An ion-association model for PbO-SiO2 melts: interpretation of thermochemical,conductivity, and density data

We propose that within PbO-SiO₂ melts the component species PbO(1) and SiO₂(1) associate to form a lead orthosilicate complex [Pb₂SiO₄(1)] according to $\text{2PbO(1) + SiO}{}_2\text{(1)}\text{a}\text{?}\text{f Pb}{}_2\text{SiO}{}_4\text{(1)}$ The association constant (K) for the above reaction is near 30 at 900 and 1000°C On the premises that the enthalpy of the above reaction is the only contributor to the enthalpy of mixing and that three melt species [PbO(1), SiO₂(1), Pb₂SiO₄(1)] mix ideally (Raoult's Law obeyed), the partial molar properties and the integral mixing properties of the melt have been calculated and have been found to accurately reproduce the measured thermochemical data.The conductivity data and density data for PbO-SiO₂ melts have been calculated using the association model. The calculated data again are remarkably consistent with the experimental data.Other silicate-melt models have been reinterpreted and that of Toop and Samis is compatible with the proposed model. In fact the Toop and Samis model implicitly assumes the formation of orthosilicate species rather than condensed polymeric species.