Isopiestic studies of some aqueous electrolyte solutions at 80.deg.

Moore, John T.; Humphries, William; Patterson, C. Stuart

doi:10.1021/je60053a035

Cited by 58 publications

(26 citation statements)

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“…The vapor pressures p x and p y were calculated using eqs , , and . Graph A of Figure shows the results at 45 °C (refs and ) and graph B those at 60 and 80 °C (refs and ). For KCl solutions, the previous constant value of 1.3 (mol·kg –1 ) −1/2 was used for parameter B (ref ), and the following best values of 0.0396, 0.0486, and 0.044 for parameter b 1 at 45, 60, and 80 °C, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…According to this figure, PI applies quite well also to the results of the concentrated solutions in these three sets. The PI parameters were then tested with the isopiestic data measured by Davis et al 31 at 45 °C, Humphries et al 32 at 60 °C, and Moore et al 33 at 80 °C in NaCl and KCl solutions. The smoothed isopiestic ratios for NaCl and KCl solutions from the data of Hellams et al 34 at 45 °C were also included in the tests.…”

Section: ■ Theorymentioning

confidence: 99%

“…However, we also included in these tests the previous quadratic equation for parameter b 1 (from ref 4) which was observed to apply sufficiently for many practical purposes for dilute NaCl solutions up to a temperature of 80 °C. This equation has the form Plot of e ip (eq 13), the deviation between the vapor pressure of water over the reference solution (NaCl = x) and that over the tested solution (KCl = y), as a function of the molality of the tested solution (m y ) in the isotonic solutions measured by Davis et al 31 at 45 °C (graph A, •), Humphries et al 32 at 60 °C (B, •), Moore et al 33 at 80 °C (B, ○), and Hellams et al 34 at 45 °C (A, ○) as a function of molality m y . The isopiestic molalities for the data reported by Hellams et al 34 were reproduced from the smoothed values reported for the isopiestic ratios (see ref 4).…”

Section: ■ Theorymentioning

confidence: 99%

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Traceable Thermodynamic Quantities for Dilute Aqueous Sodium Chloride Solutions at Temperatures from (0 to 80) °C. Part 1. Activity Coefficient, Osmotic Coefficient, and the Quantities Associated with the Partial Molar Enthalpy

Partanen

Vahteristo

2017

J. Chem. Eng. Data

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We present fully traceable two-parameter Hückel equations (with parameters B and b 1) for the activity coefficient of sodium chloride and for the osmotic coefficient of water in aqueous NaCl solutions at temperatures from (0 to 80) °C. These equations apply within experimental error to all thermodynamic data available for these solutions at least up a molality of 0.2 mol·kg–1. In our previous study (J. Chem. Eng. Data 2016, 61, 286–306), these equations were successfully tested against the literature results of electrochemical, isopiestic, and cryoscopic measurements usually in the temperature range from (0 to 25) °C. There, a constant value was employed for B, whereas a linear model with respect to the temperature was utilized for b 1. The linear model was determined from the values of b 1 at 0 °C and at 25 °C obtained from freezing-point depression data and from isopiestic and cell-potential difference data, respectively. In the present study, these two b 1 values are utilized alongside the constant value of parameter B but a new quadratic model is presented for the temperature dependence of b 1. The third data point required for this model is obtained from the direct vapor pressure measurements of Gibbard et al. (J. Chem. Eng. Data 1974, 19, 281–288) at 75 °C. The results obtained with this quadratic equation for b 1 agree well with the test results of the linear model in the previous paper (see the citation above) up to 25 °C. The most important new test results above that temperature are reported here. Our quadratic model has additionally been tested with all the high-precision calorimetric data available in the literature for NaCl solutions. In this first part (Part 1) of the study, the test results from the thermodynamic quantities associated with partial molar enthalpy are reported. In the forthcoming second part (Part 2) of the study, the results of the quantities associated with the heat capacity of NaCl solutions will be considered. In the tests of these two parts, all calculations dealing with calorimetric data are performed in a new way. Both the calorimetric data and the vapor pressure data (from both direct and isopiestic measurements) can be predicted using the new Hückel equations within experimental error in dilute NaCl solutions from (0 to 80) °C. For comparison, also other Hückel models are considered and at best these apply up to the molality of the saturated NaCl solution at various temperatures. Following the success of the new models, new values for the activity coefficients, osmotic coefficients, relative apparent molar enthalpies, and relative partial molar enthalpies for NaCl solutions at rounded molalities are reported at the end of this Article. We have good reasons to believe that the new values contain the most reliable ones available for the given thermodynamic quantities.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Theorymentioning

confidence: 99%

Section: ■ Theorymentioning

confidence: 99%

See 1 more Smart Citation

Traceable Thermodynamic Quantities for Dilute Aqueous Sodium Chloride Solutions at Temperatures from (0 to 80) °C. Part 1. Activity Coefficient, Osmotic Coefficient, and the Quantities Associated with the Partial Molar Enthalpy

