THERMODYNAMIC ASPECTS OF CAPILLARITY
THERMODYNAMIC ASPECTS OF CAPILLARITY
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毛细管现象的热力学方面
DOI：
10.1021/ie50699a008
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发表时间：
1968
影响因子：
--
通讯作者：
J. C. Melrose
中科院分区：
文献类型：
--
作者：
J. C. Melrose
毛细作用最初被认为是科学研究的一个重要领域，当时热力学定律还不清楚。直到很久以后，当物理化学发展成为化学科学中一门独特的学科时，毛细作用才成为现在所说的胶体和表面化学的一部分。由于这种侧重点的转移，最容易被热力学类型的分析所处理的那些方面已经成为主导，而其他不是严格意义上的热力学性质的方面变得有些模糊。这一发展过程解释了为什么尽管这一学科的起源相对遥远，但毛细作用的一些基本原理直到最近才被完全阐明。这一增长的理解应该会为进一步将这些原理应用于胶体和表面化学中的各种问题提供可考虑的刺激。许多技术问题都与多相流体的静力学和动力学有关。这些问题也需要有关流体/流体和流体/固体界面行为的基本知识才能解决。因此，土壤物理和石油回收等技术领域非常直接地依赖于毛细作用这一主题来理解它们的许多现象。就静力学而言，拉普拉斯和托马斯·杨用力学中的概念概述了现象学毛细作用理论的主要特征。开尔文介绍了热力学在毛细作用中的应用，吉布斯(28)对此进行了深入的探索。不幸的是，开尔文方法固有的某些局限性导致了许多混乱。即使在现在，界面张力的概念有时也被认为等同于界面吉布斯自由能。此外，许多热力学作家，特别是化学家，未能认识到吉布斯引入的一个概念的数学动机和意义，即所谓的“分割面”。这导致了一些试图绕过吉布斯治疗并提供替代方法的尝试。作为这些尝试的理由，人们经常声称或暗示吉布斯形式构成了一个模型，在该模型中，每个块状区域的属性保持不变，直到称为分割面的数学表面，然后假设该表面具有
Capillarity was first recognized as an important area of scientific study at a time when the laws of thermo-dynamics were still unknown. Only much later, when physical chemistry had developed into a distinct dis-cipline within chemical science, did capillarity become part of what is now referred to as colloid and surface chemistry. As a result of this shift in emphasis, those aspects of the subject most easily treated by a thermodynamic type of analysis have become dominant, with other aspects, not strictly thermodynamic innature, becoming somewhat obscured. This course of develop-ment explains why, in spite of the relatively remote origins of the subject, some of the basic principles of capillarity have only recently been fully elucidated. This increased understanding should provide con-siderable stimulus to the further application of these principles to a wide variety of problems in colloid and surface chemistry. Many technological problems are concerned with the statics and dynamics of multiphase fluids. These problems, too, require basic knowledge concerning the behavior of fluid/fluid and fluid/solid interfaces for their solution. Thus, such technological areas as soil physics and the recovery of petroleum rely quite directly on the subject of capillarity for an understanding of many of their phenomena. The main features of the phenomenological theory of capillarity, so far as statics is concerned, were outlined by Laplace and Thomas Young, usingconcepts drawn from mechanics. The application of thermodynamics to capillarity was introduced by Kelvin and thoroughly explored by Gibbs (28). Unfortunately, certain limita-tions inherent inKelvin’s approach have led to much confusion. Even at the present time, the concept of interfacial tension is occasionally regarded as equivalent to the interfacial Gibbs free energy. Also, many writers on thermodynamics, particularly among chemists, have failed to appreciate the mathematical motivation and significance of a concept introduced by Gibbs, the so-called “dividing surface.” This has led to a number of attempts to circumvent the Gibbs treatment and to provide alternative approaches. As justification for these attempts it is often stated or implied that the Gibbs formalism constitutes a model in which the propertiesof each bulk region persist without change up to the mathematical surface known as the dividing surface, which is then assumed to possess the