Isopiestic determination of the osmotic and activity coefficients of {yK(2)HPO(4) + (1-y)KH2PO4}(aq) at T=298.15 K

Abstract

Isopiestic measurements have been made at 55 compositions of the {yK(2)HPO(4) + (1 - y)KH2PO4}(aq) system at T = (298.15 +/- 0.01) K, 11 for each of the limiting binary solutions and 33 for mixture compositions at K2HPO4 stoichiometric ionic strength fractions y = (0.23330, 0.47671, and 0.73177), using KCl(aq) as the reference standard. Model parameters for the binary subsystems were evaluated at this temperature for an extended form of Pitzer's ion-interaction model and also for the Clegg, Pitzer and Brimblecombe model based on the mole-fraction-composition scale, using the present isopiestic results along with critically-assessed osmotic coefficients for both of these aqueous electrolytes as extracted from the published literature. The thermodynamic models for KH2PO4(aq) extend to slightly above the saturated solution molality at T = (298.15 +/- 0.01) K, whereas those for K2HPO4(aq) extend to m = 9.7429 mol.kg(-1), which is the molality of the saturated solution, also at T = (298.15 +/- 0.01) K. These results yield the CODATA-compatible standard Gibbs energy of formation Delta(f)G(m)(o)(K2HPO4 center dot 3H(2)O; cr; 298.15 K) = -(2367.70 +/- 1.60) kJ.mol(-1). The 33 osmotic coefficients for the ternary mixtures were likewise represented with these models, using both the usual Pitzer mixing terms and also Scatchard's neutral-electrolyte model mixing terms for the extended ion-interaction model. Two mixing parameters are needed for each of the three models for {yK(2)HPO(4) + (1 - y)KH2PO4}(aq), and both of these ion-interaction models give similar high-quality representations of the experimental results. However, the Clegg, Pitzer and Brimblecombe model had more difficulty in representing the osmotic coefficients of K2HPO4(aq), especially below 3 mol.kg(-1), and consequently the corresponding mixture model with two mixing parameters is slightly less accurate for representing the osmotic coefficients. The maximum difference in calculated values of the mean molality-based activity coefficients for the two recommended extended Pitzer models with the different types of mixing terms are 0.0061 for the trace activity coefficient of K2HPO4(aq) in KH2PO4(aq) but with much better agreement at most mixture compositions.