Thermodynamic Properties of Ternary Mixtures Containing Ionic Liquid and Organic Liquids: Excess Molar Volume and Excess Isentropic Compressibility

2014 ◽  
Vol 59 (4) ◽  
pp. 1140-1157 ◽  
Author(s):  
V. K. Sharma ◽  
S. Solanki ◽  
S. Bhagour
2018 ◽  
Author(s):  
◽  
Ncomeka Mgxadeni

In this study the experimental density, speed of sound, and refractive index for binary mixtures of an ionic liquid (IL): 1-butyl-3-methylimidazolium nitrate and activity coefficients at infinite dilution of organic solutes in the ionic liquid: 1-butyl-3-methylimidazolium hydrogen sulfate were determined. The density, speed of sound, and refractive index of 1-butyl-3-methylimidazolium nitrate in pyridine or acetonitrile or thiophene have been reported at T = 298.15 K, 303.15 K, 308.15 K, 313.15 K and 318.15 K using an Anton Paar DSA 5000M vibrating U-tube densimeter and a RXA 156 refractometer. The derived properties namely: excess molar volume, isentropic compressibility and change in refractive index were calculated from density, speed of sound and refractive index, respectively. The results are discussed in terms of molecular interactions (hydrogen bond, dipole-dipole, or ion-solvent or interactions). The negative deviation of excess molar volume and the positive deviation in change in refractive index clearly indicates the strong interaction of 1-butyl-3-methylimidazolium nitrate with pyridine or acetonitrile or thiophene in solution. The positive values of isentropic compressibility for the system indicates that the mixtures were more compressible than the ideal mixture. The Redlich Kister smoothing polynomial was used to fit the excess molar volume and deviation in isentropic compressibility data. The Lorentz-Lorenz equation was used to predict the experimental density, or refractive index data and to correlate the excess molar volume. Gas liquid chromatography was used to determine activity coefficients at infinite dilution for 28 polar and non-polar organic solute: alkanes, cycloalkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, aldehydes, thiophene, pyridine and acetonitrile in an IL: 1-butyl-3- methylimidazolium hydrogen sulfate ([BMIM][HSO4]). The measured values of activity coefficients at infinite dilution for the solutes in [BMIM][HSO4] were carried out at T = (313.15, 323.15, 333.15) K. Partial molar excess enthalpies at infinite dilution of the organic solutes in the ionic liquid have been calculated from the temperature dependence of activity coefficients at infinite dilution. The selectivity and capacity values for separation problems namely: hexane/benzene, heptane/benzene, cyclohexane/benzene, ethanol/benzene, heptane/pyridine, heptane/thiophene and methanol/acetone at T = 323.15 K were calculated and compared to literature values for similar ionic liquids, sulfolane and N-methyl-2- pyrolidinone (NMP). The IL [BMIM][HSO4] gave both the highest selectivity and limiting capacity for the heptane/thiophene separation and would therefore be a suitable entrainer for this separation. New data from this study reveals that [BMIM][HSO4] may be proposed as a replacement solvent for the separation of sulphur or nitrogen compounds from alkanes.


2017 ◽  
Author(s):  
◽  
Sangeeta Singh

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.


RSC Advances ◽  
2016 ◽  
Vol 6 (35) ◽  
pp. 29172-29181 ◽  
Author(s):  
Xuzhao Yang ◽  
Hao Song ◽  
Jun Wang ◽  
Wenyuan Zou

Excess molar volume VEm for the system of [MPiC6Py][NTf2]2 (1) + MeCN (2) at various temperatures; solid line, Redlich–Kister correlation.


Sign in / Sign up

Export Citation Format

Share Document