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Thermodynamics of aqueous solutions of the alkali metal sulfates

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Abstract

The available thermodynamic properties for aqueous solutions of each of the alkali metal sulfates have been combined and analyzed within the framework of the ion interaction model at temperatures up to 225°C. It was necessary to set α1 equal to 1.4kg1/2-mol−1/2 in order to obtain a satisfactory fit. The temperature dependence of the ion interaction parameters was given the functional form used by Rogers and Pitzer(1) in their study of Na2SO4(aq). With few exceptions, it was possible to reproduce the available thermodynamic data for aqueous solutions of the alkali metal to within the estimated experimental error. Thermodynamic results for Na2SO4(aq) appear to be adequate in this temperature range, but enthalpy and heat capacity data for the other alkali metal sulfate solutions are conspicuously lacking. Activity coefficients of these electrolytes decreased to less than 0.1 at moderate molalities at the higher temperatures, and their order changed with increasing temperature; two results which could be due to a combination of hydration and association effects.

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Authors and Affiliations

  1. Chemistry Division, Oak Ridge National Laboratory, 37831, Oak Ridge, TN

    H. F. Holmes & R. E. Mesmer

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  1. H. F. Holmes
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  2. R. E. Mesmer
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Research sponsored by the Division of Chemical Sciences, Office of Basic Energy Sciences of the U.S. Department of Energy under contract DE-AC05-840R21400 with the Martin Marietta Energy Systems, Inc.

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Holmes, H.F., Mesmer, R.E. Thermodynamics of aqueous solutions of the alkali metal sulfates. J Solution Chem 15, 495–517 (1986). https://doi.org/10.1007/BF00644892

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  • DOI: https://doi.org/10.1007/BF00644892

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