Thermochemistry of GaBO3 and phase equilibria in the Ga2O3–B2O3 system

Employing a Tian-Calvet-type calorimeter operating in the scanning mode at temperatures from 1120 to 1220 K, the enthalpy change, Δ_dH, associated with the decomposition of GaBO₃ (=1/2β-Ga₂O₃+1/2B₂O₃(liq.)) and the corresponding decomposition temperature, T_d, were determined: Δ_dH=30.34±0.6 kJ/mol, T_d=1190±5 K. Using the transposed-temperature-drop method the thermal enthalpy, H(T)−H(295 K), of GaBO₃ was measured as a function of temperature, T, in the region from 760 to 1610 K; the results obtained are

[H(T)−H(295 K)]/(J/mol)=104.8·(T/K)−31 300 (760 K<T<1190 K),

[H(T)−H(295 K)]/(J/mol)=138.8·(T/K)−41 480 (1190 K<T<1590 K).

On the basis of the experimental results, the enthalpy and entropy of formation, Δ_fH and Δ_fS, respectively, of GaBO₃ from the component oxides were derived:

Δ_fH=−30.34 kJ/mol,Δ_fS=−25.50 J/(K·mol) at 1190 K,

Δ_fH=−10.55 kJ/mol,Δ_fS=−5.48 J/(K·mol) at 298 K.

The enthalpy versus temperature curve shows, apart from a step associated with the decomposition of GaBO₃, a further step at 1593 K which is attributed to a monotectic equilibrium.