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Experimental determination of the activity of chromite in multicomponent spinels

Kessel, Ronit and Beckett, John R. and Stolper, Edward M. (2003) Experimental determination of the activity of chromite in multicomponent spinels. Geochimica et Cosmochimica Acta, 67 (16). pp. 3033-3044. ISSN 0016-7037. doi:10.1016/S0016-7037(03)00197-2.

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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.

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Stolper, Edward M.0000-0001-8008-8804
Additional Information:© 2003 Elsevier Ltd. Received November 26, 2001; accepted in revised form June 24, 2002. This work was supported by NASA grant NAG-10423. Discussions with Mike Baker and a written communication with Joe Goldstein led to significant improvements in the quality of this study. Ma Chi is appreciated for his help with the analytical work. The authors thank John Jones and Hugh O'Neill for their constructive reviews. Division contribution #5714. Associate editor: F. J. Ryerson.
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Caltech Division of Geological and Planetary Sciences5714
Issue or Number:16
Record Number:CaltechAUTHORS:20120823-103344245
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Official Citation:Ronit Kessel, John R. Beckett, Edward M. Stolper, Experimental determination of the activity of chromite in multicomponent spinels, Geochimica et Cosmochimica Acta, Volume 67, Issue 16, 15 August 2003, Pages 3033-3044, ISSN 0016-7037, 10.1016/S0016-7037(03)00197-2.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:33473
Deposited On:23 Aug 2012 20:57
Last Modified:09 Nov 2021 21:34

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