Thermodynamic properties and ordering in liquid NaK alloys

The thermodynamic activities of sodium and potassium were determined by vapour-phase absorption spectrophotometry of atomic resonance lines. Both components exhibit significant positive deviations from ideality. Excess Gibbs energies computed from the activity data were combined with available heat-of-mixing data to yield values for excess entropies. The entropy of mixing which was found to be ideal in the sodium-rich liquid alloys provides no support for the earlier speculations about the existence of Na₂K molecules therein. The partial molar excess entropy of sodium in dilute solution in potassium was found to be surprisingly large and negative for a system of this type. A plausible model, involving sodium-sodium pairing, is proposed to account for the loss of configurational entropy.