Calorimetric study of the stability of spinelloids in the system NiAl₂O₄-Ni₂SiO₄

Enthalpies of solution in molten 2 PbO · B₂O₃ at 974 K were measured for four spinelloids, phases I (0.75 NiAl₂O₄ · 0.25 Ni₂SiO₄), II (0.60 NiAl₂O₄ · 0.40 Ni₂SiO₄), III and IV (0.50 NiAl₂O₄ · 0.50 Ni₂SiO₄) in the system NiAl₂O₄ · Ni₂SiO₄. The enthalpies (in cal per 4-oxygen mol) of formation from NiAl₂O₄ and Ni₂SiO₄ spinels are: phase I, 945±366; phase II, 1072±360; phase III, 2253±390; phase IV, 3565±544. Using these enthalpy data in combination with phase relations at high pressure at 1373 K, positive entropies of formation of the spinelloids from NiAl₂O₄ and Ni₂SiO₄ spinels were estimated (in cal mol^-1 K^-1): phase I, 1.2; phase II, 1.5; phase III, 2.0-2.3; phase IV, 3.0-3.1. The thermochemical data obtained above suggest that the spinelloids are "entropy-stabilized" phases with partially disordered cation distributions. The configurational entropies of the spinelloids were calculated based on the observed cation distribution in each spinelloid phase. The positive entropies of formation of the spinelloids from the spinel endmembers are due primarily to the configurational entropies although small positive vibrational entropy changes may also exist.