The Dielectric Properties of Crystalline Long-Chain n-Primary Alcohols at Low Frequencies

In a previous paper it was reported that certain crystalline forms of long-chain secondary alcohols show abnormally large dielectric absorption and dispersion of the dielectric constant at audio and radio frequencies. The present paper describes an extension of the investigation to n-primary alcohols and discusses the results in terms of the previously suggested theory of dielectric absorption due to the presence of hydrogen-bonded chains of hydroxyl groups. The most significant feature of the results is that the absorption is larger and occurs at much lower frequencies than for the secondary alcohols. This is considered to be due to the end-to-end arrangement of the molecules in n-primary alcohol crystals, which gives double layers of hydroxyl groups and enables the formation of more extensive hydrogen-bond chains. The dielectric constants at the lowest frequencies are almost as large as those previously reported by Hoffmann and Smyth (1949) for the " waxy " forms of n-primary alcohols. Further aspects described are the changes in dielectric properties during storage, the differences between the melted and recrystallized forms, and the effect of dispersing the molecules in an inert solid solvent. In each of these aspects the observed behaviour is similar to that previously reported for the secondary alcohols.