Dielectric Study of Tetraalkylammonium and Tetraalkylphosphonium Levulinate Ionic Liquids.

ABSTRACT

Broadband dielectric spectroscopy in a broad temperature range was employed to study ionic conductivity and dynamics in tetraalkylammonium- and tetraalkylphosphonium-based ionic liquids (ILs) having levulinate as a common anion. Combining data for ionic conductivity with data obtained for viscosity in a Walden plot, we show that ionic conductivity is controlled by viscosity while a strong association of ions takes place. Higher values for ionic conductivities in a broad temperature range were found for the tetraalkylphosphonium-based IL compared to its ammonium homolog in accordance with its lower viscosity. Levulinate used in the present study as anion was found to interact and associate stronger with the cations forming ion-pairs or other complexes compared to the NTf2 anion studied in literature. In order to analyze dielectric data, different fitting approaches were employed. The original random barrier model cannot well describe the conductivity especially at the higher frequencies region. In electric modulus representation, two overlapping mechanisms contribute to the broad low frequencies peak. The slower process is related to the conduction mechanism and the faster to the main polarization process of the complex dielectric permittivity representation. The correlation of the characteristic time scales of the previous relaxation processes was discussed in terms of ionic interactions.