The Dielectric Properties of Symmetrical Long-Chain Secondary Alcohols in the Solid State

Abstract

Symmetrical long-chain secondary alcohols in the solid state show very high dielectric loss at audio and radio frequencies. This can be explained by the presence of chains of hydroxyl groups linked by hydrogen bonding and capable of reversing their direction. Further evidence of hydrogen bonding is provided by a study of the melting points of the secondary alcohols and related compounds. The amount of dielectric loss depends markedly on the manner of formation of the solid, being smallest for samples formed by recrystallization from solvents at low temperatures and largest for specimens obtained by slow cooling from the melt. The alcohols of molecular chain-lengths of 13, 15,17, and 19 carbon atoms show a considerable decrease of absorption on storing at room temperature. For alcohols of between 23 and 43 carbon atoms the loss is rather smaller with a peak at higher frequencies, but remains more constant in time. These results are interpreted in terms of competing influences of van der Waals forces and hydrogen bonds during crystal formation ; the former, which lead to a structure unsuitable for the formation of hydrogen-bond chains, are predominant at low temperatures, but become more rapidly neutralized by thermal motion, especially for the shorter molecules. The high temperature modification of the lower homologues is unstable at room temperature, and a molecular diffusion process causes the bond chains to break. Dilute systems of secondary alcohols with hydrocarbons or paraffin wax of similar molecular chain-length show very small dielectric loss suggesting a solid solution in which bond chains cannot be formed ; if the paraffin molecules are appreciably longer, the absorption is large and decreases on storing, presumably owing to the presence of a pure alcohol phase. I.