Lanthanide Salts Solutions:  Representation of Osmotic Coefficients within the Binding Mean Spherical Approximation

Ruas, Alexandre; Moisy, Philippe; Simonin, Jean‐Pierre; Bernard, Olivier; Dufrêche, Jean‐François; Turq, Pierre

doi:10.1021/jp0450991

Cited by 34 publications

(71 citation statements)

References 44 publications

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“…This model has been applied recently to the case of lanthanide and actinide ions in solution (Ruas et al, 2005a(Ruas et al, , b, 2006a. Sketch of the new BiMSA model.…”

Section: Application To Associating Electrolytesmentioning

confidence: 99%

Description of the Thermodynamic Properties of Aqueous Ionic Solutions within the Mean Spherical Approximation

Simonin

Bernard

Blum

2008

Oil & Gas Science and Technology - Rev. IFP

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Résumé -Description des propriétés thermodynamiques de solutions aqueuses ioniques dans l'approximation sphérique moyenne -Les propriétés thermodynamiques de solutions aqueuses ioniques sont décrites dans l'approximation sphérique moyenne (MSA). Le modèle MSA original et celui avec association (BiMSA) ont été complétés de façon à inclure les effets de la solvatation. On montre que le modèle est capable de représenter la thermodynamique des solutions ioniques dans un large domaine de concentration, généralement jusqu'à la saturation, dans le cas des électrolytes forts et associés. Ce modèle constitue une alternative intéressante au modèle de Pitzer. Abstract -Description of the Thermodynamic Properties of Aqueous Ionic Solutions within the Mean Spherical Approximation -The thermodynamic properties of ionic solutions are described within the mean spherical approximation (MSA

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“…This model has been applied recently to the case of lanthanide and actinide ions in solution (Ruas et al, 2005a(Ruas et al, , b, 2006a. Sketch of the new BiMSA model.…”

Section: Application To Associating Electrolytesmentioning

confidence: 99%

Description of the Thermodynamic Properties of Aqueous Ionic Solutions within the Mean Spherical Approximation

Simonin

Bernard

Blum

2008

Oil & Gas Science and Technology - Rev. IFP

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“…The parameters used for this purpose were found to have plausible adjusted values. 6 The studied salts included several analogues of the most interesting actinide(III) salts for nuclear spent fuel treatment (in the beginning of the lanthanide series). The adjusted parameters are σ + (0) , the hydrated lanthanide(III) diameter at infinite dilution, σ (1) , reflecting the (hydrated) cation diameter change with concentration, R, reflecting the permittivity change with concentration, and K, the cation-anion association constant.…”

Section: Comparison Of Experimental Cerium Salts Data With Predicted mentioning

confidence: 99%

“…The modified parameter values are given in Table 2, in which we show, for the studied concentration region, the discrepancy between the resulting osmotic coefficient calculated by the BIMSA theory and the available experimental data. 8,9,[11][12][13][14][15] In practice, the modifications of the initial parameters shown in ref 6 were so small that they did not appreciably worsen the agreement between the calculated and experimental osmotic coefficients from refs 8,9, and 11-15. From the ionic radius of cerium(III) 7 ( Table 1) and variation of all the parameters with the ionic radius from lanthanum nitrate (respectively, chloride) to samarium nitrate (respectively, chloride) (eqs 7-13), we recalculated and proposed a set of these parameters for the cerium nitrate (respectively, chloride) salt ( Table 3).…”

Section: Comparison Of Experimental Cerium Salts Data With Predicted mentioning

confidence: 99%

Experimental Determination of Water Activity for Binary Aqueous Cerium(III) Ionic Solutions: Application to an Assessment of the Predictive Capability of the Binding Mean Spherical Approximation Model

et al. 2005

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This work is aimed at a description of the thermodynamic properties of actinide salt solutions at high concentration. The predictive capability of the binding mean spherical approximation (BIMSA) theory to describe the thermodynamic properties of electrolytes is assessed in the case of aqueous solutions of lanthanide(III) nitrate and chloride salts. Osmotic coefficients of cerium(III) nitrate and chloride were calculated from other lanthanide(III) salts properties. In parallel, concentrated binary solutions of cerium nitrate were prepared in order to measure experimentally its water activity and density as a function of concentration, at 25 degrees C. Water activities of several binary solutions of cerium chloride were also measured to check existing data on this salt. Then, the properties of cerium chloride and cerium nitrate solutions were compared within the BIMSA model. Osmotic coefficient values for promethium nitrate and promethium chloride given by this theory are proposed. Finally, water activity measurements were made to examine the fact that the ternary system Ce(NO3)3/HNO3/H2O and the quaternary system Ce(NO3)3/HNO3/N2H5NO3/H2O may be regarded as "simple solutions" (in the sense of Zdanovskii and Mikulin).

