Institute for Atmospheric and Climate Science, ETH Zürich, Universitätstrasse 16, 8092 Zürich, Switzerland.
Ircelyon, CNRS and Universite Lyon 1, Villeurbanne, France.
Phys Chem Chem Phys. 2023 Apr 26;25(16):11055-11074. doi: 10.1039/d3cp00322a.
The liquid-air surface tension of aqueous solutions is a fundamental quantity in multi-phase thermodynamics and fluid dynamics and thus relevant in many scientific and engineering fields. Various models have been proposed for its quantitative description. This Perspective gives an overview of the most popular models and their ability to reproduce experimental data of ten binary aqueous solutions of electrolytes and organic molecules chosen to be representative of different solute types. In addition, we propose a new model which reproduces sigmoidal curve shapes (Sigmoid model) to empirically fit experimental surface tension data. The surface tension of weakly surface-active substances is well reproduced by all models. In contrast, only few models successfully model the surface tension of aqueous solutions with strongly surface-active substances. For substances with a solubility limit, usually no experimental data is available for the surface tension of supersaturated solutions and the pure liquid solute. We discuss ways in which these can be estimated and emphasize the need for further research. The newly developed Sigmoid model best reproduces the surface tension of all tested solutions and can be recommended as a model for a broad range of binary mixtures and over the entire concentration range.
水溶液的气液表面张力是多相热力学和流体动力学的基本参数，因此在许多科学和工程领域都具有重要意义。已经提出了各种模型来对其进行定量描述。本文综述了最流行的模型及其对十种二元电解质和有机分子水溶液实验数据的再现能力，这些溶液选择的代表性溶质类型不同。此外，我们提出了一个新的模型，该模型采用经验拟合实验表面张力数据的 Sigmoid 曲线形状（Sigmoid 模型）。所有模型都能很好地再现弱表面活性物质的表面张力。相比之下，只有少数模型能够成功地模拟具有强表面活性物质的水溶液的表面张力。对于具有溶解度极限的物质，通常没有实验数据可用于过饱和溶液和纯液态溶质的表面张力。我们讨论了估计这些数据的方法，并强调了进一步研究的必要性。新开发的 Sigmoid 模型能够最好地再现所有测试溶液的表面张力，可以推荐该模型用于广泛的二元混合物以及整个浓度范围内。
