Heat capacity equations for nonstoichiometric solids

The equations for heat capacity measured under isodynamical conditions (fixed activity of a single component) are derived for partly open systems exchanging one component with the surroundings while keeping the contents of all other components constant. Compared to conventional isobaric (and isoplethal) heat capacity of a strictly stoichiometric phase, the isodynamical heat capacity of a nonstoichiometric phase is found to involve two additional terms—the saturation contribution due to incorporation (or release) of the free component and the contribution due to deviation from stoichiometry reflecting a different number of the involved phonon modes (due to different free component content) and in some cases a variation of free component incorporation mechanism.