The Engel–Brewer method and the Miedema model, the Witusiewicz,
Sommer, Faber relations and the Hard-Sphere model
have been reviewed and evaluated for their suitability for calculating
mixing properties of liquid solutions. For this purpose, these
methods have been applied to different groups of binary systems
and the results have been compared with the experimental data.
Analysis of the results on the enthalpy of mixing obtained by the
Engel–Brewer method and the Miedema model contra-indicated
the application of the Engel–Brewer method even for transition
metals and actinides, while the Miedema model is considered successful
for calculating the enthalpy of mixing. Moreover, the Witusiewicz
relation and Hard-Sphere model successfully predicted
the entropy of mixing of the majority of liquid alloys. However, it
was shown that the Hard-Sphere model cannot be reliable for
the case of d10 transition metals/metalloids alloyed with alkali/
alkaline earth metals. It is proposed that for systems with no or
few experimental thermodynamic property data, a Miedema/Witusiewicz
model or Miedema/Hard-Sphere model can be used as
thermodynamic property first approximations. When combined
FIGURE 6. Prediction of the Ag–Cu phase diagram using Engel–Brewer method (—), Miedema–Witusiewicz (- - -) and the Miedema–Hard-Sphere models (...) in comparison
with experimental data ([82]: j, [68]: + and [83]: 4).
FIGURE 7. Prediction of the Pu–U phase diagram using Engel–Brewer method (—) Miedema–Witusiewicz (- - -) and the CALPHAD method assuming the Miedema–
Witusiewicz model as the first approximation of thermodynamic property (...) in comparison with experimental data of Peterson and Foltyn [84]: s.
90 G. Arzpeyma et al. / J. Chem. Thermodynamics 57 (2013) 82–91
with phase equilibrium data and the CALPHAD method this can result
in the usefull prediction of thermodynamic properties of liquid
binary liquid alloys. Application of these models is not limited to
binary systems. Using the Muggianu, Kohler or Toop models, Miedema/Witusiewicz
or Miedema/Hard-Sphere models can also be
extended to ternary systems or higher order systems.