The aqueous two-phase systems (ATPSs)
are widely used for the extraction
of biomolecules such as proteins and pharmaceuticals using polymer–salt and ionic liquid–salt
systems. In this work, we correlated the experimental data of the
17 ATPSs containing ionic liquids and salts, comprised of 292 tie-lines.
First, to obtain the interaction parameters of salt–water,
the mean activity coefficients of the 11 binary aqueous electrolyte
systems were regressed, and then, the liquid–liquid equilibrium
calculations were performed to correlate the ATPSs. In the present
work, three symmetrical local composition models such as NRTL-NRF,
UNIQUAC-NRF, and UNIQUAC along with symmetric Pitzer–Debye–Hückel
(PDH) theory were used. The local composition models and PDH theory
were applied for the short-range and long-range interactions, respectively,
by assuming complete dissociation of salts for the PDH term and ion-pair
approach for the salts, water, and ionic liquids in the local composition
models. The molecular volume and the structural parameters of the
ionic liquids such as the surface area are obtained using the literature
data; however, these parameters for 1-ethyl-2,3-dimethylimidazolium
ethyl sulfate are calculated by Jmol software (an open-source Java
viewer for chemical structures in three-dimensional). Furthermore,
using the calculated molecular volume, the dielectric constant for
1-propyl-3-methylimidazolium tetrafluoroborate was estimated by the
method proposed by Singh et al. (J. Phys. Chem. B, 2008, 112(41) 12968–12972).
The results of the correlation of the ATPSs were in very good agreement
with the experiment using NRTL-NRF and UNIQUAC-NRF models and gave
more accurate results than the UNIQUAC model.