Abstract
We developed a FORTRAN program based on the Pitzer equations to calculate densities of electrolyte solutions at subzero temperatures. Data from the published literature collected at -28.9, -17.8, -12.2, -6.7, 0, and 25°C were used to calculate the Pitzer-equation parameters and to evaluate model performance. Three approaches to estimating the molar volume of the solute at infinite dilution were evaluated: (1) extrapolation of apparent molar volumes to zero square-root ionic strength; (2) calculation with the Tanger and Helgeson model; and (3) global fit of the data in which the molar volume of the solute at infinite dilution was estimated along with the Pitzer-equation parameters. The last approach gave parameter estimates that reproduced the experimental data most accurately. The parameterized model predicted accurately densities of single-electrolyte and multielectrolyte solutions at -28.9, -17.8, -12.2, -6.7, 0, and 25°C. Available experimental data are generally quite poor. Accordingly, Pitzer-equation parameters estimated for subzero temperatures should be viewed as conditional until improved measurements of single-electrolyte solution densities at subzero temperatures are made.
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Mironenko, M.V., Grant, S.A. & Marion, G.M. Calculation of densities of aqueous electrolyte solutions at subzero temperatures. J Solution Chem 26, 433–460 (1997). https://doi.org/10.1007/BF02767600
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DOI: https://doi.org/10.1007/BF02767600