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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]
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 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 ...
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 ...
Key: G = Gibbs free energy p = Pressure H = Enthalpy S = Entropy U = Internal energy V = Volume F = Helmholtz free energy T = Temperature. The thermodynamic square (also known as the thermodynamic wheel, Guggenheim scheme or Born square) is a mnemonic diagram attributed to Max Born and used to help determine thermodynamic relations.
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 heat content of an ideal gas is independent of pressure (or volume), but the heat content of real gases varies with pressure, hence the need to define the state for the gas (real or ideal) and the pressure. Note that for some thermodynamic databases such as for steam, the reference temperature is 273.15 K (0 °C).
In thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol ) is a thermodynamic potential that can be used to calculate the maximum amount of work, other than pressure–volume work, that may be performed by a thermodynamically closed system at constant temperature and pressure.