Partanen

Vahteristo

2017

J. Chem. Eng. Data

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“…Patterson and his students have published two quite helpful isopiestic studies of BaCl 2 (aq) (66,67) at temperatures of approximately 318 K and 353 K. The Italian school also has some cell potential results for BaCl 2 (aq) (74) at low molalities and temperatures to about 343 K. The vapor pressure measurements of Liu and Lindsay (16) for MgCl 2 (aq) at elevated temperatures could not be fit with the present model and an acceptable error of fit-a discrepancy which was noted in our earlier work. In figure 3 we compare experimental osmotic coefficients from our previous study (3) of MgCl 2 (aq) and calculated values from the present model for the same temperatures.…”

Section: Excess Gibbs Free Energymentioning

confidence: 99%

Aqueous solutions of the alkaline-earth metal chlorides at elevated temperatures. Isopiestic molalities and thermodynamic properties

Holmes

Mesmer

1996

The Journal of Chemical Thermodynamics

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“…The proposed procedure for prediction of activity and osmotic coefficients is here illustrated for a number of electrolytewater systems. The vapor pressure lowering AP were evaluated from known osmotic coefficients of one molal solutions of KCl (Patterson et al, 1960;Hellams et al, 1965;Lindsay and Liu, 1971;Moore et al, 1972;Herrington and Jackson, 1973;Snipes et al, 1975;Davies et al, 1985;Patil et al, 1991) (Soldano and Patterson, 1962;Soldano and Meek, 1963;Lindsay and Liu, 1971;Holmes et al, 1978;Palaban and Pitzer, 1988) and for CaCl, (Holmes et al, 1978). A very nice agreement between the calculated and experimental osmotic coefficients was observed.…”

Section: Numerical Resultsmentioning

confidence: 77%

Activity and osmotic coefficients in electrolyte solutions at elevated temperatures

Apelblat¹

1993

AIChE Journal

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In this article, a numerical procedure is proposed for prediction of activity and osmotic coefficients at elevated temperatures based on the vapor pressure lowering of electrolyte splutions available at room and intermediate temperatures.The vapor pressure lowering of electrolyte solutions can be correlated over a wide temperature range by equation, In AP=A+B/T+C(ln T-T/2TC), where A, B and C are adjustable parameters and T, is the critical temperature of pure water. The procedure is illustrated in the cases of KCI, CaCl, and especially LiCl solutions. An analytical expression for osmotic coefficients in the Meissner approach is derived by an integration of the Bjerrum equation.Thermodynamic properties of aqueous solutions of strong electrolytes at high temperatures are of considerable importance in many areas of chemical industry, in geochemistry, in desalination and steam power generation. However, with few exceptions, the available experimental data are confined to temperatures which are not far from room temperatures. In recent years, our knowledge about activity and osmotic coefficients comes mainly from isopiestic measurements performed at elevated temperatures by the Holmes and Mesmer group. Unfortunately, these measurements constitute only a small part of industrially important electrolyte-water systems and therefore procedures for prediction of activity and osmotic coefficients must be considered. Since in the case of electrolyte solutions, a linear temperature dependence of the coefficients is rarely observed, ordinary interpolation and extrapolation techniques have rather limited value. For example, if one molal solution is considered, osmotic coefficients as a function of temperature in the 273-573 K range have a distinct maximum for NaCI, KCl and CsC1, they decrease monotonically for LiCl and for CaCl, remain practically constant up to about temperature of 373 K but after they decrease with temperature increasing (Lindsay and Liu, 1971 ;Holmes et al., 1978;Holmes and Mesmer, 1981).In our previous works on the subject, estimation procedures were proposed for activity and osmotic coefficients at elevated temperatures based on data at one or two temperatures (Apelblat et al., 1988) and on the application of the Moriyama rule (Apelblat et al., 1987). In this work, it is considered a new extrapolation technique to predict activity and osmotic coefficients which is based on plentiful data available at room and . intermediate temperatures (for example, Robinson and Stokes, 1965;Hamer and Wu, 1972;Goldberg, 1981; Lob0 and Quaresma, 1989). The proposed numerical procedure is illustrated in the cases of KCI, CaCl, and especially LiCl solutions (lithium chloride is very soluble in water).. Representation of Osmotic and Activity Coefficients as a Function of Temperature and Concentration

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Isopiestic studies of some aqueous electrolyte solutions at 80.deg.

Cited by 58 publications

References 1 publication

Traceable Thermodynamic Quantities for Dilute Aqueous Sodium Chloride Solutions at Temperatures from (0 to 80) °C. Part 1. Activity Coefficient, Osmotic Coefficient, and the Quantities Associated with the Partial Molar Enthalpy

Traceable Thermodynamic Quantities for Dilute Aqueous Sodium Chloride Solutions at Temperatures from (0 to 80) °C. Part 1. Activity Coefficient, Osmotic Coefficient, and the Quantities Associated with the Partial Molar Enthalpy

Aqueous solutions of the alkaline-earth metal chlorides at elevated temperatures. Isopiestic molalities and thermodynamic properties

Activity and osmotic coefficients in electrolyte solutions at elevated temperatures

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