Dielectric relaxation of lithium and sodium perchlorates in 1,2-dimethoxyethane and propylene carbonate

Abstract

The complex permittivity of LiClO4 and NaClO4 solutions in 1,2-dimethoxyethane (DME) has been measured in the frequency range 0.140–123.2 GHz. The data have been analysed according to a model for the reorientation of ion pairs given in a previous paper. The dielectric data are supplemented by conductivity measurements in a broad concentration range (10−4–1 mol/L) which evidence the large extent of salt association. The main result is that the solvation of Li+ and Na+ by DME cannot be described as simply as in the case of other solvents, such as tetrahydrofuran or ethyl acetate, as far as the dielectric properties are concerned: while the assumption of rigidly bound solvating molecules was acceptable for the latter solvents, some freedom in the reorientation of these molecules has to be taken into account for the case of DME. LiClO4 solutions in propylene carbonate (PC) + benzene and PC + DME mixtures have also been studied. The data, for the latter, can be qualitatively interpreted under the assumption that PC molecules take the place of DME molecules in the solvation sheath, even at low PC concentration.