Thermodynamics of CoAl2O4-CoGa2O4 solid solutions

Kristina I. Lilova, Alexandra Navrotsky, Brent C. Melot, Ram Seshadri

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

CoAl2O4, CoGa2O4, and their solid solution Co(GazAl1-z)2O4 have been studied using high temperature oxide melt solution calorimetry in molten 2PbO·B2O3 at 973 K. There is an approximately linear correlation between lattice parameters, enthalpy of formation from oxides, and the Ga content. The experimental enthalpy of mixing is zero within experimental error. The cation distribution parameters are calculated using the O'Neill and Navrotsky thermodynamic model. The enthalpies of mixing calculated from these parameters are small and consistent with the calorimetric data. The entropies of mixing are calculated from site occupancies and compared to those for a random mixture of Ga and Al ions on octahedral site with all Co tetrahedral and for a completely random mixture of all cations on both sites. Despite a zero heat of mixing, the solid solution is not ideal in that activities do not obey Raoult's Law because of the more complex entropy of mixing.

Original languageEnglish (US)
Pages (from-to)1266-1271
Number of pages6
JournalJournal of Solid State Chemistry
Volume183
Issue number6
DOIs
StatePublished - Jun 2010
Externally publishedYes

Keywords

  • Cation distribution
  • CoAlO-CoGaO solid solution
  • Configurational entropy
  • Enthalpy of mixing
  • High temperature oxide melt solution calorimetry
  • O'Neill and Navrotsky thermodynamic model
  • Spinels

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Ceramics and Composites
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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