Über die extrem hohe thermodynamische Stabilität von Pd-Th-Legierungen / On the Extremely High Thermodynamic Stability of Pd-Th Alloys

Abstract

The thermodynamic properties of Pd-Th solid solutions containing up to 16 at.% Th have been determined by the e.m.f. method between 700 and 800 °C with CaF2 solid electrolyte cells. The mixing behaviour of the alloys is characterized by extreme negative deviations from ideality, up to -410 kJ/mol for the partial molar excess free energy of Thorium. The extraordinary stability is attributed to electronic interactions brought about by the transfer of the Thorium valence electrons to the electron gas of the alloy. At vanishing Thorium concentration the resulting bonding contribution to the thermodynamic excess quantities is determined by the difference of the Fermi energies of the pure components, approximately equal to the difference of the work functions. Including the lattice distortion as a small additional effect, the mixing behaviour of these and other palladium alloys can be well described