Constitution and thermodynamics of Pt-La alloys

A complete set of thermodynamic functions was determined for the Pt-La system from electromotive force measurements on galvanic cells in the temperature range from 923 to 1073 K using CaF2 single crystals as solid electrolytes. The phases on the platinum-rich side show pronounced negative deviations from ideal mixing behaviour; at 1073 K and infinite dilution, for instance, the relative partial excess Gibbs energy of La was determined to be -315 kJ/mol. Two effects are discussed to account for the deviations from ideal mixing behaviour: the transfer of the valence electrons of La to the electron gas of the alloy and the lattice distortion brought about by the size difference of the components. The phase relations were investigated by means of thermal, and X-ray analyses. The thermodynamic description of the system was optimized using experimental data from the present thermodynamic and phase diagram work. The calculated thermodynamic functions as well as the calculated phase diagram turned out to be in excellent accordance with the experimental results. (c) 2005 Elsevier B.V. All rights reserved.