding

Abstract

A new type of effect of dielectric saturation, as found by J. Mal/ecki in alcohols and their solutions in nondipolar solvents, consists in the fact that an external electric field raises the dielectric permittivity of solutions of low concentration and lowers that of strong ones. The rise in permittivity (positive saturation effect) is due to the presence of dimers, whereas its decrease (negative saturation effect)—to multimers, chiefly tetramers. The latter effect is essentially one of orientation of the multimers in the electric field. In addition, the proton shift due to the electric field introduces a small variation in the electric moment of the multimers, but raises that of the dimers very considerably, leading to the positive saturation effect in alcohol solutions of low concentration.