van Sluijs Tom B, Stoter Stein K F, van Brummelen E Harald
Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
Langmuir. 2025 Feb 4;41(4):2141-2155. doi: 10.1021/acs.langmuir.4c01724. Epub 2025 Jan 21.
Surface-active agents (surfactants) release potential energy as they migrate from one of two adjacent fluids onto their fluid-fluid interface, a process that profoundly impacts the system's energy and entropy householding. The continuum thermodynamics underlying such a surfactant-enriched binary-fluid system has not yet been explored comprehensively. In this article, we present a mathematical description of such a system, in terms of balance laws, equations of state, and permissible constitutive relations and interface conditions, that satisfies the first and second law of thermodynamics. The interface conditions and permissible constitutive relations are revealed through a Coleman-Noll analysis. We characterize the system's equilibrium by defining equilibrium equivalences and study an example system. With our work, we aim to provide a systematically derived framework that combines and links various elements of existing literature, and that can serve as a thermodynamically consistent foundation for the (numerical) modeling of full surfactant-enriched binary-fluid systems.
表面活性剂从两种相邻流体之一迁移到它们的流体 - 流体界面时会释放势能，这一过程深刻影响系统的能量和熵的平衡。这种富含表面活性剂的二元流体系统的连续介质热力学尚未得到全面探索。在本文中，我们根据平衡定律、状态方程以及允许的本构关系和界面条件，给出了这样一个系统的数学描述，该描述满足热力学第一和第二定律。通过科尔曼 - 诺尔分析揭示了界面条件和允许的本构关系。我们通过定义平衡等价关系来表征系统的平衡，并研究一个示例系统。通过我们的工作，旨在提供一个系统推导的框架，该框架结合并联系现有文献的各种元素，并可作为完整的富含表面活性剂的二元流体系统（数值）建模的热力学一致基础。
