Microwave Dielectric Relaxation of Univalent and Bivalent Electrolyte Solutions

The microwave dielectric relaxation of aqueous solutions of univalent (KCl, NaCl, NaI) and bivalent (CaCl_2, MgCl₂) electrolytes at concentrations between 0.1 and 1 M at 25 °C was investigated using a vector network analyzer (0.5≤ ν ≤ 40 GHz). The spectra of these electrolyte systems are characterized by a symmetrical broadening of the main relaxation peak and were fitted using the Cole-Cole equation. In our analysis, we provide insights into the underlying physics of the relaxation events at microscopic and mesoscopic scales by using a 3D phase space trajectory that is based on the interactions of the relaxing dipole units with their surroundings and Frohlich’s B function. The effect of the solutes on the H-bond network of water with increasing concentration is evident in the microwave dielectric spectra through decreasing dielectric strengths and relaxation times. It was found that the number of perturbed water molecules is higher in the case of bivalent electrolytes and appears to be proportional to the ionic radius. In our approach, the particular dependence between the broadening parameter α and the relaxation times τ reflects the rate of interactions between the elementary dipole units and their surroundings. We provide a quantitative analysis of the level of perturbation caused by the presence of ions in the hydrogen-bond network of water. It was found that the H-bonded network of water is highly perturbed in univalent systems compared to bivalent systems due to weaker bonded hydration shells. Finally, we found significant differences between the dielectric response of NaCl and NaI. The differences, originating in the counterions Cl^- and I^-, which are characterized by large ionic radii and consequently weaker electric fields in their vicinity, confirm that the effect of weakly hydrated ions should not be neglected in microwave dielectric spectra analysis.