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Pure Appl. Chem., 2002, Vol. 74, No. 10, pp. 1793-1800

Calculation of the free Gibbs energy of phase transitions using solubility data. 1. The system Na2SO4-Na2Se04-H2O at 15 °C: Stable and metastable

Chr. Balarew

Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bontchev Str., Bl.11, 1113 Sofia, Bulgaria

Abstract: The solubility isotherms of the systems Na2SO4 ·10H2O–Na2SeO4·10H2O–H2O and Na2SO4·7H2O–Na2SeO4 ·7H2O–H2O have been investigated at 15 °C. It is established that discontinuous series of mixed crystals are formed in both systems. Two methods of calculation of the free Gibbs energy of phase transition at the interruption point of the solubility diagrams are used: (i) on the basis of the composition of the two mixed crystal types, which are in equilibrium with the saturated solution in the eutonic point of the system, and (ii) from the distribution coefficients between each of the mixed crystal phases and their saturated solution, using both experimentally obtained values and calculated distribution coefficients for ideal isomorphic mixing. The data found by the two methods exhibit very good agreement. It is established that the free Gibbs energy of the phase transition in the case of decahydrates is lower than in the case of heptahydrates. This fact is considered as a confirmation of the buffering action of water molecules with respect to the distortion of the crystal structures of the pure salts provoked by the formation of mixed crystals.