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Thermodynamic Model for BiPO4(cr) and Bi(OH)3(am) Solubility in the Aqueous Na+–H+–\(\mathrm{H}_{2}\mathrm{PO}_{4}^{-}\)–\(\mathrm{HPO}_{4}^{2-}\)–\(\mathrm{PO}_{4}^{3-}\)–OH−–Cl−–H2O System

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Abstract

Prior to this study no data for the solubility product of BiPO4(cr) or the complexation constants of Bi with phosphate were available. The solubility of BiPO4(cr) was studied at 23±2 °C from both the over- and under-saturation directions as functions of a wide range in time (6–309 days), pH values (0–15), and phosphate concentrations (reaching as high as 1.0 mol⋅kg−1). HCl or NaOH were used to obtain a range in pH values. Steady state concentrations and equilibrium were reached in <6 days. The data were interpreted using the SIT model. These extensive data provided a solubility product value for BiPO4(cr) and an upper limit value for the formation of BiPO4(aq). Because the aqueous system in this study involved relatively high concentrations of chloride, reliable values for the complexation constants of Bi with chloride were required to accurately interpret the solubility data. Therefore as a part of this investigation, existing Bi–Cl data were critically reviewed and used to obtain values of equilibrium constants for various Bi–Cl complexes at zero ionic strength along with the values for various SIT ion interaction parameters. Predictions based on these thermodynamic quantities agreed closely with our experimental data, the chloride concentrations of which ranged as high as 0.7 mol⋅kg−1. The study showed that BiPO4(cr) is stable at pH values <9.0. At pH values >9.0, Bi(OH)3(am) is the solubility controlling phase. Reliable values for the Bi(OH)3(am) solubility reactions involving Bi(OH)3(aq) and \(\mathrm{Bi}(\mathrm{OH})_{4}^{-}\) and the formation constants of these aqueous species are also reported.

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Authors and Affiliations

  1. Rai Enviro-Chem, LLC, PO Box 784, Yachats, OR, 97498, USA

    Dhanpat Rai

  2. Japan Atomic Energy Agency, Tokai Works, Tokai-mura, Japan

    Mikazu Yui & Akira Kitamura

  3. Pacific Northwest National Laboratory, Richland, WA, 99352, USA

    H. Todd Schaef

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  1. Dhanpat Rai
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  2. Mikazu Yui
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  3. H. Todd Schaef
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  4. Akira Kitamura
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Correspondence to Dhanpat Rai.

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Rai, D., Yui, M., Schaef, H.T. et al. Thermodynamic Model for BiPO4(cr) and Bi(OH)3(am) Solubility in the Aqueous Na+–H+–\(\mathrm{H}_{2}\mathrm{PO}_{4}^{-}\)–\(\mathrm{HPO}_{4}^{2-}\)–\(\mathrm{PO}_{4}^{3-}\)–OH−–Cl−–H2O System. J Solution Chem 39, 999–1019 (2010). https://doi.org/10.1007/s10953-010-9561-6

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