Based on the concepts of statistical thermodynamics of athermal mixtures, an approach is developed which is capable of quantitatively explaining the thermodynamic properties of binary silicate systems. Expressions for the ionic fractions of various anionic linear and nonlinear chain polymers are derived. The developed expressions for free energy of mixing are tested by applying these to the system PbO-SiO2. The ionic fractions of various chain polymers in this system are calculated. The two cases, namely, of linear and nonlinear chain polymers are compared with each other.Limitations of earlier models are pointed out.