Energetics of brannerite-type solid solutions: The systems ZnV2O6LiMoVO6 and MgV2O6LiMoVO6

K. Mocala, A. Navrotsky

Research output: Contribution to journalArticlepeer-review

5 Scopus citations


Enthalpies of mixing in brannerite-type solid solutions ZnV2O6LiMoVO6 and MgV2O6LiMoVO6 were determined by transposed temperature-drop solution calorimetry into a molten sodium molybdate solvent at 702°C. The ZnV2O6LiMoVO6 system shows zero heats of mixing (to ± 2 kJ/mole) and symmetrical negative excess volumes of mixing. The MgV2O6LiMoVO6 system shows more complex behavior, with positive enthalpies of mixing at MgV2O6-rich end and negative heats of mixing at LiMoVO6-rich compositions. Volumes of mixing are negative at MgV2O6-rich compositions and essentially zero on the LiMoVO6-rich side. This complex behavior suggests that several effects compete to result in the observed energetic and structural behavior. These factors may be (a) strain energy associated with size-mismatch, (b) the relaxation of rather long MgO bonds in MgV2O6 upon solid solution formation, and (c) the effect of simultaneous coupled substitution of Li on Mg sites and of Mo on V sites, possibly with some short-range order.

Original languageEnglish (US)
Pages (from-to)224-234
Number of pages11
JournalJournal of Solid State Chemistry
Issue number1
StatePublished - Mar 1988
Externally publishedYes

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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