The solubility equation in ternary water-Salt systems Communication 4. Systems with unlike ions

Kirgintsev, A. N.; Luk'yanov, A. V.

doi:10.1007/bf00848899

Cited by 3 publications

(13 citation statements)

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“…c Molalities of Rb 2 SO 4 (aq) for the Series 14 and 15 experiments were corrected for the presence of impurities. In addition to the results given in tables 2 and 3, there are some previous isopiestic studies for both Rb 2 SO 4 (aq) and Cs 2 SO 4 (aq) at T = 298.15 K, (6,(25)(26)(27)(28)(29) and for Cs 2 SO 4 (aq) and parameters. (19) Molalities without asterisks are from the higher-quality experiments for which the uncertainty of the average molalities is 0.001 · m for m > 0.5 mol · kg −1 and 0.002 · m for m < 0.5 mol · kg −1 .…”

Section: Methodsmentioning

confidence: 93%

“…It is not necessary to correct these earlier published isopiestic molalities to the values of the molar masses accepted for the present study, because these corrections are considerably smaller than the typical experimental uncertainty. The article by Kirgintsev and Luk'yanov (25) was published in the English translation journal Soviet Radiochemistry, where it is claimed that the compositions of the solutions at isopiestic equilibrium are reported as "molarities", i.e. with units of mol · dm −3 , rather than with the much more typical units of mol · kg −1 .…”

Section: Analysis Of Published Thermodynamic Information For Rbmentioning

confidence: 98%

“…Table 4 summarizes these studies and lists their molality ranges, experimental temperature(s), the reference standard used, and the number of isopiestic equilibrations. The reference standard for the majority of these studies is NaCl(aq), (1,(26)(27)(28)(29) but Cudd and Felsing (6) used Na 2 SO 4 (aq) for this purpose, and Kirgintsev and Luk'yanov (25) used H 2 SO 4 (aq).…”

Section: Analysis Of Published Thermodynamic Information For Rbmentioning

confidence: 99%

“…Values of φ reported in tables 2 and 3 were computed from the listed equilibrium molalities and from values of φ * of NaCl(aq) calculated from the extended Pitzer model of Archer, (19) as were the φ of Rb 2 SO 4 (aq) and Cs 2 SO 4 (aq) from all but two of the published isopiestic studies listed in table 4. Osmotic coefficients of the reference standard from the study of Cudd and Felsing (6) were recalculated on the basis of the parameters of our extended Pitzer model for Na 2 SO 4 (aq) at T = 298.15 K, (4) and those of Kirgintsev and Luk'yanov (25) on the basis of the model of Clegg et al (30) for H 2 SO 4 (aq). It is not necessary to correct these earlier published isopiestic molalities to the values of the molar masses accepted for the present study, because these corrections are considerably smaller than the typical experimental uncertainty.…”

Section: Analysis Of Published Thermodynamic Information For Rbmentioning

confidence: 99%

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Isopiestic determination of the osmotic and activity coefficients of Rb 2SO4 (aq) and Cs 2SO 4(aq) at T= (298.15 and 323.15) K, and representation with an extended ion-interaction (Pitzer) model

Palmer

Rard

Clegg

2002

The Journal of Chemical Thermodynamics

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Isopiestic vapor-pressure measurements were made for Rb 2SO 4(aq) from molalitym = (0.16886 to 1.5679 )mol · kg - 1atT = 298.15 K and from m = (0.32902 to 1.2282 )mol · kg - 1at T = 323.15 K, and for Cs 2SO4 (aq) from m = (0.11213 to 3.10815 )mol · kg - 1at T = 298.15 K and fromm = (0.11872 to 3.5095 )mol · kg - 1atT = 323.15 K, with NaCl(aq) as the reference standard. Published thermodynamic information for these systems were reviewed and the isopiestic equilibrium molalities and dilution enthalpies were critically assessed and recalculated in a consistent manner. Values of the four parameters of an extended version of Pitzer‘s model for osmotic and activity coefficients with an ionic-strength dependent third virial coefficient were evaluated for both systems at both temperatures, as were those of the usual three-parameter Pitzer model. Similarly, parameters of Pitzer‘s model for the relative apparent molar enthalpies of dilution were evaluated at T = 298.15 K for both Rb 2SO 4(aq) and Cs 2SO 4(aq) for the more restricted range of m 0.101 mol · kg - 1. Values of the thermodynamic solubility product Ks(Rb2 SO 4, cr, 298.15 K ) = (0.1392 ± 0.0154) and the CODATA compatible standard molar Gibbs free energy of formation?fGmo (Rb 2SO 4, cr, 298.15 K ) = - (1316.91 ± 0.59)kJ · mol - 1, standard molar enthalpy of formation?fHmo (Rb 2SO 4, cr, 298.15 K ) = - (1435.07 ± 0.60)kJ · mol - 1, and standard molar entropy S mo(Rb2 SO 4, cr, 298.15 K ) = (199.60 ± 2.88)J · K - 1· mol - 1were derived. A sample of one of the lots of Rb 2SO 4(s) used for part of our isopiestic measurements was analyzed by ion chromatography, and was found to be contaminated with potassium and cesium in amounts that significantly exceeded the claims of the supplier. In contrast, analysis by ion chromatography of a lot of Cs 2SO 4(s) used for some of our experiments showed it was highly pure

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Section: Methodsmentioning

confidence: 93%

Section: Analysis Of Published Thermodynamic Information For Rbmentioning

confidence: 98%

Section: Analysis Of Published Thermodynamic Information For Rbmentioning

confidence: 99%

Section: Analysis Of Published Thermodynamic Information For Rbmentioning

confidence: 99%

See 2 more Smart Citations

Isopiestic determination of the osmotic and activity coefficients of Rb 2SO4 (aq) and Cs 2SO 4(aq) at T= (298.15 and 323.15) K, and representation with an extended ion-interaction (Pitzer) model

