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Helmholtz free energy


In thermodynamics, the Helmholtz free energy is a thermodynamic potential that measures the “useful” work obtainable from a closed thermodynamic system at a constant temperature and volume. The negative of the difference in the Helmholtz energy is equal to the maximum amount of work that the system can perform in a thermodynamic process in which volume is held constant. If the volume is not held constant, part of this work will be performed as boundary work. The Helmholtz energy is commonly used for systems held at constant volume. Since in this case no work is performed on the environment, the drop in the Helmholtz energy is equal to the maximum amount of useful work that can be extracted from the system. For a system at constant temperature and volume, the Helmholtz energy is minimized at equilibrium.

The Helmholtz free energy was developed by Hermann von Helmholtz, a German physicist, and is usually denoted by the letter A  (from the German “Arbeit” or work), or the letter F . The IUPAC recommends the letter A  as well as the use of name Helmholtz energy. In physics, the letter F can also be used to denote the Helmholtz energy, as Helmholtz energy is sometimes referred to as the Helmholtz function, Helmholtz free energy, or simply free energy (not to be confused with Gibbs free energy or free enthalpy).

While Gibbs free energy is most commonly used as a measure of thermodynamic potential, especially in the field of chemistry, it is inconvenient for some applications that do not occur at constant pressure. For example, in explosives research, Helmholtz free energy is often used since explosive reactions by their nature induce pressure changes. It is also frequently used to define fundamental equations of state of pure substances.


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