Experimental determination of the activity of chromite in multicomponent spinels

We determined activity–composition relationships in Pt-Cr and Pt-Fe-Cr alloys at 1300°C experimentally and used the results to constrain the thermodynamic properties of chromite–picrochromite spinels. The Pt-Cr binary is characterized by strong negative deviations from ideality throughout the investigated composition range and the activity–composition relationship can be fit by a four-suffix asymmetric regular solution with three binary interaction parameters. The ternary alloy was modeled as a four-suffix asymmetric regular solution; the three ternary interaction parameters in this model were constrained by combining interaction parameters for the three bounding binaries taken from this and previous work with results for a set of experiments in which the activity of Cr in Pt-Fe-Cr-alloys was fixed by coexisting Cr_(2)O_3 at known fO_2. The free energy of formation of FeCr_(2)O_4 at 1300°C was determined using the activities of Fe and Cr in Pt-alloys in equilibrium with oxide mixes of FeCr_(2)O_4 and Cr_(2)O_3. The free energy of formation of chromite from Fe+Cr_(2)O_3+O_2 is −202.7 ± 0.4 kJ/mol (1σ), indistinguishable from literature values. The corresponding free energy of formation of FeCr_(2)O_4 from the elements is −923.5 ± 2.1 kJ/mol (1σ), and the enthalpy of formation at 298 K is −1438 kJ/mol. The activity–composition relationship for the chromite component in (Fe,Mg)Cr_(2)O_4 solid solutions was determined from a set of experiments in which Pt-alloys were equilibrated with spinel + Cr_(2)O_3. (Fe,Mg)Cr_(2)O_4 spinels are nearly ideal at 1300°C; modeling our data with a one-site symmetric regular solution yields an interaction parameter of +2.14 ± 0.62 kJ/mol (1σ), similar to values based on data from the literature