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  • 1
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-8927
    Keywords: Thorium (IV) ; sulfate ; bisulfate ; ammonium ion ; alkali metal ions ; aqueous ; thermodynamic ; complexation ; high ionic strength
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An aqueous thermodynamic model that is valid from zero to high concentration is proposed for the Na+−K+−Li+−NH 4 + −Th4+−SO 4 2− −HSO 4 − −H2O system. The model is based on the aqueous ion-interaction model of Pitzer and coworkers. The thorium sulfate complex species Th(SO4)2(aq) and Th(SO4) 3 2− are also included in the model. The final thermodynamic model presented here accurately predicts all reliable thermodynamic data, including solvent extraction and solubility data, for the Na+−K+−Li+−NH 4 + −Th4+−SO 4 2− −HSO 4 − −H2O system to high concentration. The aqueous thermodynamics of high-valence (3:2, 4:2), electrolytes are complicated by very strong specific ion interactions or ion pairing in dilute solution and by an effective redissociation of aqueous complex species at high concentration. Methods of treating these complications, in terms of valid aqueous thermodynamic models, are discussed in detail for the high-valence Th4+−SO 4 2− −H2O system.
    Type of Medium: Electronic Resource
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  • 3
    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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  • 4
    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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  • 5
    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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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 27 (1998), S. 435-454 
    ISSN: 1572-8927
    Keywords: EDTA ; HEDTA ; NTA ; IDA ; solubility ; strontium ; calcium ; waste processing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effects of calcium, hydroxide, and carbonate on the displacement of Sr from four organic chelates: ethylenedinitrilotetraacetic acid (EDTA), N-(2-hydroxyethyl)ethylenedinitrilotriacetic acid (HEDTA) nitrilotriacetic acid (NTA), and iminidiacetic acid (IDA) was studied in solutions with high base and carbonate concentration. Comparison of solutions with and without added chelators allowed the speciation changes in solution to be directly determined. Increases in both carbonate and calcium concentration were effective in displacing Sr from the chelators even under high carbonate concentration. Increases in hydroxide were ineffective in removal of Sr from the chelators, even at base concentrations as high as 6M. Under certain specific conditions, most notably when both CaCO3(s) and SrCO3(s) are present in solution, chemical equilibrium constraints result in cancelation of activity coefficient changes for aqueous Sr and Ca organic chelate complexes. Under such conditions the predicted ratios of chelated Ca and Sr become independent of the ionic media and predictive relations using known equilibrium constants give very good representations of the experimental data. These results indicate that manipulation of metal ion displacement reactions during chemical processing of Sr–chelate solutions can result in the displacement of Sr from organic chelators. The implications of such strategies in processing high level waste supernatants stored at Department of Energy (DOE) sites is discussed.
    Type of Medium: Electronic Resource
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  • 7
    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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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 21 (1992), S. 525-532 
    ISSN: 1572-8927
    Keywords: Calcium ; molybdate ; aqueous ; thermodynamic ; complexation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The solubility of powellite [CaMoO4(c)] was studied in aqueous Na2MoO4, CaCl2 and Ca(NO3)2 solutions ranging in concentrations from 1×10−4M to 1.0M and over equilibration times extending to 36 days. Our experimental data were interpreted using the aqueous ion-interaction model of Pitzer and coworkers. The Ca2+−MoO 4 2− ion-interactions were found to be analogous to Ca2+−SO 4 2− . The use of Ca2+−MoO 4 2− ion-interactions parameters (β(0)=0.2, β(1) = 3.1973 and β(2)) and a logK sp of −7.93 gave excellent predictions of all of the experimental data. Commonion ternary interaction parameters such as MoO 4 2− −Cl− or MoO 4 2− −NO 3 − were not required.
    Type of Medium: Electronic Resource
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