Thermodynamic model for the solubility of ThO2(am) in the aqueous Na+-H+-OH--NO3--H2O-EDTA system

Verfasser / Beitragende:
[Yuanxian Xia, Andrew R. Felmy, Linfeng Rao, Zheming Wang, Nancy J. Hess]
Ort, Verlag, Jahr:
2003
Enthalten in:
Radiochimica Acta/International journal for chemical aspects of nuclear science and technology, 91/12/2003(2003-12-01), 751-760
Format:
Artikel (online)
ID: 378878425
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024 7 0 |a 10.1524/ract.91.12.751.23416  |2 doi 
035 |a (NATIONALLICENCE)gruyter-10.1524/ract.91.12.751.23416 
245 0 0 |a Thermodynamic model for the solubility of ThO2(am) in the aqueous Na+-H+-OH--NO3--H2O-EDTA system  |h [Elektronische Daten]  |c [Yuanxian Xia, Andrew R. Felmy, Linfeng Rao, Zheming Wang, Nancy J. Hess] 
520 3 |a The solubility of ThO2(am) in the aqueous Na+-H+-OH--NO3--H2O-EDTA system as a function of pCH⁺ (= -log[H+]) and variable NaNO3 (0.5M to 6.0M) has been determined. The experimental observations show that between pCH⁺ values 4.2 to 8.2, a stoichiometric 1:1 Th-EDTA complex forms that completely saturates the added chelate concentration. Th concentrations then decrease linearly with increasing pCH⁺ at pCH⁺>9.0. These changes in solubility are not predicted by currently available thermodynamic models. The ion-interaction model of Pitzer was used to interpret these solubility data. Thermodynamic analysis indicates that the speciation under basic conditions is dominated by monomeric mixed Th-OH-EDTA complexes. X-ray absorption near-edge spectroscopy confirmed the absence of the higher order ( e.g. dimeric) species. The equilibrium constants for the following reactions were determined from analysis of the solubility data: ThO2(am) + EDTA4- + 2H2O ↔ Th(OH)2EDTA2- + 2OH-, log K = -6.0; and ThO2(am) + EDTA4- + 2H2O ↔ Th(OH)3EDTA3- + OH-, log K∼-7.5. Pitzer ion-interaction parameters for the Th(OH)2EDTA2- and the Th(OH)3EDTA3- species were calculated. It was also determined that the solubility method for examining the complexation of tetravalent actinides with EDTA is limited to relatively high aqueous EDTA concentrations, relative to the amount of ThO2(am) precipitate, owing to the adsorption of the EDTA chelator by the solid phase. 
540 |a © 2003 Oldenbourg Wissenschaftsverlag GmbH 
690 7 |a Laboratory techniques, experiments  |2 nationallicence 
690 7 |a Analytical chemistry  |2 nationallicence 
690 7 |a Inorganic chemistry  |2 nationallicence 
700 1 |a Xia  |D Yuanxian  |4 aut 
700 1 |a Felmy  |D Andrew R.  |4 aut 
700 1 |a Rao  |D Linfeng  |4 aut 
700 1 |a Wang  |D Zheming  |4 aut 
700 1 |a Hess  |D Nancy J.  |4 aut 
773 0 |t Radiochimica Acta/International journal for chemical aspects of nuclear science and technology  |d Oldenbourg Wissenschaftsverlag GmbH  |g 91/12/2003(2003-12-01), 751-760  |x 0033-8230  |q 91:12/2003<751  |1 2003  |2 91  |o ract 
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950 |B NATIONALLICENCE  |P 700  |E 1-  |a Felmy  |D Andrew R.  |4 aut 
950 |B NATIONALLICENCE  |P 700  |E 1-  |a Rao  |D Linfeng  |4 aut 
950 |B NATIONALLICENCE  |P 700  |E 1-  |a Wang  |D Zheming  |4 aut 
950 |B NATIONALLICENCE  |P 700  |E 1-  |a Hess  |D Nancy J.  |4 aut 
950 |B NATIONALLICENCE  |P 773  |E 0-  |t Radiochimica Acta/International journal for chemical aspects of nuclear science and technology  |d Oldenbourg Wissenschaftsverlag GmbH  |g 91/12/2003(2003-12-01), 751-760  |x 0033-8230  |q 91:12/2003<751  |1 2003  |2 91  |o ract 
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