The Thermodynamics of Aqueous Sodium Chloride Solutions from 0 to 40° from Electromotive Force Measurements

Harned, Herbert S.; Cook, Melvin A.

doi:10.1021/ja01871a077

Cited by 20 publications

(21 citation statements)

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“…Those for 25 °C are given in graph A where PII was used in the calculations because of quite concentrated solutions only being considered. The following data have been included in this graph: Robinson, Messikomer and Wood, Craft and Van Hook, Parker (the data smoothed by Ensor and Anderson were used), Harned and Cook, and Smith and Hirtle . The corresponding heat of dilution data of refs , , , and have been considered above.…”

Section: Resultsmentioning

confidence: 99%

“…The corresponding heat of dilution data of refs , , , and have been considered above. Harned and Cook determined thermodynamically their partial molar enthalpies from results of the amalgam cell measurements at various temperatures by Harned and Nims . Smith and Hirtle determined their values from the amalgam cell results of Harned and Nims and their own boiling-point elevation data.…”

Section: Resultsmentioning

confidence: 99%

“…The small clear trends observed in the graph have the same background as that described above in connection with Figure A because partial molar enthalpies are functionally related to the apparent ones. The amalgam cell data considered by Harned and Cook, however, did not give good enthalpy values above 1.0 mol·kg –1 and these values were omitted from the graph. Also the Δ H m,2 value of Smith and Hirtle at m = 0.05 mol·kg –1 shows a large error, and the enthalpy values of the sets from this source are not considered here further.…”

Section: Resultsmentioning

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: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

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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“…As a result, this leads to very good predictions for the MIAC. Four Table A. isotherms of the MIAC of aqueous NaCl solutions are shown in Figure 11 for temperatures in the range 288-333 K [82][83][84][85][86][87][88]. Correctly representing the experimental trend at low concentrations, SAFT-VRE Mie allows one to predict the decrease of the MIAC with increasing temperature for aqueous solutions of NaCl, thereby illustrating the predictive capability of the approach.…”

Section: Mean Ionic Activity Coefficient and Osmotic Coefficientmentioning

confidence: 95%

Development of intermolecular potential models for electrolyte solutions using an electrolyte SAFT-VR Mie equation of state

et al. 2016

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We present a theoretical framework and parameterisation of intermolecular potentials for aqueous electrolyte solutions using the statistical associating fluid theory based on the Mie interaction potential (SAFT-VR Mie), coupled with the primitive, non-restricted mean-spherical approximation (MSA) for electrolytes. In common with other SAFT approaches, water is modelled as a spherical molecule with four off-centre association sites to represent the hydrogen-bonding interactions; the repulsive and dispersive interactions between the molecular cores are represented with a potential of the Mie (generalised Lennard-Jones) form. The ionic species are modelled as fully dissociated, and each ion is treated as spherical: Coulombic ion-ion interactions are included at the centre of a Mie core; the ion-water interactions are also modelled with a Mie potential without an explicit treatment of iondipole interaction. A Born contribution to the Helmholtz free energy of the system is included to account for the process of charging the ions in the aqueous dielectric medium. The parameterisation of the ion potential models is simplified by representing the ion-ion dispersive interaction energies with a modified version of the London theory for the unlike attractions. By combining the Shannon estimates of the size of the ionic species with the Born cavity size reported by Rashin and Honig, the parameterisation of the model is reduced to the determination of a single ion-solvent attractive interaction parameter. The resulting SAFT-VRE Mie parameter sets allow one to accurately reproduce the densities, vapour pressures, and osmotic coefficients for a broad variety of aqueous electrolyte solutions; the activity coefficients of the ions, which are not used in the parameterisation of the models, are also found to be in good agreement with the experimental data. The models are shown to be reliable beyond the molality range considered during parameter estimation. The inclusion of the Born free-energy contribution, together with appropriate estimates for the size of the ionic cavity, allows for accurate predictions of the Gibbs free energy of solvation of the ionic species considered. The solubility limits are also predicted for a number of salts; in cases where reliable reference data are available the predictions are in good agreement with experiment.

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“…3, 370. (Critical studies of the vapour pressure data for sodium chloride have been made by Harned & Cook (1939) and Janis & Ferguson (1939).) Johnson (1940) used glycerol solutions for humidity control.…”

Section: Rhmentioning

confidence: 99%

Control of Humidity with Potassium Hydroxide, Sulphuric Acid, or other Solutions

Solomon¹

1951

Bull. Entomol. Res.

516

160

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Methods of preparing solutions of graded density for the accurate control of atmospheric relative humidity are described, and some pitfalls in their use and in the use of saturated salt solutions are indicated.For graded solutions of potassium hydroxide and of sulphuric acid, data from the International Critical Tables or more recent sources are used as the basis of tables giving the concentrations (wt.%) and densities corresponding to relative humidities in steps of 5 per cent. R.H. Sources of similar data for calcium chloride, sodium hydroxide, sodium chloride, and glycerol solutions are given.As an addition to the compilation of the available data on humidities in contact with various saturated salt solutions by O'Brien (1948), some more recent figures are quoted.

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The Thermodynamics of Aqueous Sodium Chloride Solutions from 0 to 40° from Electromotive Force Measurements

Cited by 20 publications

References 0 publications

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

Development of intermolecular potential models for electrolyte solutions using an electrolyte SAFT-VR Mie equation of state

Control of Humidity with Potassium Hydroxide, Sulphuric Acid, or other Solutions

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