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“…BiMSA BiMSA (7) and the total osmotic coefficient is (8) in which ΔA BiMSA and ΔΦ BiMSA are the BiMSA contributions to the Helmholtz energy per volume unit and the osmotic coefficient (eqs 5−18 in ref 9), and ρ t is the total number density, ρ t ≡ ρ + + ρ − . Besides, Δln γ ± HS and ΔΦ HS are the hard sphere contributions to the mean ionic activity and osmotic coefficients, respectively.…”

Section: Hsmentioning

confidence: 99%

Solutions of Alkylammonium and Bulky Anions: Description of Osmotic Coefficients within the Binding Mean Spherical Approximation

Papaïconomou

Simonin

Bernard

2012

Ind. Eng. Chem. Res.

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The binding mean spherical approximation (BiMSA) is used to describe osmotic coefficients for aqueous solutions of salts containing alkylammonium cations or bulky anions. A total of 35 salt solutions is accurately described at 25°C over the whole concentration range, up to very high concentrations such as 20 mol·kg −1 for methylammonium chloride or 24 mol·kg −1 for ammonium thiocyanate. The ion diameters, the permittivity of solution, and the association constant are adjustable parameters within the BiMSA model. New diameter values are assigned to alkylammonium cations and bulky anions such as tetrafluoroborate, alkanesulfonates, methylsulfate, trifluoroacetate, or trifluoromethanesulfonate anions. Alkylammonium sizes are in reasonable agreement with literature values. Besides, association constants values obtained within the BiMSA model compare well with literature values when available. INTRODUCTIONThe mean spherical approximation (MSA) 1−4 is a statistical thermodynamic model for the representation of the thermodynamic properties of electrolyte solutions, regarding an ion i as a charged sphere of diameter σ i immersed in a solvent of permittivity ε. The MSA model uses parameters (ion sizes and relative solution permittivity) that have some physical meaning. For applications to real solutions, crystallographic values are taken for the halide anions radii and the size of a given cation at infinite dilution is the same for all salts containing this cation. 5 Within the binding MSA (BiMSA) version of the model, 6,7 an effective association constant is introduced, taking into account the pairing or association of unlike ions. This model has been shown to provide good description for deviations from ideality in aqueous solutions of salts such as alkali halides, nitrates, perchlorates, sulfates, 6−8 or, more recently, lanthanide salts 9,10 or mixtures of salts. 5,7,10 The BiMSA model has been widely used to describe monatomic cations. An attempt at describing salts containing a tetramethyl-, tetraethyl-, or tetrapropylammonium cation and a halide anion has previously been reported. 6 Nevertheless, the results obtained at the time are not satisfying, because despite an accurate description of the osmotic coefficients of tetraalkylammonium halide solutions, the values for the adjusted parameters, such as the cation diameter, were not plausible.Therefore, in order to extend the number of solutions described within the BiMSA model and in order to describe solutions containing large and polyatomic cations or anions, we apply here the BiMSA model to the description of aqueous solutions containing tetraalkylammonium salts with methyl, ethyl, or propyl alkyl chains and with the chloride, bromide, iodide, or nitrate anion. Because micelles might be formed

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Lanthanide Salts Solutions: Representation of Osmotic Coefficients within the Binding Mean Spherical Approximation

Cited by 34 publications

References 44 publications

Description of the Thermodynamic Properties of Aqueous Ionic Solutions within the Mean Spherical Approximation

Description of the Thermodynamic Properties of Aqueous Ionic Solutions within the Mean Spherical Approximation

Experimental Determination of Water Activity for Binary Aqueous Cerium(III) Ionic Solutions: Application to an Assessment of the Predictive Capability of the Binding Mean Spherical Approximation Model

Solutions of Alkylammonium and Bulky Anions: Description of Osmotic Coefficients within the Binding Mean Spherical Approximation

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