Heat capacities and thermodynamics of formation of ε-Keggin MAl12 Selenates (M = Al(III), Ga(III), or Ge(IV))

Dana Reusser, Jacob Schliesser, Brian F. Woodfield, Alexandra Navrotsky

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

Abstract We report enthalpies of formation from the elements and oxides, ΔfH° = -(22,673.44 ± 30.19) kJ·mol-1 and Δf,oxH = -(869.68 ± 28.75) kJ·mol-1, for [GeO4Al12(OH)24(H2O)12](SeO4)4·12H2O(cr) (GeAl12) measured using high temperature oxide-melt solution calorimetry. This material is the selenate salt of the germanium-substituted polynuclear Al137+ ion in the ε-Keggin structure. We also report heat capacities from temperatures of (2 to 300) K on this GeAl12 selenate and its other heterometal substituted forms, Na[AlO4Al12(OH)24(H2O)12](SeO4)4·12H2O(cr) (AlAl12) and Na[GaO4Al12(OH)24(H2O)12](SeO4)4·12H2O(cr) (GaAl12), measured using a Quantum Design Physical Property Measurement System (PPMS). These measurements were used to calculate entropies and subsequently free energies of formation for these three materials. All three MAl12 selenates, where M = Al(III), Ga(III), or Ge(IV), have similar heat capacities from temperatures (2 to 300) K and similar characteristic Debye temperatures, ΘD, suggesting similar lattice vibrational densities of states.

Original languageEnglish (US)
Article number4260
Pages (from-to)296-305
Number of pages10
JournalJournal of Chemical Thermodynamics
Volume89
DOIs
StatePublished - Jun 25 2015
Externally publishedYes

Keywords

  • Al
  • Enthalpy of formation
  • Heat capacity
  • Keggin
  • Polyoxocation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Materials Science(all)
  • Physical and Theoretical Chemistry

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