Thermodynamics study of oxygen in liquid lead-tin alloys

The activity coefficients of oxygen in liquid Pb-Sn alloys have been measured between 550 and 1100°C by use of solid oxide galvanic cells: Pt, Ni-NiO | Zr02 Solid electrolyte | O (Pb + Sn), Cermet, Pt; and Pt, Fe-FeO | Zr02 Solid electrolyte | 0(Pb + Sn), Cermet, Pt. Alcock and Richardson's quasi-chemical equation, with the coordination number of atoms set to 2, is found to predict successfully the activity coefficients of oxygen in these alloys. The relative partial molar enthalpy and entropy of oxygen at 1 atom per cent in the alloys have been calculated from the variation of the activity coefficient with temperature. The addition of Sn to an unsaturated solution of O in Pb is shown to decrease significantly both the partial molar enthalpy and entropy of O. As the measurements were restricted to a narrow range between 750 and 1100°C in Pb-rich alloys, however, the pronounced variation of the partial molar enthalpy of O with temperature at constant alloy composition predicted by the quasi-chemical model could not be verified.