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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.
Therefore, only relative free energy values, or changes in free energy, are physically meaningful. The free energy is the portion of any first-law energy that is available to perform thermodynamic work at constant temperature, i.e., work mediated by thermal energy. Free energy is subject to irreversible loss in the course of such work. [1]
The Gibbs–Helmholtz equation is a thermodynamic equation used to calculate changes in the Gibbs free energy of a system as a function of temperature.It was originally presented in an 1882 paper entitled "Die Thermodynamik chemischer Vorgänge" by Hermann von Helmholtz.
In thermodynamics, the Helmholtz free energy (or Helmholtz energy) is a thermodynamic potential that measures the useful work obtainable from a closed thermodynamic system at a constant temperature . The change in the Helmholtz energy during a process is equal to the maximum amount of work that the system can perform in a thermodynamic process ...
The energy is replaced by the characteristic potential of that ensemble, the Gibbs Free Energy. The letter Z stands for the German word Zustandssumme , "sum over states". The usefulness of the partition function stems from the fact that the macroscopic thermodynamic quantities of a system can be related to its microscopic details through the ...
The surface energy of a liquid may be measured by stretching a liquid membrane (which increases the surface area and hence the surface energy). In that case, in order to increase the surface area of a mass of liquid by an amount, δA, a quantity of work, γ δA, is needed (where γ is the surface energy density of the liquid).
The free energy of activation, ΔG ‡, is defined in transition state theory to be the energy such that ‡ = ‡ ′ holds. The parameters ΔH ‡ and ΔS ‡ can then be inferred by determining ΔG ‡ = ΔH ‡ – TΔS ‡ at different temperatures.
This free-energy map is also known as a potential of mean force (PMF). Free-energy perturbation calculations only converge properly when the difference between the two states is small enough; therefore it is usually necessary to divide a perturbation into a series of smaller "windows", which are computed independently.