The Mechanism of Orientation in i-Butyl and i-Amyl Bromide Glasses

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Abstract
The relaxation times of two typical, unassociated polar molecules have been calculated from experimental dispersion data. Both Stokes' law and absolute reaction rate theories have been applied to show that the inner friction constant in the usual Debye relaxation formula must be considered in terms of a mechanism involving higher activation energies than those obtaining in ordinary viscousflow. Hence, the macroscopic viscosity will generally be inadequate as an inner friction constant for relaxation. Slight alterations in the structure of these molecules are found apparently to change their relative orientations and hence energies of interaction. Rotational motion in viscousflow of lesser degree but similar kind to that of relaxation is indicated by the parallelism between the respective energies in i‐butyl and i‐amyl bromides. Possible generalizations have been extended to relaxation and flow phenomena in liquid crystals, where effectively the co‐existence of phases derived from a single component over a temperature range makes the structure considerations simpler than in the usual case of solutions.

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