NDLI: PuPO$_{4}$(cr, hyd.) Solubility Product and Pu$^{3+}$ Complexes with Phosphate and Ethylenediaminetetraacetic Acid

Content Provider	Springer Nature Link
Author	Rai, Dhanpat Moore, Dean A. Felmy, Andrew R. Rosso, Kevin M. Bolton, Harvey
Copyright Year	2010
Abstract	To determine the solubility product of PuPO$_{4}$(cr, hyd.) and the complexation constants of Pu(III) with phosphate and EDTA, the solubility of PuPO$_{4}$(cr, hyd.) was investigated as a function of: (1) time and pH (varied from 1.0 to 12.0), and at a fixed 0.00032 mol⋅L$^{−1}$ phosphate concentration; (2) NaH$_{2}$PO$_{4}$ concentrations varying from 0.0001 mol⋅L$^{−1}$ to 1.0 mol⋅L$^{−1}$ and at a fixed pH of 2.5; (3) time and pH (varied from 1.3 to 13.0) at fixed concentrations of 0.00032 mol⋅L$^{−1}$ phosphate and 0.0004 mol⋅L$^{−1}$ or 0.002 mol⋅L$^{−1}$ Na$_{2}$H$_{2}$EDTA; and (4) Na$_{2}$H$_{2}$EDTA concentrations varying from 0.00005 mol⋅L$^{−1}$ to 0.0256 mol⋅L$^{−1}$ at a fixed 0.00032 mol⋅L$^{−1}$ phosphate concentration and at pH values of approximately 3.5, 10.6, and 12.6. A combination of solvent extraction and spectrophotometric techniques confirmed that the use of hydroquinone and Na$_{2}$S$_{2}$O$_{4}$ helped maintain the Pu as Pu(III). The solubility data were interpreted using the Pitzer and SIT models, and both provided similar values for the solubility product of PuPO$_{4}$(cr, hyd.) and for the formation constant of PuEDTA$^{−}$. The log $_{10}$ of the solubility product of PuPO$_{4}$(cr, hyd.) [PuPO$_{4}$(cr, hyd.) $\rightleftarrows$ $\mathrm{Pu}^{3+}+\mathrm{PO}_{4}^{3-}$ ] was determined to be −(24.42±0.38). Pitzer modeling showed that phosphate interactions with Pu$^{3+}$ were extremely weak and did not require any phosphate complexes [e.g., PuPO$_{4}$(aq), $\mathrm{PuH}_{2}\mathrm{PO}_{4}^{2+}$ , $\mathrm{Pu(H}_{2}\mathrm{PO}_{4})_{2}^{+}$ , Pu(H$_{2}$PO$_{4}$)$_{3}$(aq), and $\mathrm{Pu(H}_{2}\mathrm{PO}_{4})_{4}^{-}$ ] as proposed in existing literature, to explain the experimental solubility data. SIT modeling, however, required the inclusion of $\mathrm{PuH}_{2}\mathrm{PO}_{4}^{2+}$ to explain the data in high NaH$_{2}$PO$_{4}$ concentrations; this illustrates the differences one can expect when using these two different chemical models to interpret the data. Of the Pu(III)-EDTA species, only PuEDTA$^{−}$ was needed to interpret the experimental data over a large range of pH values (1.3–12.9) and EDTA concentrations (0.00005–0.256 mol⋅L$^{−1}$). Calculations based on density functional theory support the existence of PuEDTA$^{−}$ (with prospective stoichiometry as Pu(OH$_{2}$)$_{3}$EDTA$^{−}$) as the chemically and structurally stable species. The log $_{10}$ value of the complexation constant for the formation of PuEDTA$^{−}$ [ $\mathrm{Pu}^{3+}+\mathrm{EDTA}^{4-}\rightleftarrows \mathrm{PuEDTA}^{-}$ ] determined in this study is −20.15±0.59. The data also showed that PuHEDTA(aq), $\mathrm{Pu(EDTA)}_{4}^{5-}$ , Pu(EDTA)(HEDTA)$^{4−}$, Pu(EDTA)(H$_{2}$EDTA)$^{3−}$, and Pu(EDTA)(H$_{3}$EDTA)$^{2−}$, although reported in the literature, have no region of dominance in the experimental range of variables investigated in this study.
Starting Page	778
Ending Page	807
Page Count	30
File Format	PDF
ISSN	00959782
Journal	Journal of Solution Chemistry
Volume Number	39
Issue Number	6
e-ISSN	15728927
Language	English
Publisher	Springer US
Publisher Date	2010-06-12
Publisher Place	Boston
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Thermodynamics Solubility Pu(III) EDTA PuEDTA$^{−}$ Pitzer model Pu(III) phosphate complexes Solubility product PuPO$_{4}$(cr,hyd.) Condensed Matter Physics Inorganic Chemistry Oceanography Geochemistry Industrial Chemistry/Chemical Engineering Physical Chemistry
Content Type	Text
Resource Type	Article
Subject	Biochemistry Molecular Biology Biophysics Physical and Theoretical Chemistry

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