Standard thermodynamic properties of H3PO4(aq) over a wide range of temperatures and pressures.
The densities and heat capacities of solutions of phosphoric acid, 0.05 to 1 mol kg-1, were measured using flow vibrating tube densitometry and differential Picker-type calorimetry at temperatures up to 623 K and at pressures up to 28 MPa. The standard molar volumes and heat capacities of molecular H3PO4(aq) were obtained, via the apparent molar properties corrected for partial dissociation, by extrapolation to infinite dilution. The data on standard derivative properties were correlated simultaneously with the dissociation constants of phosphoric acid from the literature using the theoretically founded SOCW model. This made it possible to describe the standard thermodynamic properties, particularly the standard chemical potential, of both molecular and ionized phosphoric acid at temperatures up to at least 623 K and at pressures up to 200 MPa. This representation allows one to easily calculate the first-degree dissociation constant of H3PO4(aq). The performance of the SOCW model was compared with the other approaches for calculating the high-temperature dissociation constant of the phosphoric acid. Using the standard derivative properties, sensitively reflecting the interactions between the solute and the solvent, the high-temperature behavior of H3PO4(aq) is compared with that of other weak acids.
Ballerat-Busserolles
Karine
K
Laboratoire de Thermodynamique des Solutions et des Polymères, Université Blaise Pascal Clermont-Ferrand/CNRS, 63177 Aubière, France.
Sedlbauer
Josef
J
Majer
Vladimir
V