Designing the ammonium cation to achieve a higher hydrophilicity of bistriflimide-based ionic liquids.

In this work, we have found complete water miscibility for a priori, water immiscible (highly hydrophobic) ionic liquids by chemical manipulation of the quaternary ammonium cation grafted with hydroxyethyl moieties. Specifically, we were able to obtain bistriflimide-based ionic liquids completely miscible with water, even below room temperature. The underlying reason is the full integration of the OH groups of the cation in the continuous H-bonded network of water.

Fluorination effects on the thermodynamic, thermophysical and surface properties of ionic liquids.

This paper reports the thermal, thermodynamic, thermophysical and surface properties of eight ionic liquids with fluorinated alkyl side chain lengths equal or greater than four carbon atoms. Melting and decomposition temperatures were determined together with experimental densities, surface tensions, refractive indices, dynamic viscosities and ionic conductivities in a temperature interval ranging from 293.15 to 353.15 K. The surface properties of these fluorinated ionic liquids were discussed and several thermodynamic functions, as well as critical temperatures, were estimated. Coefficients of isobaric thermal expansion, molecular volumes and free volume effects were calculated from experimental values of density and refractive index and compared with previous data. Finally, Walden plots were used to evaluate the ionicity of the investigated ionic liquids.

Viscosity minima in binary mixtures of ionic liquids + molecular solvents.

The viscosity (η) of four binary mixtures (ionic liquids plus molecular solvents, ILs+MSs) was measured in the 283.15 < T/K < 363.15 temperature range. Different IL/MS combinations were selected in such a way that the corresponding η(T) functions exhibit crossover temperatures at which both pure components present identical viscosity values. Consequently, most of the obtained mixture isotherms, η(x), exhibit clear viscosity minima in the studied T-x range. The results are interpreted using auxiliary molecular dynamics (MD) simulation data in order to correlate the observed η(T,x) trends with the interactions in each mixture, including the balance between electrostatic forces and hydrogen bonding.

Shifts in the temperature of maximum density (TMD) of ionic liquid aqueous solutions.

This work investigates for the first time shifts in the temperature of maximum density (TMD) of water caused by ionic liquid solutes. A vast amount of high-precision volumetric data--more than 6000 equilibrated (static) high-precision density determination corresponding to ∼90 distinct ionic liquid aqueous solutions of 28 different types of ionic liquid--allowed us to analyze the TMD shifts for different homologous series or similar sets of ionic solutes and explain the overall effects in terms of hydrophobic, electrostatic and hydrogen-bonding contributions. The differences between the observed TMD shifts in the -2 < t/°C < 4 range and salting-in or salting-out effects produced by the same type of ions in aqueous solutions at higher temperatures are discussed taking into account the different types of possible solute-water interactions that can modify the structure of the aqueous phase. The results also reveal different insights concerning the nature of the ions that constitute typical ionic liquids and are consistent with previous results that established hydrophobic and hydrophilic scales for ionic liquid ions based on their specific interactions with water and other probe molecules.