Part X – October 1969 - Papers - Galvanic Cell Studies Using a Molten Oxide Electrolyte: Part III-Thermodynamic Properties of the Pb-Ag-Au System

The thermodynamics properties of the liquid Pb-Ag-Au system have been determined from galvanic cell measurments five pseudobinary systems of fixed XAg/XAu ratio. The galvanic cell employed a molten PbO-SiO2 electrolyte and was operated between 775" and 1030°C. The thermodynamics properties of lead were obtained directly from the experimental data, whereas the excess integral molar properties and the activities of silver and gold were obtained by means of the Gibbs-Duhem equation. The calculated proper -ties of the Ag-Au system agree well with the published properties. The liquidus surface of the Pb-Ag-Au system has been determined at 1200°K. In Parts I' and 11' the galvanic cell Mo,Pb(l)|(PbO-SiO2)(l) SiO2(s) |Pb(alloy)(l), Mo [I] was used to determine the thermodynamics properties of the Pb-Ag and Pb-Au systems, respectively. The use of cell I, in which a molten oxide electrolyte is employed rather than the classical fused-salt electrolyte, was shown to result in more accurate ther-modynamic measurements in that the displacement reaction at the alloy-electrolyte interface (l/Zb)B(alloy) + (I/za)A+Za = (1/Za)A(alloy) + (1/Zb)B+zb [1] was minimized. For the Pb-Ag system, where B = Ag(l), the error in the activity of lead (aPd) re-sulting from Reaction [I] was calculated to be less than 1 pct.l For the Pb-Au system the error in aPb was calculated to be less than 0.5 pct.2 Also, electro-transport measurements on the PbO-SiO2 electro-lyte1,2 established that the conduction was entirely ionic and that lead was present only in the divalent state. In the present study the experimental technique is extended to an investigation of the thermodynamic properties of the liquid Pb-Ag-Au system. Five pseudobinary systems of fixed X Ag/XAu ratio were selected. The experimental results were then combined with the previous measurements on the component binary systems Pb-Ag1 and Pb-AU2 to calculate, by means of the Gibbs-Duhem equation, the molar and partial molar mixing properties for the liquid ternary solutions.