Thermodynamic properties and phase equilibria for Pt-Rh alloys

The activity of rhodium in solid Pt-Rh alloys is measured in the temperature range from 900 to 1300 K using the solid-state cell The activity of platinum and the free energy, enthalpy, and entropy of mixing are derived. Activities exhibit moderate negative deviation from Raoult’s law. The mixing properties can be represented by a pseudosubregular solution model in which excess entropy has the same type of functional dependence on composition as the enthalpy of mixing, The negative enthalpy of mixing obtained in this study is in qualitative agreement with predictions of semiempirical models of Miedema and co-workers and Colinet et al. The results of this study do not support the solid-state miscibility gap suggested in the literature, but are consistent with liquidus data within experimental uncertainty limits.