163.
The regular associated solution model for binary systems has been modified by incorporating the size of the complex as an
explicit variable. The thermodynamic properties of the liquid alloy and the interactions between the
A
μB type of complex and the unassociated atoms in an
A-B binary have been evaluated as a function of relative size of the complex using the activity coefficients at infinite dilution
and activity data at one other composition in the binary. The computational procedure adopted for determining the concentration
of clusters and interaction energies in the associated liquid is similar to that proposed by Lele and Rao. The analysis has
been applied to the thermodynamic mixing functions of liquid Al-Ca alloys believed to contain Al
2Ca associates. It is found that the size of the cluster significantly affects the interaction energies between the complex
and the unassociated atoms, while the equilibrium constant and enthalpy change for the association reaction exhibit only minor
variation, when the equations are fitted to experimental data. The interaction energy between unassociated free atoms remains
virtually unaltered as the size of the complex is varied between extreme values. Accurate data on free energy, enthalpy, and
volume of mixing at the same temperature on alloy systems with compound forming tendency would permit a rigorous test of the
proposed model.
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