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Thermodynamics of the magnetite-ulvöspinel (Fe3O4-Fe2TiO4) solid solution
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Kristina I. Lilova
Published/Copyright:
April 2, 2015
Abstract
The thermodynamics of mixing and its dependence on cation distribution in the Fe3O4-Fe2TiO4 (magnetite-ulvöspinel) spinel solid solution were studied using high-temperature oxide melt solution calorimetry and a range of structural and spectroscopic probes. The enthalpies of formation of ilmenite and ulvöspinel from the oxides and from the elements were obtained using oxidative drop solution calorimetry at 973 K in molten sodium molybdate. The enthalpy of mixing, determined from the fit to the measured enthalpies of drop solution calorimetry, is endothermic and represented by a quadratic formalism, ΔHmix = (22.60 ± 8.46)x(1 - x) kJ/mol, where x is the mole fraction of ulvöspinel. The entropies of mixing are more complex than those for a regular solution and have been calculated based on average measured and theoretical cation distributions. Calculated free energies of mixing show evidence for a solvus at low temperature in good agreement with that observed experimentally.
Received: 2011-12-12
Accepted: 2012-4-10
Published Online: 2015-4-2
Published in Print: 2012-8-1
© 2015 by Walter de Gruyter Berlin/Boston
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Keywords for this article
Titanomagnetite;
magnetite-ulvöspinel solid solution;
enthalpies of mixing;
calorimetry
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