Abstract

Water may be involved in reverse micelle formation either in the form of a hydration shell or as a solubilisate. Both cases have been analyzed within the framework of a theory based on the mass action law and the definition of the critical micelle concentration (CMC) via the constant of this law. In the first case, it is supposed that a surfactant is primordially hydrated, and water is a priori incorporated into the surfactant. Its amount is determined from the volume of the hydrated core of a micelle, while the aggregation number of the surfactant is calculated from the packing conditions for spherical, cylindrical, and platelike micelles. The CMC is, in turn, found from its dependence on the aggregation number, with this dependence being determined by the general theory. In the second case, water is taken into account as a separate component of a micelle, but in the form of a solubilisate (hydration water is, as before, introduced into the chemical formula of the surfactant). Here, the CMC appears to depend on not only the overall concentration of water (with no regard to its hydration form), but also on the value of the critical degree of water micellization. The effect of water on micellization has been analyzed at both its preset chemical potential and its constant amount. All versions of the theory lead to the conclusion that CMC decreases with an increase in water content, thereby confirming the prediction put forward by Eicke and Christen (Eicke, H-F. and Christen, H., Helv. Chim. Acta, 1978, vol. 61, p. 2258).

中文翻译：

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反胶束的热力学：水对胶束的影响

摘要

水可以以水合壳的形式或以增溶剂形式参与反胶束的形成。在基于质量作用定律和通过该定律的常数定义胶束浓度（CMC）的理论框架内对这两种情况进行了分析。在第一种情况下，假定表面活性剂是原始水合的，并且水是先验掺入表面活性剂中的。其量由胶束的水合核的体积确定，而表面活性剂的聚集数由球形，圆柱形和板状胶束的填充条件计算。反过来，从其对聚集数的依赖性中找到CMC，这种依赖性由一般理论确定。在第二种情况下 水被视为胶束的单独成分，但以增溶形式存在（水化水如前所述被引入表面活性剂的化学式中）。在这里，CMC似乎不仅取决于水的总浓度（不考虑其水合形式），还取决于水胶束临界程度的值。在预设的化学势和恒定量下都分析了水对胶束的影响。该理论的所有版本都得出结论，CMC随着水含量的增加而降低，从而证实了Eicke和Christen（Eicke，HF。and Christen，H.，CMC似乎不仅取决于水的总浓度（不考虑其水合形式），还取决于水胶束临界程度的值。在预设的化学势和恒定量下都分析了水对胶束的影响。该理论的所有版本都得出结论，CMC随着水含量的增加而降低，从而证实了Eicke和Christen（Eicke，HF。and Christen，H.，CMC似乎不仅取决于水的总浓度（不考虑其水合形式），还取决于水胶束临界程度的值。在预设的化学势和恒定量下都分析了水对胶束的影响。该理论的所有版本都得出结论，CMC随着水含量的增加而降低，从而证实了Eicke和Christen（Eicke，HF。and Christen，H.，Helv。詹。Acta，1978，第1卷。第61页 2258）。