Dielectric properties of glycerol/water mixtures at temperatures between 10 and 50 °c

At six temperatures T between 10 and 50 °C and at mole fractions xg of glycerol (0< xg ≤0.9) the complex (electric) permittivity ε (ν) of glycerol/water mixtures has been measured as a function of frequency ν between 1 MHz and 40 GHz. The spectra of the glycerol/water mixtures can be well represented by a Davidson-Cole [J. Chem. Phys. 18, 1417 (1950)] relaxation function that reveals an unsymmetric relaxation time distribution. The effective dipole orientation correlation factor derived from the static permittivity displays an unspectacular behavior upon mixture composition. The dielectric relaxation time reveals a simple relation to the shear viscosity of the mixtures, but both quantities are not proportional to one another. The relaxation times at high temperatures nicely complement previously determined low temperature data, following a Vogel-Fulcher-Tammann-Hesse [Z. Phys. 22, 645 (1925); J. Am. Chem. Ceram. Soc. 8, 339 (1923); Z. Anorg. Allg. Chem. 156, 245 (1926)] (VFTH) temperature dependence. When the Eyring behavior is assumed a limiting high temperature form of the VFTH relation, enthalpy, and entropy of activation values are found which adopt significantly higher values in the glycerol rich mixtures than in the water rich liquids. The relaxation time distribution parameter at high water content indicates a dynamically heterogeneous structure of the liquids. Likely there exist glycerol rich and water rich microphases.