Cloud point extraction is a versatile method aimed at separating compounds from complex mixtures and arouses great technological interest, particularly among the biochemical industries. However, one must have deep knowledge of the liquid–liquid equilibrium behavior of systems to properly use the method. Thus, we used thermodynamic parameters to evaluate the effect of citrate, sulfate, and tartrate anions on the phase separation of water + Triton X-114® mixtures at 283.2 K, 293.2 K, and 303.2 K. In these systems, increasing the temperature and the anion molar fraction expanded the biphasic region in the following order: C6H5O73-> SO42- > C4H4O62−. Unlike other studies based on the Hofmeister series, the Gibbs free energy of micellization correlated the anion effect on the biphasic region with the spontaneity of the micelle formation. The water molecules structured around these anions were evaluated according to the shell volume of the immobilized water by electrostriction, volume of water around the hydration shell, Gibbs free energy of hydration, and Gibbs free energy of electrostriction (ΔGel12). The citrate anion presented a higher ΔGel12 of −1781.49 kJ mol−1, due to the larger number of electrons around it. In addition, the partition coefficient of the surfactant in the two liquid phases revealed a linear dependence upon the anion mole fractions by following the previous anion sequence and temperature in the phase separation.
