Laboratoire de Chimie, CNRS, UMR 5182, Ecole Normale Supérieure de Lyon, 46, Allée d'Italie, 69364, Lyon, Cedex 07, France.
State Key Laboratory of Chem/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, 410082, Changsha, China.
Nat Commun. 2023 Apr 1;14(1):1824. doi: 10.1038/s41467-023-36970-7.
Disjoining pressure was discovered by Derjaguin in 1930's, which describes the difference between the pressure of a strongly confined fluid and the corresponding one in a bulk phase. It has been revealed recently that the disjoining pressure is at the origin of distinct differential and integral surface tensions for strongly confined fluids. Here we show how the twin concept, disjoining chemical potential, arises in a reminiscent way although it comes out eighty years later. This twin concept advances our understanding of nanoscale thermodynamics. Ensemble-dependence (or environment-dependence) is one hallmark of thermodynamics of small systems. We show that integral surface tension is ensemble-dependent while differential surface tension is not. Moreover, two generalized Gibbs-Duhem equations involving integral surface tensions are derived, as well as two additional adsorption equations relating surface tensions to adsorption-induced strains. All the results obtained in this work further evidence that an approach alternative of Hill's nanothermodynamics is possible, by extending Gibbs surface thermodynamics instead of resorting to Hill's replica trick. Moreover, we find a compression-expansion hysteresis without any underlying phase transition.
分压力由德热那于 20 世纪 30 年代发现，它描述了强受限流体的压力与相应的体相压力之间的差异。最近已经揭示，分压力是强受限流体产生独特的微分和积分表面张力的原因。在这里，尽管晚了 80 年，我们以一种怀旧的方式展示了孪生概念，即分位化学势是如何产生的。这一双重概念推进了我们对纳米尺度热力学的理解。系综依赖性（或环境依赖性）是小系统热力学的一个显著特征。我们表明，积分表面张力是系综依赖性的，而微分表面张力则不是。此外，还推导出了两个涉及积分表面张力的广义吉布斯-杜汉姆方程，以及两个将表面张力与吸附诱导应变相关联的附加吸附方程。这项工作中获得的所有结果进一步证明，通过扩展吉布斯表面热力学而不是诉诸希尔的复制技巧，替代希尔的纳米热力学的方法是可能的。此外，我们发现了一种没有任何潜在相变的压缩-膨胀滞后现象。
