Experimental measurement of thermodynamic properties and of phase equilibrium for some systems is
complicated since these systems may be reactive and/or expensive to study. They may contain radioactive
or scarce components and be otherwise highly unusual for bench top manipulation. For these systems,
predicting thermodynamic properties using theoretical and/or empirical methods is of great
interest. In this paper, the Engel–Brewer method, the Witusiewicz, Sommer and Faber relations, the Miedema
and Hard-Sphere model have been reviewed and evaluated on their suitability for calculating mixing
properties of liquid solutions. Analysis of the results indicated that the Engel–Brewer method is not
robust, while the Miedema model, with some modifications, has been evaluated as an appropriate one for
predicting enthalpy of mixing of liquid solutions. Moreover, the Witusiewicz relation and Hard-Sphere
model were proved to be more reliable compared to that of Sommer and Faber for predicting entropy
of mixing of liquid alloys. Finally, based on the current work, the combined Miedema–Witusiewicz or
Miedema/Hard-Sphere models are recommended for parameterizing Gibbs free energy of mixing for
liquid solutions.