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Modelling aqueous solutions near the critical point of water
Authors:Graham Morrison
Affiliation:(1) Center for Chemical Technology, Thermophysics Division, National Bureau of Standards, 20899 Gaithersburg, MD
Abstract:We review the thermodynamic properties of dilute solution near the critical point of the solvent. Two examples are discussed, a solution of a non-electrolyte and a solution of an electrolyte. The limiting behavior of the electrolyte solutions is modelled with a Debye-Huckel term in the Helmholtz free energy. The partial molar properties, in particular the volume and isobaric thermal expansion are examined in detail. The derivation of these properties is introduced by considering the geometry of the thermodynamic surfaces near to and far from the critical point of the solvent. We conclude that the properties of solutions near the solvent critical point are dominated by that feature; solution properties cannot be adequately modelled without including the functional forms associated with the critical point.
Keywords:Critical point  nonelectrolyte  Helmholtz free energy  partial molar volumes  isobaric thermal expansion
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