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Diagram of thermodynamic surface from Maxwell's book Theory of Heat.The diagram is drawn roughly from the same angle as the upper left photo above, and shows the 3D axes e (energy, increasing downwards), ϕ (entropy, increasing to the lower right and out-of-plane), and v (volume, increasing to the upper right and into-plane).
The technique is closely related to using gas adsorption to measure pore sizes, but uses the Gibbs–Thomson equation rather than the Kelvin equation.They are both particular cases of the Gibbs Equations of Josiah Willard Gibbs: the Kelvin equation is the constant temperature case, and the Gibbs–Thomson equation is the constant pressure case. [1]
The discontinuity in , and other properties, e.g. internal energy, , and entropy,, of the substance, is called a first order phase transition. [12] [13] In order to specify the unique experimentally observed pressure, (), at which it occurs another thermodynamic condition is required, for from Fig.1 it could clearly occur for any pressure in the range .
The Gibbs adsorption isotherm for multicomponent systems is an equation used to relate the changes in concentration of a component in contact with a surface with changes in the surface tension, which results in a corresponding change in surface energy. For a binary system, the Gibbs adsorption equation in terms of surface excess is
A century later Gibbs [3] proposed a modification to Young's equation to account for the volumetric dependence of the contact angle. Gibbs postulated the existence of a line tension, which acts at the three-phase boundary and accounts for the excess energy at the confluence of the solid-liquid-gas phase interface, and is given as:
Gibbs emphasized that for solids, the surface free energy may be completely different from surface stress (what he called surface tension): [14]: 315 the surface free energy is the work required to form the surface, while surface stress is the work required to stretch the surface. In the case of a two-fluid interface, there is no distinction ...
The Marangoni effect (also called the Gibbs–Marangoni effect) is the mass transfer along an interface between two phases due to a gradient of the surface tension. In the case of temperature dependence, this phenomenon may be called thermo-capillary convection [ 1 ] or Bénard–Marangoni convection .
Two methods to extract the Gibbs free energy based on the value of CMC and exist; Phillips method [3] based on the law of mass action and the pseudo-phase separation model. The law of mass action postulates that the micelle formation can be modeled as a chemical equilibrium process between the micelles M n {\displaystyle M_{n}} and its ...