Traceable Thermodynamic Quantities for Dilute Aqueous NaCl Solutions at Temperatures from (353.15 to 383.15) K and for Dilute Aqueous KCl Solutions from (273.15 to 383.15) K

Partanen, Jaakko I.; Partanen, Lauri; Vahteristo, Kari P.

doi:10.1021/acs.jced.8b00423

Cited by 6 publications

(32 citation statements)

References 46 publications

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“…It is important to emphasize the fully traceable and transparent nature of the best parametrization presented here and in our previous studies, − in addition to its ability to predict experimental results. A critical reader can reproduce all calculations using the presented results with the appropriate literature data.…”

Section: Introductionmentioning

confidence: 74%

“…Our recent NaCl studies show that an extended version of the simple Hückel equation applies well to experimental data from various sources in the temperature range from 273.15 to 373.15 K. − With our best parametrization for the temperature dependence, the extended Hückel equation could predict all calorimetric data reported in the literature up to 373 K for dilute NaCl solutions, even though these data were not included in the parameter estimation. In the present study, we demonstrate that by extending our parametrization with a quadratic molality term, we can predict all the thermodynamic properties of NaCl solutions from 273.15 to 373.15 K at all temperatures up to the saturated solutions.…”

Section: Introductionmentioning

confidence: 75%

“…In aqueous solutions of many salts at least up to an ionic strength ( I m ) of 1 mol·kg –1 , the following extended Hückel equations can be used to predict the mean activity coefficient (γ) of the salt and the osmotic coefficient (ϕ) of water: , − where for the standard Hückel equation the parameter b 2 is set equal to zero. In eqs and , m is the molality, m o is 1 mol·kg –1 , z + and z – are the charge numbers of the cation and anion, respectively, α is the Debye–Hückel parameter, and B , b 1 , and b 2 are electrolyte dependent parameters.…”

Section: Theorymentioning

confidence: 99%

“…Similarly, the exact values from Kell for both V m,1 * (liq) and p 1 * were utilized when possible in eq . When interpolation was needed, it was based on the equations presented in ref : where in eq the symbol p o is the unit of the pressure (i.e., p o = 1 Pa) and in eqs to T 0 is equal to 273.15 K.…”

Section: Theorymentioning

confidence: 99%

“…To tackle this issue, we have previously determined traceable and highly accurate activity and osmotic coefficients for solutions of the common reference electrolytes NaCl and KCl at 298.15 K . These values have been utilized in all our subsequent studies containing isopiestic data − including this one. Due to the abundance of theoretical models, we mainly compare our results against different types of experimental data and reserve alternative activity models for future publications.…”

Section: Introductionmentioning

confidence: 99%

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Traceable Values for Activity and Osmotic Coefficients in Aqueous Sodium Chloride Solutions at Temperatures from 273.15 to 373.15 K up to the Saturated Solutions

Partanen

2020

J. Chem. Eng. Data

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We present traceable three-parameter extended Hückel equations for the activity coefficient of sodium chloride and for the osmotic coefficient of water in aqueous NaCl solutions from 273.15 to 373.15 K. In this temperature range, our equations seem to apply within experimental error to all thermodynamic data available for these solutions up to the molality of the saturated solution. Our previous studies (J. Chem. Eng. Data 2017, 62, 2617–2632 and 2019, 64, 16–33) showed that, from 273.15 to 373.15 K, two-parameter Hückel equations can successfully explain the literature results of electrochemical, isopiestic, and cryoscopic measurements at least up to a molality of 0.2 mol·kg–1. The model recommended in this study employs the values of our previous two-parameter model for the ion-size parameter in the original Debye–Hückel equation, B, and for the coefficient of the linear term with respect to the molality, b 1. In addition, it includes a quadratic term with respect to the molality with the coefficient b 2. Both b 1 and b 2 are quadratically dependent on temperature. With the introduction of b 2, our model is able to explain the existing vapor pressure, electrochemical, and solubility data from 273.15 to 373.15 K up to the saturated solution. A comparison with the most important literature values for the activity and osmotic coefficients revealed that the agreement is always at least satisfactory, but is best for temperatures below 363 K. On the basis of these results, our activity and osmotic coefficients are the most reliable values for these thermodynamic quantities so far. We propose this is true also for the values from 363 to 373 K.

