PNNL

Abstract

To determine the solubility product of PuPO4(cr, hyd.) and the complexation constants of Pu(III) with phosphate and EDTA, the solubility of PuPO4(cr, hyd.) was investigated as a function of: 1) time and pH varying from 1.0 to 12.0 and at a fixed 0.00032 M phosphate concentration; 2) NaH2PO4 concentrations varying from 0.0001 M to 1.0 M and at a fixed pH value of 2.5; 3) time and pH varying from 1.3 to 13.0 at fixed concentrations of 0.00032 M phosphate and 0.0004 M or 0.002 M Na2H2EDTA; and 4) Na2H2EDTA concentrations varying from 0.00005 M to 0.0256 M at a fixed 0.00032 M 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 Na2S2O4 helped maintain Pu as Pu(III). The solubility data were interpreted using Pitzer and SIT models, and both provided similar values for the solubility product of PuPO4(cr, hyd.) and for the formation constant of PuEDTA-. The log10 of the solubility product of PuPO4(cr, hyd.) (PuPO4(cr, hyd.) = Pu3+ + PO4 ) was determined to be –(24.42 ± 0.38). Pitzer modeling showed that phosphate interactions with Pu3+ were extremely weak and did not require any phosphate complexes (e.g., PuPO4(aq), PuH2PO42+, Pu(H2PO4)2+, Pu(H2PO4)3(aq), and Pu(H2PO4)4-), as proposed in existing literature, to explain the experimental data. SIT modeling, however, required the inclusion of PuH2PO42+ to explain the data in high NaH2PO4 concentrations; this illustrates the differences one can expect when using these two chemical models to interpret the data. As the Pu(III)-EDTA species, only PuEDTA- was needed to interpret the experimental data in a large range in pH values (1.3–12.9) and EDTA concentrations (0.00005–0.256 M). Calculations based on density functional theory support the existence of PuEDTA- (with prospective stoichiometry as Pu(OH2)3EDTA-) as the chemically and structurally stable species. The log10 of the complexation constant for the formation of PuEDTA- [Pu3+ + EDTA4- = PuEDTA-] determined in this study is -20.15 ± 0.59. The data also showed that PuHEDTA(aq), Pu(EDTA)25-, Pu(EDTA)(HEDTA)4-, Pu(EDTA)(H2EDTA)3-, and Pu(EDTA)(H3EDTA)2-, reported in the literature, have no region of dominance in the experimental range of variables investigated in this study.