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

• Published in: Journal of chemical and engineering data 2017-09, Vol.62 (9), p.2617-2632
• Main Authors: Partanen, Jaakko I, Partanen, Lauri J, Vahteristo, Kari P
• Format: Article
• Language: English
• ISSN: 0021-9568; 1520-5134
• DOI: 10.1021/acs.jced.7b00091

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 mo