During numerous visits to our Laboratory professor Johannes (Hans) Lyklema emphasized the importance of a holistic view on thermodynamics. In order to fulfill this aim he assembled the monumental Fundamentals of Interface and Colloid Science series. The basic state functions (internal energy, enthalpy and free energies) are interrelated by Gibbs and Helmholtz relationships. First-order phase transitions are characterized by first-order state variables (temperature, pressure, entropy, volume). Interactions are, however best expressed by second-order partial derivatives (compressibility, heat capacity and expansivity). They are related to the first-order state variables by relaxation contributions quantifying the degree of cooperativity of self-assembly processes leading to phase separation. In particular they exhibit the limit when phase transitions are changed to second-order processes. This was the focus of my first review dedicated to the memory of professor Lyklema, "Characterization of van der Waals type bimodal,- lambda,- meta- and spinodal phase transitions in liquid mixtures, solid suspensions and thin films" (ACIS 253 (2018) 66). In the present review the attention is placed on short and medium chain-length surfactant self-assembly in aqueous solutions without additives (salts or solubilizates). The dependence of state functions described above on concentration, temperature and pressure is compared to corresponding dynamic molecular processes occurring on different time, frequency and length scales including structure analysis. It is convincingly shown that Hartley-Tanford space filled spherical anhydrous micelle core - polar shell model designed for long chain-length surfactants (cmc < 0.01 mol/dm3, N > 50) cannot be enforced on short and medium chain-length surfactant non-sperical micelles (cmc close to unity, N < 20). Moreover, it is shown that a proper validity evaluation of proposed models for micelle formation is seriously undermined by their application to only a narrow concentration range near critical micelle concentration (cmc). When successful each model should characterize all self-assembly processes occurring (also at limiting association concentration, lac, at second critical concentration, 2cc and at third critical concen-tration, 3cc) within the entire concentration range of thermodynamically stable surfactant solutions. All other self-assembly processes except micelle formation are rarely considered. The pre-micelle formation at lac is, for example omitted as deviations from presented models. The reviewed reports are therefore selected on the basis of maximum investigated concentration range and of largest possible number of homologues.

中文翻译：

---

对水溶液中短链和中链表面活性剂自组装模型的严格评估。

在多次访问我们的实验室教授约翰内斯（汉斯）的过程中，莱克利马强调了对热力学的整体看法的重要性。为了实现这一目标，他组装了具有纪念意义的“界面和胶体科学基础知识”系列。基本状态函数（内部能量，焓和自由能）通过吉布斯和亥姆霍兹关系相互关联。一阶相变的特征在于一阶状态变量（温度，压力，熵，体积）。但是，相互作用最好用二阶偏导数（可压缩性，热容量和膨胀性）表示。通过松弛贡献量化与导致相分离的自组装过程的协同程度，它们与一阶状态变量相关。特别地，当相变更改为二阶过程时，它们表现出极限。这是我为纪念Lyklema教授所做的第一篇评论的重点，“液体混合物，固体悬浮液和薄膜中范德华型双峰，-λ，-和旋节线型相变的表征”（ACIS 253（2018 ）66）。在本综述中，注意力集中在不含添加剂（盐或增溶剂）的水溶液中的短链和中链表面活性剂的自组装上。将上述状态函数对浓度，温度和压力的依赖性与在包括结构分析在内的不同时间，频率和长度尺度上发生的相应动态分子过程进行比较。令人信服地表明，为长链表面活性剂（cmc <0.01 mol / dm3，N> 50）设计的Hartley-Tanford空间填充球形无水胶束芯-极性壳模型不能在非短链和中链表面活性剂上使用。精微胶束（cmc接近统一，N <20）。此外，表明通过仅将其应用于临界胶束浓度（cmc）附近的狭窄浓度范围会严重破坏所提出的胶束形成模型的正确有效性评估。当成功时，每个模型都应表征在热力学稳定的表面活性剂溶液的整个浓度范围内发生的所有自组装过程（也在极限缔合浓度lac，第二临界浓度2cc和第三临界浓度3cc时）。很少考虑除胶束形成以外的所有其他自组装过程。在lac处的胶束前形成被忽略，例如与所提出模型的偏差。因此，根据最大的研究浓度范围和最大可能的同系物选择审查的报告。