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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    Journal of radioanalytical and nuclear chemistry 130 (1989), S. 333-346 
    ISSN: 1588-2780
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The reliability of two solvent extraction techniques for the determination of Pu oxidation states in solution was tested with low-ionic-strength solutions and with high-Na and high-Mg brines that contained Pu concentrations sufficient for spectrophotometric analysis. One procedure only differentiates between reduced Pu [Pu(III) and Pu(IV)] and oxidized Pu [Pu(V) and Pu(VI)], whereas the second procedure was designed to differentiate between Pu(IV), Pu(V), and Pu(VI) in solution. Both procedures successfully differentiated between oxidized and reduced Pu in both dilute solutions and brines when tested with samples that contained only the Pu(IV), Pu(V), or Pu(VI) oxidation states. However, when the second solvent extraction procedure, which differentiates between Pu(V) and Pu(VI), was employed for solutions that did not contain a strong oxidant to maintain the Pu(VI) oxidation state, significant quantities of Pu(VI) were reduced to Pu(V) during extraction, indicating that accurate quantification of Pu(V) and Pu(VI) is not possible with this procedure.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 27 (1998), S. 1109-1122 
    ISSN: 1572-8927
    Keywords: Isosaccharinic acid ; solubility product ; aqueous complexes ; Ca complexes ; thermodynamic data
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The solubility of calcium isosaccharinate Ca(ISA)2(c) was determined at 23°C as a function of pH (1–14) and calcium ion molality (0.03–0.52). The similarity of solubility from the over- and undersaturation directions for different equilibration periods indicated that equilibrium in these solutions was reached rapidly (〈 7 days) and that these data can be used to develop thermodynamic equilibrium constants. The solubility data were interpreted using the Pitzer ion–interaction model. The logarithms of the thermodynamic equilibrium constants determined from these data were 1.30 for the dominant reaction at pH 〈 4.5 [Ca(ISA)2(c) + 2H+ ⇌ Ca2+ + 2HISA(aq)], and −2.22 for the dominant reaction at 4.5 [Ca(ISA)2(c)+ ⇌ Ca(ISA)2(aq)]. In addition, the logarithm of the dissociation constant of HISA [HISA(aq) ⇌ ISA- + H+] was calculated to be −4.46.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 28 (1999), S. 533-553 
    ISSN: 1572-8927
    Keywords: Actinides ; thermodynamic data ; Pitzer ion–interaction parameters ; trivalent actinides ; tetravalent actinides ; pentavalent actinides ; hexavalent actinides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A review of the applicability of Pitzer's equations to the aqueous thermodynamics of actinide species in natural waters is presented. This review includes a brief historical perspective on the application of Pitzer's equations to actinides, information on the difficulties and complexities of studying and modeling the different actinide oxidation states, and a discussion of the use of chemical analogs for different actinide oxidation states. Included are tables of Pitzer ion–interaction parameters and associated standard state equilibrium constants for each actinide oxidation state. These data allow the modeling of the aqueous thermodynamics of different actinide oxidation states to high ionic strength.
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 19 (1990), S. 175-185 
    ISSN: 1572-8927
    Keywords: Solubility ; barite ; celestite ; activity coefficient ; equilibrium constants
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The solubilities of barite [BaSO4(c)] and celestite [SrSO4(c)] in Na2SO4 were studied and found to be significantly lower than the experimental values reported in the literature. Our new solubility data are in excellent agreement with the predictions of ion interaction models, which have previously been parameterized primarily from solubility data obtained in chloride media. Our solubility data were analyzed both in terms of aqueous thermodynamic models that included ion association species and in terms of ion interaction models that did not require the explicit recognition of such species. In the case of SrSO4, although both ion association and ion interaction models can accurately model our solubility data, the ion interaction approach is preferred because it is easier to extend to higher concentrations. In the case of BaSO4, the aqueous ion interactions appear to be stronger than those for SrSO4, and so the explicit recognition of a BaSO4(aq) ion association species is preferred. The logarithms of the thermodynamic solubility products (log K sp ) for celestite and barite were −6.62±0.02 and −10.05±0.05, respectively. When the data were analyzed using models that include ion association species, the logarithms of the thermodynamic equilibrium constants for the SrSO4(aq) and BaSO4(aq) association reactions were 1.86±0.03 and 2.72±0.09, respectively.
