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

IF 1.4 4区 化学 Q4 CHEMISTRY, PHYSICAL Journal of Solution Chemistry Pub Date : 2023-09-10 DOI:10.1007/s10953-023-01322-y
Lauri J. Partanen, Jaakko I. Partanen
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Abstract

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.

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从 T = (273.15 至 373.15) K 到饱和溶液的氯化钠水溶液的热力学可溯源量热结果:第 1 部分--与部分摩尔焓相关的量
参数为B、b1和b2的三参数扩展Hückel方程最近已成功地针对NaCl水溶液在(273至373)K温度下的现有蒸气压、电化学和溶解度数据进行了测试(Partanen和Partanen在J.Chem.Eng.data 65:5226–52392020中)。在本研究中,我们将该模型扩展到这些溶液的表观和偏摩尔焓数据。焓方程是使用一种新的计算方法确定的,该方法给出的结果实际上与之前另一项研究中使用的结果相同(Partanen等人在J.Chem.Eng.Data 62:2617–26322017中),但新方法要简单得多。在之前的焓研究中,将NaCl溶液稀释至m = 0.2 mol·kg−1被认为在T的范围内 = 273至353 K。继三参数扩展的Hückel模型在不同温度下的整个浓度范围内取得成功后,我们将NaCl溶液在四舍五入摩尔数下的相对表观摩尔焓和部分摩尔焓的新值制成表格。所得值与文献值进行了广泛的对比测试。在288 K以下和313至353 K之间的温度下获得了最佳一致性。在其他地方,至少获得了合理的一致性。由于在估计我们的模型参数时没有使用焓值或热容数据,并且该模型在解释其他高精度热力学数据方面表现出色,我们认为,即使在由于与文献值相关的潜在问题而仅合理一致的温度下,也应首选推荐的焓值。研究中也考虑了这些问题。图形摘要
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来源期刊
Journal of Solution Chemistry
Journal of Solution Chemistry 化学-物理化学
CiteScore
2.30
自引率
0.00%
发文量
87
审稿时长
3-8 weeks
期刊介绍: Journal of Solution Chemistry offers a forum for research on the physical chemistry of liquid solutions in such fields as physical chemistry, chemical physics, molecular biology, statistical mechanics, biochemistry, and biophysics. The emphasis is on papers in which the solvent plays a dominant rather than incidental role. Featured topics include experimental investigations of the dielectric, spectroscopic, thermodynamic, transport, or relaxation properties of both electrolytes and nonelectrolytes in liquid solutions.
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