On the Coupling between Ionic Conduction and Dipolar Relaxation in Deep Eutectic Solvents: Influence of Hydration and Glassy Dynamics

Abstract: We have studied the ionic conductivity and the dipolar reorientational dynamics of aqueous solutions of a prototypical deep eutectic solvent (DES), ethaline, by using dielectric spectroscopy on a broad range of frequency (MHz-Hz) and for temperatures ranging from 128 to 283 K. The fraction of water in the DES was varied systematically to cover different regimes, starting from pure DES and its water-in-DES mixtures to the diluted electrolyte solutions. Depending on these parameters, different physical states were examined, including low viscosity liquid, supercooled viscous liquid, amorphous solid and freeze-concentrated solution. The ionic conductivity and the reorientational relaxation both exhibited characteristic features of glassy dynamics that could be quantified from the deviation from Arrhenius temperature dependence and non-exponential decay of the relaxation function. A transition occurred between the water-in-DES regime, (< 40 wt %),where the dipolar relaxation and ionic conductivity remained inversely proportional to each other, and the DES-in-water regime, (> 40 wt %), where a clear rotation-translation decoupling was observed. This suggests that for low water content, on the timescale covered by this study (~10-6 s to 1 s), the rotational and transport properties of ethaline aqueous solutions obey classical hydrodynamic scaling despite these systems being presumably spatially microheterogeneous. A fractional scaling is observed in the DES-in-water regime, due to the formation of a maximally freeze-concentrated DES aqueous solution coexisting with frozen water domains at sub-ambient temperature.