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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 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
The UNIQUAC model can be considered a second generation activity coefficient because its expression for the excess Gibbs energy consists of an entropy term in addition to an enthalpy term. Earlier activity coefficient models such as the Wilson equation and the non-random two-liquid model (NRTL model) only consist of enthalpy terms.
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:
Thus, they are essentially equations of state, and using the fundamental equations, experimental data can be used to determine sought-after quantities like G (Gibbs free energy) or H . [1] The relation is generally expressed as a microscopic change in internal energy in terms of microscopic changes in entropy , and volume for a closed system in ...
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 equation is very clearly derived in Gibbs, however. What is not derived in Gibbs is the phase rule. Gibbs uses his equation 97 (the Gibbs-Duhem equation) to quickly argue its likelihood, but never changes his variables from intensities (the same in each phase) to concentrations (different in each phase).
By normalizing the above equation by the extent of a system, such as the total number of moles, the Gibbs–Duhem equation provides a relationship between the intensive variables of the system. For a simple system with I {\displaystyle I} different components, there will be I + 1 {\displaystyle I+1} independent parameters or "degrees of freedom".