Dielectric Relaxation and Hydration Interactions for Protic and Aprotic Ionic Liquids using Time Domain Reflectometry

H-Bonding abilities of ionic liquids (ILs) along with hydrophobicity and cooperativity effects increases their hydration numbers making them capable for dissolving sparingly soluble organic molecules in aqueous or polar nonaqueous media, and hence ILs are potential candidates in pharmaceutical and medicinal sciences besides the different technological and academic interests. In this work, dielectric spectra were measured and analyzed for diethylammonium-based protic ionic liquids (PILs), imidazolium-based aprotic ionic liquids (APILs), and their aqueous solutions (∼0.02 to ∼0.8 mol·dm^-3) over a frequency range from 0.01 to 50 GHz using time domain reflectometry at 298.15 K. The Cole-Cole (CC) model for neat ILs and a combination of the Debye and Cole-Cole (D+CC) models for their aqueous solutions best describes the experimental dielectric relaxation spectra. Higher values of static permittivity and relaxation time were observed for less viscous PILs compared to more viscous APILs due to the existence of hydrogen bonding in PILs, ionic translational motion, and the existence of transient, short-lived proton transfer responsible for solvent polarization. For aqueous solutions of ionic liquids, the fast collective relaxation of solvent (bulk water) observed at higher frequencies (∼20 GHz) and slow relaxation is detected at lower frequency (∼5 to ∼10 GHz) due to hydrophobic hydration with or without cooperative H-bonding effect. The apparent concentrations of bulk water, c_bw^ap, and slow water, c_sw^ap, were used to obtain effective hydration numbers to understand the ion solvation. Hydration numbers revealed that imidazolium-based APILs are weakly hydrated than the diethylammonium-based PILs. Static permittivity and relaxation time of pure ILs and of aqueous solutions of studied ILs are discussed in terms of effect on alkyl chain length of cation/anion, H-bonding abilities of ions, dipole moments of ions, viscosity, hydrophobic effects, etc.