Thermodynamic properties of nonstoichiometric urania-gadolinia solid solutions in the temperature range 700–1100° C

Partial molar thermodynamic quantities for urania-gadolinia solid solutions of compositions U_1−yGd_yO_2+x, with y values of 0.04 to 0.27, have been obtained using a solid electrolyte galvanic cell technique. The measurements were made for O/M ratios ranging from near stoichiometry to 2.20, and for temperatures ranging from 700 to 1100°C. The results for pure UO_2+x are in accordance with data reported earlier. The oxygen potentials for U_1−yGd_yO_2+x are higher than for pure UO_2+x and increase positively with increasing Gd content or excess oxygen. They can be represented as a function of the mean U valence, except at the stoichiometric composition. Both the partial molar entropy and enthalpy increase negatively with increasing Gd content or excess oxygen.