Thermo-physical properties and activity coefficients at infinite dilution for ionic liquid systems at several temperatures

Abstract

The thermodynamic properties of mixtures involving ionic liquids (ILs) with organic acid (acetic acid or propanoic acid) or acetonitrile at different temperatures were determined. The ILs used were imidazolium-based: 1-ethyl-3-methylimidazolium ethyl sulphate [EMIM]+[EtSO4]-, 1-butyl- 3-methylimidazolium thiocyanate [BMIM]+[SCN]- and 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide ([BMIM]+[Tf2N]-.

The ternary excess molar volume (V E

), isentropic compressibility (ks) and deviation in isentropic

compressibility ( ks123 ) were determined for four ternary liquid mixtures of {[EMIM]+[EtSO4]- or [BMIM]+[SCN]− + acetic or propionic acid + acetonitrile} at different temperatures (293.15, 298.15, 303.15, 308.15 and 313.15) K and at a pressure of 0.1 MPa with aid of the experimental density (ρ), speed of sound (u) data. The calculated data were correlated by using the Cibulka equation with the help of Redlich–Kister parameters obtained from fitting the Redlich–Kister equation for the corresponding binary systems.

Furthermore, the density and speed of sound were also measured for eight corresponding binary systems at the same experimental conditions. The binary excess molar volume, isentropic compressibility and deviation in isentropic compressibility were also calculated for measured systems and fitted to the Redlich–Kister equation to obtain the Redlich–Kister parameters as well as to check the accuracy of measured data which were used to correlated experimental data using Cibulka equation. These results were discussed, in terms of how the sign and magnitude of thermodynamic functions were influenced by the addition of a third component to liquid systems. Also, the possible molecular and pair-wise interactions between component molecules and the effect of temperature on the thermophysical and thermodynamic properties were predicted.

In addition, the work focussed on application of ([BMIM]+[Tf2N]-) ionic liquid for the separations of (alkane/aromatic), (alkane/alk-1-ene), (cycloalkane/aromatic) and (water/alkan-1-ol) using gas- liquid chromatography (GLC) technique. The activity coefficients at infinite dilution, , for 31 organic solutes (alkanes, cycloalkanes, alkenes, alkynes, aromatics, alkanol and ketones) and water in ionic liquid were measured at temperatures of (323.15, 333.15, 343.15, 353.15 and 363.15) K. Stationary phase loadings of (42.83 and 68.66) % by mass were used to ensure repeatability of E ,

measurements. Partial molar excess enthalpies at infinite dilution,

H1

, were also determined.

The selectivities, S , and capacities, k , were determined for the above separations. The separating ij j ability of the investigated ionic liquid was compared with previously investigated ionic liquids and industrial solvents such as sulfolane, n-methyl-2-pyrrolidine (NMP) and n-formylmorpholine (NFM). The results obtained suggested that in general, the [BMIM]+[Tf2N]− had outperformed the conventional solvents such as sulfolane, NMP and NFM in terms of selectivity, while the [BMIM][Tf2N] had in general, performed better overall when the performance index was used for comparison.