Effect of the Alkyl Chain Length of the Cation on the Interactions between Water and Ammonium-Based Ionic Liquids: Experimental and COSMO-RS Studies

To improve the understanding of the molecular interactions of water with tetraalkyl ammonium-based ionic liquids (ILs) such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide, thermophysical properties such as density (ρ), speed of sound (u), viscosity (n) and refractive index (n_D) were measured and a computational study using COSMO-RS was performed. The derived properties such as excess volumes (V^E), deviation in isentropic compressibilities (Δκ_s), deviation in viscosities (Δ), and deviation in refractive indices (Δn_D) under the same experimental conditions for these systems were also estimated. The observed V^E and Δκ_s values are negative over the entire composition of ILs at all investigated temperatures, whereas Δ and Δn_D values are positive under the same experimental conditions. These results reveal that the ammonium-based ILs significantly affect the intermolecular interactions between the solvent molecules. The computational study allows a qualitative analysis of the results in terms of the ion-dipole interactions, ion-pair formation, and hydrogen bonding between ammonium-based ILs and water.