Using the CALPHAD technique, an assessment of the binary EuCl 3 -MgCl 2 and EuCl 3 -BaCl 2 systems has been carried out in this study. The modified quasi-chemical model was defined to describe the Gibbs energies of the liquid phases, and the model parameters were optimized from the experimental phase diagram data. The phase diagrams and enthalpies of mixing of the EuCl 3 -MgCl 2 and EuCl 3 -BaCl 2 systems were calculated. The calculated results by the present method agree well with the experimental data. The Gibbs energies of formation of Mg Cl 13 from the pure components were predicted.