Thermodynamic properties of SrAl₁₂O₁₉ and SrAl₄O₇

Strontium aluminates are important compounds with interesting properties such as long-duration phosphorescence and elastico-deformation luminescence. They have potential application in flexible light emitting panels. Since there are serious discrepancies in available thermodynamic data for these compounds, a redetermination of their Gibbs energies of formation was undertaken using solid-state electrochemical cells incorporating single-crystal SrF₂ as the electrolyte in the temperature range from 1000 to 1300 K. However, the measurements were restricted to SrAl₁₂O₁₉ and SrAl₄O₇ because of the formation of strontium oxyfluoride phase between SrAl₂O₄ and SrF₂. For the reactions, SrO + 6 Al₂O₃ → SrAl₁₂O₁₉, ΔG ^o/J mol⁻¹ (± 280) = −83386 − 25.744 (T/K), and SrO + 2Al₂O₃ → SrAl₄O₇, ΔG ^o/J mol⁻¹ (± 240) = −80187 − 25.376 (T/K). The high entropy of SrAl₄O₇ and SrAl₁₂O₁₉ can be partly related to their complex structures. The results of this study are consistent with calorimetric data on enthalpy of formation of other Sr-rich aluminates and indicate only marginal stability for SrAl₄O₇ relative to its neighbours, SrAl₁₂O₁₉ and SrAl₂O₄. The thermodynamic data explain the difficulty in direct synthesis of phase pure SrAl₄O₇ and the formation of SrAl₂O₄ as the initial ternary phase when reacting SrO and Al₂O₃ or crystallizing from amorphous state, irrespective of composition.