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Isopiestic determination of the osmotic coefficients of Na2SO4(aq) at 25 and 50 degrees C, and representation with ion-interaction (Pitzer) and mole fraction thermodynamic models

Journal

JOURNAL OF SOLUTION CHEMISTRY
Volume 29, Issue 1, Pages 1-49

Publisher

KLUWER ACADEMIC/PLENUM PUBL
DOI: 10.1023/A:1005182316790

Keywords

isopiestic measurements; sodium sulfate; osmotic coefficient; thermodynamics; Pitzer's model

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Isopiestic vapor-pressure measurements were made for Na2SO4(aq) from 0.11 to 3.74 mol-kg(-1) at 25.00 degrees C and from 0.12 to 3.57 mol-kg(-1) at 50.00 degrees C, using NaCl(aq) as the reference standard. Published isopiestic data, direct vapor pressures, emfs of reversible cells, freezing temperature depressions, boiling temperature elevations, heat capacities, and dilution enthalpies for this system have been critically assessed and recalculated in a consistent manner. Parameters for Fitter's model and a mole fraction-based thermodynamic model were evaluated. The mole fraction-based thermodynamic model for Na2SO4(aq) is valid from the freezing temperatures of the solutions to 150.5 degrees C. Fitter's model represents the osmotic coefficients and emfs essentially to experimental accuracy at 25 and 50 degrees C provided that the third virial coefficient was ionic-strength dependent.

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