    Type of Medium: Electronic Resource
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  • 15
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 24 (1995), S. 735-752 
    ISSN: 1572-8927
    Keywords: Solubility ; equilibrium constants ; solubility product ; Fe2(SeO3)3·6H2O(c) ; ferric selenite ; selenite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The aqueous solubility of Fe2(SeO3)3·6H2O(c) was studied in deionized water adjusted to a range in pH values from 0.77 to 5.1 and in Na2SeO3 solutions ranging in concentrations from 0.0002 to 0.02 mol-dm−3. The studies were conducted from both the undersaturation and oversaturation directions, with equilibration periods ranging from 7 to 1725 days. Stoichiometric dissolution of the solid was observed in solutions with pH values up to nearly 4. In general, concentrations of both Se and Fe decreased as pH increased from 1 to 4. Analyses of the equilibrated suspensions confirmed the equilibrium solid to be Fe2(SeO3)3·6H2O(c) and the aqueous Se to be selenite. Pitzer's ion-interaction model was used with selected ion pairs to interpret the solubility data. The logarithm of the solubility product of ferric selenite $$Fe_2 (SeO_3 )_3 .6H_2 O(c) \begin{array}{*{20}c} \to \\ \leftarrow \\ \end{array} 2Fe^{3 + } + 3SeO_3^{2 - } + 6H_2 O$$ was found to be −41.58±0.11. This value is less than any reported in the literature for a ferric selenite by more than 10 orders of magnitude. The solubility data and calculations show an extremely strong interaction between aqueous Fe3+ and SeO 3 2− ; interpretation of these data requires the inclusion of FeSeO 3 + i.e. $$Fe^{3 + } + SeO_3^{2 - } \begin{array}{*{20}c} \to \\ \leftarrow \\ \end{array} FeSeO_3^ + , log K = 11.15 \pm 0.11$$
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 24 (1995), S. 879-895 
    ISSN: 1572-8927
    Keywords: Solubility ; crystalline NdPO4 ; sulfate complexes ; Nd ; Am ; Pitzer parameters ; solubility product
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effects of Nd(III)/Am(III) complexation with sulfate were studied by 1) re-examining existing data for the Am−SO4 system using more, advanced aqueous electrolyte models valid to high concentration to obtain reliable thermodynamic data for SO 4 2− complexes or ion interactions with Nd3+ and Am3+ and 2) conducting experimental solubility studies of NdPO4(c), an analog phase of AmPO 4 (c), a possibly important phase in high level nuclear wastes, in the presence of SO 4 2− to test the newly developed thermodynamic model and show the possible influence of sulfate in a repository environment. The data showed that the increase in the solubility of NdPO 4 (c) resulted primarily from the increase in ionic strength. Slightly higher observed Nd concentrations in the presence of sulfate, as compared with concentrations predicted at the experimental ionic strengths, resulted from the weak complexes or ion interactions involving Nd 3+ −SO 4 2− . The Pitzer ion interaction parameters, applicable to 0.5m sulfate, were obtained for Am 3+ −SO 4 2− from a reinterpretation of known solvent extraction data. These parameters are also consistent with literature data for Am 3+ /Na+ exchange and solvent extraction in the presence of sulfate. When used for the analogous Nd 3+ −SO 4 2− system to predict NdPO 4 (c) solubility in the presence of sulfate, they provided excellent agreement between the predicted and the observed solubilities, indicating that they can be reliably used to determine Nd 3+ or Am 3+ ion interactions with SO 4 2− in all ground waters where SO 4 2− is less than 0.5m
    Type of Medium: Electronic Resource
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  • 17
    ISSN: 1572-8927
    Keywords: Solubility ; equilibrium constants ; activity coefficient ; hydrolysis ; β-Cd(OH)2(c) ; ion-interaction parameters ; cadmium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The solubility of Cd(OH)2(c) was studied in 0.01M NaClO4 solutions, from both the over- and the undersaturation directions, with OH− ion concentration ranging from 10−6 to 1.0 mol-L−1, and the equilibration period ranging from 2 to 28 days. Equilibrium Cd concentrations were reached in less than 2 days. The Cd(OH)2(c) solubility showed an amphoteric behavior. In the entire range of OH−/H+ investigated, the only dominant aqueous Cd(II) species required to explain the solubility of Cd(OH)2(c) are Cd2+, Cd(OH) 2 0 , and Cd(OH) 4 2− . The logarithms of the thermodynamic equilibrium constants of the Cd(OH)2(c) solubility reactions involving these species, that is, the reactions $$\begin{gathered} {\text{ }}Cd(OH)_2 (c) \rightleftarrows Cd^{2 + } + 20H^ - ,{\text{ }}Cd(OH)_2 (c) \rightleftarrows Cd(OH)_2^0 , \hfill \\ and Cd(OH)_2 (c) + 20H^ - \rightleftarrows Cd(OH)_4^{2 - } \hfill \\ \end{gathered}$$ were found to be −14.14±0.21, −7.04±0.21, and −5.62±0.32, respectively. The ion-interaction parameters reported in the literature, in conjunction with the values for Cd(OH) 2 0 −Na+(−0.20), Cd(OH) 4 2− −Na+ (β0 = 0.41, β1 = 0.7), and Cd(OH) 4 2− −K+ (β0 = 0.44, β1 = 1.44) obtained in this study, show that our low-ionic strength solubility data are also consistent with Cd(OH)2(c) solubility data obtained in solutions as concentrated as 10M in NaOH or KOH and 7M in Na(OH, ClO4).
    Type of Medium: Electronic Resource
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