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Section: Introductionmentioning

confidence: 74%

Section: Introductionmentioning

confidence: 75%

Section: Theorymentioning

confidence: 99%

Section: Theorymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Traceable Values for Activity and Osmotic Coefficients in Aqueous Sodium Chloride Solutions at Temperatures from 273.15 to 373.15 K up to the Saturated Solutions

Partanen

2020

J. Chem. Eng. Data

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Thermodynamically Traceable Calorimetric Results for Aqueous Sodium Chloride Solutions from T = (273.15 to 373.15) K up to the Saturated Solutions: Part 1—The Quantities Associated with the Partial Molar Enthalpy

Partanen,

Partanen

2023

J Solution Chem

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The three-parameter extended Hückel equations with parameters B, b1, and b2 have recently been successfully tested against existing vapor pressure, electrochemical, and solubility data for aqueous NaCl solutions at temperatures from (273 to 373) K (Partanen and Partanen in J. Chem. Eng. Data 65:5226–5239, 2020). In the present study, we extend this model to the apparent and partial molar enthalpy data of these solutions. The enthalpy equations were determined using a new calculation method that gives practically the same results as that used in another previous study (Partanen et al. in J. Chem. Eng. Data 62:2617–2632, 2017), but the new method is much simpler. In the previous enthalpy study, dilute NaCl solutions up to m = 0.2 mol⋅kg−1 were considered in the range from T = 273 to 353 K. Following the success of the three-parameter extended Hückel model within the whole concentration range at various temperatures, we tabulate new values for relative apparent and partial molar enthalpies for NaCl solutions at rounded molalities. The resulting values are extensively tested against the literature ones. The best agreement is obtained for temperatures below 288 K and between 313 and 353 K. Elsewhere, at least a reasonable agreement is obtained. As no enthalpy or heat capacity data were used in the estimation of our model’s parameters and as the model has excelled in explaining other high-precision thermodynamic data, we argue that the recommended enthalpy values should be preferred even for the temperatures where the agreement is only reasonable due to potential problems associated with the literature values. These problems are also considered in the study. Graphical Abstract

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Thermodynamically Traceable Calorimetric Results for Aqueous Sodium Chloride Solutions from T = (273.15 to 373.15) K up to the Saturated Solutions: Part 2 —The Quantities Associated with the Partial Molar Heat Capacity

Partanen,

Partanen

2024

J Solution Chem

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In previous articles (Partanen and Partanen in J. Chem. Eng. Data 65: 5226 − 5239 (2020), J. Solution Chem. 52: 1352 − 1385 (2023)), we presented a traceable and transparent three-parameter model for thermodynamic activity and enthalpy quantities in aqueous NaCl solutions. The model is based on extended Hückel equations with parameters B, b1, and b2 and it applies from T = 273.15 to 373.15 K up to the saturated solutions. These studies demonstrate that the model explains the literature data of almost all thermodynamic quantities including apparent and partial molar enthalpies within experimental error. In the model, the ion-size parameter in the Debye–Hückel equation, B, is regarded as a constant while the parameters of the coefficients of the linear and quadratic molality terms, b1 and b2, respectively, possess quadratic temperature dependences. In this study, the results obtained for the heat capacity quantities of NaCl(aq) are considered. We show that the available heat capacity literature for these solutions can be predicted at least satisfactorily up to the saturated solutions with our new model. Following this success, we supplement the existing thermodynamic tables with the new values for the relative apparent and partial molar heat capacities for NaCl solutions. It is likely that the new tables contain the most reliable values determined so far even though no calorimetric data were used in the parameter estimation of our model. Graphical Abstract

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Traceable Thermodynamic Quantities for Dilute Aqueous NaCl Solutions at Temperatures from (353.15 to 383.15) K and for Dilute Aqueous KCl Solutions from (273.15 to 383.15) K

Cited by 6 publications

References 46 publications

Traceable Values for Activity and Osmotic Coefficients in Aqueous Sodium Chloride Solutions at Temperatures from 273.15 to 373.15 K up to the Saturated Solutions

Traceable Values for Activity and Osmotic Coefficients in Aqueous Sodium Chloride Solutions at Temperatures from 273.15 to 373.15 K up to the Saturated Solutions

Thermodynamically Traceable Calorimetric Results for Aqueous Sodium Chloride Solutions from T = (273.15 to 373.15) K up to the Saturated Solutions: Part 1—The Quantities Associated with the Partial Molar Enthalpy

Thermodynamically Traceable Calorimetric Results for Aqueous Sodium Chloride Solutions from T = (273.15 to 373.15) K up to the Saturated Solutions: Part 2 —The Quantities Associated with the Partial Molar Heat Capacity

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