Palmer

Rard

Clegg

2002

The Journal of Chemical Thermodynamics

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“…The apparatus, proposed by Kirgintsev et al (5) and improved by Majima et al (6) (7), is schematically illustrated in Fig. 1.…”

Section: Methodsmentioning

confidence: 99%

Determination of Water and Solute Activities in H2SO4–In2(SO4)3–H2O System

Yamauchi

Sakao

1987

Trans. JIM

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The activities of water of the system H2SO4-In2(SO4)3-H2O are determined by using the isopiestic method at 298 K. The results obtained satisfactorily obey the Zdanovskii's empirical rule. From the water activities determined isopiestically, the mean ionic activity coefficients of the solutes are calculated by applying the Mckay-Perring method. Furthermore, the applicability of the Meissner's empirical procedure to estimation of the mean ionic activity coefficient of indium sulfate and that of the RobinsonBower equation to evaluate the water activity to the present solution system are also discussed. (Received October 16, 1986) Keywords: water activity, mean ionic activity coefficient, sulfuric acid, indium sulfate, isopiestic method, electrolyte aqueous solution. ‡T . Introduction Most of the valuable metals utilized as functional materials are frequently recovered as byproducts from the production processes of mass-produced metals. In this case, the separation between them may be made occasionally by precipitation operation by neutralization of the leaching solution containing sulfuric acid and metal sulfates. As a theoretical background for the precipitation operation, we commonly refer to the ion activity-pH diagrams of simple metal-H2O systems. It is, however, questionable whether such a simple theory can be applied to more complicated systems containing sulfate ions, which have a strong tendency to form sulfato-complexes with metal ions.From this viewpoint a series of investigations have been made by the authors on the pH-dependence of the solubility of IIIb-metal hydroxysalts(1)-(3). However, to analyse the experimental results obtained, some thermodynamic information about the systems H2SO4-M2(SO4)3-H2O (M:Ga,In) was needed. The objective of this paper is, therefore, to present information on the water and solute activities in the system H2SO4-In2(SO4)3-H2O, being not available yet.

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Improvement of the Zdanovskii−Stokes−Robinson Model for Mixtures Containing Solutes of Different Charge Types

Clegg

Seinfeld

2004

J. Phys. Chem. A

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The Zdanovskii−Stokes−Robinson (ZSR) relationship [Stokes and Robinson (J. Phys. Chem. 1966, 70, 2126−2130)] enables the solvent content of a liquid mixture to be estimated, for a specified solvent activity, from data for pure solutions of each of the individual solutes. There is an analogous relationship for the activity coefficients of the solutes. The method has been shown to be exact, in the limit of extreme dilution, only for mixtures containing either all uncharged (neutral) solutes or electrolytes all of the same charge type, and in practice it is found to be most accurate for such mixtures. Here we derive an addition to the ZSR equations which removes this limitation by incorporating simple Debye−Hückel terms into the equations for solvent mass and solute activity coefficients. This addition, in its simplest form, does not involve any new fitted parameters or require any further thermodynamic information. The relationship is general, and not limited to particular Debye−Hückel expressions. Application of the revised model to activity and osmotic coefficient data for the system NaCl−Na2SO4−H2O at 298.15 K shows that errors are reduced, compared to predictions of the standard model, by up to a factor of 2. Solubilities of NaCl(cr), Na2SO4·10H2O(cr), and Na2SO4(cr) in that system are similarly better predicted. Activity coefficients of uncharged solutes in salt solutions calculated using the revised model are now largely consistent with the empirically observed Setchenow relationship.

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The solubility equation in ternary water-Salt systems Communication 4. Systems with unlike ions

Cited by 3 publications

References 1 publication

Isopiestic determination of the osmotic and activity coefficients of Rb 2SO4 (aq) and Cs 2SO 4(aq) at T= (298.15 and 323.15) K, and representation with an extended ion-interaction (Pitzer) model

Isopiestic determination of the osmotic and activity coefficients of Rb 2SO4 (aq) and Cs 2SO 4(aq) at T= (298.15 and 323.15) K, and representation with an extended ion-interaction (Pitzer) model

Determination of Water and Solute Activities in H<SUB>2</SUB>SO<SUB>4</SUB>–In<SUB>2</SUB>(SO<SUB>4</SUB>)<SUB>3</SUB>–H<SUB>2</SUB>O System

Improvement of the Zdanovskii−Stokes−Robinson Model for Mixtures Containing Solutes of Different Charge Types

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The solubility equation in ternary water-Salt systems Communication 4. Systems with unlike ions

Cited by 3 publications

References 1 publication

Isopiestic determination of the osmotic and activity coefficients of Rb 2SO4 (aq) and Cs 2SO 4(aq) at T= (298.15 and 323.15) K, and representation with an extended ion-interaction (Pitzer) model

Isopiestic determination of the osmotic and activity coefficients of Rb 2SO4 (aq) and Cs 2SO 4(aq) at T= (298.15 and 323.15) K, and representation with an extended ion-interaction (Pitzer) model

Determination of Water and Solute Activities in H<SUB>2</SUB>SO<SUB>4</SUB>&ndash;In<SUB>2</SUB>(SO<SUB>4</SUB>)<SUB>3</SUB>&ndash;H<SUB>2</SUB>O System

Improvement of the Zdanovskii−Stokes−Robinson Model for Mixtures Containing Solutes of Different Charge Types

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Determination of Water and Solute Activities in H<SUB>2</SUB>SO<SUB>4</SUB>–In<SUB>2</SUB>(SO<SUB>4</SUB>)<SUB>3</SUB>–H<SUB>2</SUB>O System