Isopiestic determination of the activity coefficients of some aqueous rare earth electrolyte solutions at 25.degree.C. 3. The rare earth nitrates

Rard, Joseph A.; Shiers, Loren E.; Heiser, David J.; Spedding, F. H.

doi:10.1021/je60074a015

Cited by 76 publications

(121 citation statements)

References 18 publications

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“…Trends in mean molal activity coefficients and water activities for aqueous rare earth nitrates when plotted against the ionic radii of the rare earth ions at T = 298.15 K have been found to be different from those trends obtained for the aqueous rare earth chlorides and perchlorates [6][7][8][9]. Such differences are believed to be indicative of a higher degree of complex formation within the rare earth nitrate systems.…”

Section: The Effects Of Complex Formationmentioning

confidence: 58%

“…In this paper, we turn our attention to aqueous rare earth nitrate systems in which the degree of complex formation, as judged from the available complex formation 0021-9614/$ -see front matter Ó 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.jct.2004.08.010 constants (see [5] and references therein) and also the results of isopiestic [6][7][8][9] and electrical conductance measurements [10], is greater than that for the chlorides but still considerably less than that found for sulfate systems. Values for stability constants reported in the literature indicate that nitrate complex formation is more prevalent for the light rare earths than the heavy rare earths with a maximum occurring approximately at samarium [11].…”

Section: Introductionmentioning

confidence: 95%

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Apparent molar volumes and apparent molar heat capacities of Pr(NO3)3(aq), Gd(NO3)3(aq), Ho(NO3)3(aq), and Y(NO3)3(aq) at T=(288.15, 298.15, 313.15, and 328.15) K and p=0.1 MPa

Hakin

Liu

Erickson

et al. 2005

The Journal of Chemical Thermodynamics

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Apparent molar volumes and apparent molar heat capacities of Pr(NO 3 ) 3 (aq), Gd(NO 3 ) 3 (aq), Ho(NO 3 ) 3 (aq), and Y(NO 3 ) 3 (aq) at T = (288.15, 298.15, 313.15, and 328.15) K and p = 0.1 MPa AbstractRelative densities and relative massic heat capacities have been measured for acidified solutions of Y(NO 3 ) 3 (aq), Pr(NO 3 ) 3 (aq), and Gd(NO 3 ) 3 (aq) at T = (288. 15, 298.15, 313.15, and 328.15) K and p = 0.1 MPa. In addition, relative densities and massic heat capacities have been measured at the same temperatures and pressure for Y(NO 3 ) 3 (aq) and Ho(NO 3 ) 3 (aq) solutions without excess acid (n.b. measurements at T = 328.15 K for Ho(NO 3 ) 3 (aq) were not performed due to the limited volume of solution available). Apparent molar volumes and apparent molar heat capacities for the aqueous salt solutions have been calculated from the experimental apparent molar properties of the acidified solutions using YoungÕs rule, whereas the apparent molar properties of the solutions without excess acid were calculated directly from the measured densities and massic heat capacities. The two sets of data for the Y(NO 3 ) 3 (aq) systems provide a check of the internal consistency of the YoungÕs rule approach we have utilised.The concentration dependences of the apparent molar volumes and heat capacities of the aqueous salt solutions have been modelled at each investigated temperature using the Pitzer ion interaction equations to yield apparent molar properties at infinite dilution.Complex formation within the aqueous rare earth nitrate systems is discussed qualitatively by probing the concentration dependence of apparent molar volumes and heat capacities. In spite of the complex formation in the aqueous rare earth nitrate systems, there is a high degree of self-consistency between the apparent molar volumes and heat capacities at infinite dilution reported in this manuscript and those previously reported for aqueous rare earth perchlorates.

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Section: The Effects Of Complex Formationmentioning

confidence: 58%

Section: Introductionmentioning

confidence: 95%

Apparent molar volumes and apparent molar heat capacities of Pr(NO3)3(aq), Gd(NO3)3(aq), Ho(NO3)3(aq), and Y(NO3)3(aq) at T=(288.15, 298.15, 313.15, and 328.15) K and p=0.1 MPa

Hakin

Liu

Erickson

et al. 2005

The Journal of Chemical Thermodynamics

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“…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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“…With c in mind, looking at Figure 2, we wonder about the reliability of the measurements for La(NO 3 ) 3 at low concentrations 53 despite the re-evaluation of stock solution analyses (which had adversely impacted earlier studies 54,55 ).…”

Section: Journal Of Chemical and Engineering Datamentioning

confidence: 99%

Comparison of the Pitzer and Hückel Equation Frameworks for Activity Coefficients, Osmotic Coefficients, and Apparent Molar Relative Enthalpies, Heat Capacities, and Volumes of Binary Aqueous Strong Electrolyte Solutions at 25 °C

Rowland

May

2015

J. Chem. Eng. Data

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Detailed numerical analysis of literature data for five key thermodynamic properties (activity coefficients, osmotic coefficients, apparent molar relative enthalpies, heat capacities, and volumes) of well-characterized aqueous strong electrolyte solutions shows that equally good fits are generally obtained from the Pitzer and Huckel equations when both frameworks have the same number of adjustable parameters. Fifty-seven strong electrolyte systems with published values at 25°C have been examined: the differences found between the two frameworks are never large and are only significant with the activity and osmotic coefficients of eight systems. Most of these eight exceptions involve a lanthanide salt that has been characterized by just one research group. For describing the solution thermodynamics of binary (single) strong electrolytes, the Pitzer equations are found to possess no fundamental theoretical advantage over an extended Huckel framework. On the other hand, slight additional flexibility inherent in the Pitzer formalism makes it more susceptible than the Huckel equations to the numerical effects of experimental error. Comparing the fits achieved by the Pitzer and Huckel equation frameworks can help to identify (a) the simple behavior characteristic of strong electrolytes even at high concentration and (b) signs of error in experimental data sets lacking confirmation by independent measurement.

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Isopiestic determination of the activity coefficients of some aqueous rare earth electrolyte solutions at 25.degree.C. 3. The rare earth nitrates

Cited by 76 publications

References 18 publications

Apparent molar volumes and apparent molar heat capacities of Pr(NO3)3(aq), Gd(NO3)3(aq), Ho(NO3)3(aq), and Y(NO3)3(aq) at T=(288.15, 298.15, 313.15, and 328.15) K and p=0.1 MPa

Apparent molar volumes and apparent molar heat capacities of Pr(NO3)3(aq), Gd(NO3)3(aq), Ho(NO3)3(aq), and Y(NO3)3(aq) at T=(288.15, 298.15, 313.15, and 328.15) K and p=0.1 MPa

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

Comparison of the Pitzer and Hückel Equation Frameworks for Activity Coefficients, Osmotic Coefficients, and Apparent Molar Relative Enthalpies, Heat Capacities, and Volumes of Binary Aqueous Strong Electrolyte Solutions at 25 °C

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