Electrochemical Determination of Activities in Cr2 O 3 ‐ Al2 O 3 Solid Solution

Abstract

The activity of in solid solution has been determined in the temperature range 800°–1320°C from electromotive force measurements on the solid oxide galvanic cellThe activities of and in the solid solution show both positive and negative deviations from Raoult's law. The heat and entropy of mixing of the solid solution obtained from the temperature dependence of the emf can be expressed asThe entropy of mixing is 10% lower than that predicted by the Temkin model. The large positive heat of mixing in the solid solution, however, suggests that this apparent entropy discrepancy originates with the clustering of positive ions on the cation sublattice. The asymmetric miscibility gap exhibited in the system below 900°C is consistent with the thermodynamic data trends recorded at the more elevated temperatures.