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Concept# Thermodynamic potential

Summary

A thermodynamic potential (or more accurately, a thermodynamic potential energy) is a scalar quantity used to represent the thermodynamic state of a system. Just as in mechanics, where potential energy is defined as capacity to do work, similarly different potentials have different meanings. The concept of thermodynamic potentials was introduced by Pierre Duhem in 1886. Josiah Willard Gibbs in his papers used the term fundamental functions.
One main thermodynamic potential that has a physical interpretation is the internal energy U. It is the energy of configuration of a given system of conservative forces (that is why it is called potential) and only has meaning with respect to a defined set of references (or data). Expressions for all other thermodynamic energy potentials are derivable via Legendre transforms from an expression for U. In other words, each thermodynamic potential is equivalent to other thermodynamic potentials; each potential is a different expression of the others.
In thermodynamics, external forces, such as gravity, are counted as contributing to total energy rather than to thermodynamic potentials. For example, the working fluid in a steam engine sitting on top of Mount Everest has higher total energy due to gravity than it has at the bottom of the Mariana Trench, but the same thermodynamic potentials. This is because the gravitational potential energy belongs to the total energy rather than to thermodynamic potentials such as internal energy.
Five common thermodynamic potentials are:
where T = temperature, S = entropy, p = pressure, V = volume. Ni is the number of particles of type i in the system and μi is the chemical potential for an i-type particle. The set of all Ni are also included as natural variables but may be ignored when no chemical reactions are occurring which cause them to change. The Helmholtz free energy is in ISO/IEC standard called Helmholtz energy or Helmholtz function. It is often denoted by the symbol F, but the use of A is preferred by IUPAC, ISO and IEC.

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Helmholtz free energy

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 (isothermal). 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 in which temperature is held constant. At constant temperature, the Helmholtz free energy is minimized at equilibrium.

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