JOURNAL OF THE AMERICAN CERAMIC SOCIETY, vol.75, no.6, pp.1399-1406, 1992 (SCI-Expanded)
Activities of NiO were measured in the oxide and spinel solutions of the system MnO-NiO-Al2O3 at 1300-degrees and 1400-degrees-C with the aim of deriving information on the thermodynamic properties of the spinel phases. Synthetic samples in selected phase assemblages of the system were equilibrated with metallic nickel and a gas phase of known oxygen partial pressures at a total pressure of 1 atm. The data on NiO activities and directions of conjugation lines between coexisting oxide and spinel phases were used to establish the activity-composition relations in spinel solid solutions at 1300-degrees and 1400-degrees-C. The MnAl2O4-NiAl2O4 solid solutions exhibit considerable negative deviations from ideality at these temperatures. The free energy of formation of MnAl2O4 from its oxide components (MnO + Al2O3) at 1300-degrees and 1400-degrees-C is calculated to be -24.97 and -26.56 kJ . mol-1, respectively. The activities determined in the stoichiometric spinel solid solutions are more negative as compared with those predicted from cation distribution models.