A thermodynamic description of the system Pd–Rh–H–D–T

Abstract

The quinary system D–H–Pd–Rh–T has been described thermodynamically by the CALPHAD approach. Previous descriptions of the binary subsystems have been used. To model the high pressure data an equation of state for the gases D2 and T2 compatible with the CALPHAD approach has been obtained similar to that previously used for H2. A complete literature search has been undertaken for the three ternary systems H–Pd–Rh, D–Pd–Rh and Pd–Rh–T and the most significant experimental data have been selected for a thermodynamic assessment of these systems. In order to complement the available data, pressure–composition curves have been measured at different temperatures for the two last systems in the present work. Calculations and optimization of the system under para-equilibrium conditions, i.e. in pseudo-binary systems (Pd,Rh)–H, (Pd,Rh)–D or (Pd,Rh)–T, have been achieved using a pseudo-atom describing the Pd–Rh solid solution. This special method allows the presence of a miscibility gap in the binary metallic system to be dealt with. We show that a simple combination of the binary systems alone is unable to properly describe these ternary systems and that ternary interaction parameters have to be introduced. The binary and ternary systems may then be combined to perform calculations in the quinary D–H–Pd–Rh–T system. It is believed that extrapolation in systems containing different isotopes are fairly accurate provided that the so-called Toop model is used.