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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
Combining expressions for the Gibbs–Duhem equation in each phase and assuming systematic equilibrium (i.e. that the temperature and pressure is constant throughout the system), we recover the Gibbs' phase rule. One particularly useful expression arises when considering binary solutions. [9] At constant P and T it becomes:
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:
The definition of the Gibbs function is = + where H is the enthalpy defined by: = +. Taking differentials of each definition to find dH and dG, then using the fundamental thermodynamic relation (always true for reversible or irreversible processes): = where S is the entropy, V is volume, (minus sign due to reversibility, in which dU = 0: work other than pressure-volume may be done and is equal ...
When perfectly pure, the interface between fluids usually displays only surface tension. [1] The stress within a fluid interface can be affected by the adsorption of surfactants in several ways: Change in the surface concentration of surfactants when the in-plane flow tends to alter the surface area of the interface (Gibbs' elasticity).
In thermodynamics, the phase rule is a general principle governing multi-component, multi-phase systems in thermodynamic equilibrium.For a system without chemical reactions, it relates the number of freely varying intensive properties (F) to the number of components (C), the number of phases (P), and number of ways of performing work on the system (N): [1] [2] [3]: 123–125
In thermodynamics, the reduced properties of a fluid are a set of state variables scaled by the fluid's state properties at its critical point.These dimensionless thermodynamic coordinates, taken together with a substance's compressibility factor, provide the basis for the simplest form of the theorem of corresponding states.