Abstract
The thermodynamic activities of MgO in the NaCl-type solid solutions which can exist in “x MgO + (1 − x) MnO’ have been determined in the temperature range 1163 to 1318 K from a solid-state galvanic cell incorporating MgF 2 as the solid electrolyte. The activities of MnO have been calculated by a graphical Gibbs-Duhem integration method. The activities of both the components exhibit positive deviations from ideality over the entire composition range. The excess molar enthalpies are found to be positive. Further, “x MgO + (1 − x) MnO’ does not conform to regular-solution behaviour. The origin of the excess thermodynamic properties is discussed in relation to the cationic size disparity and the crystal-field effects.
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