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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 .
The maximum work is thus regarded as the diminution of the free, or available, energy of the system (Gibbs free energy G at T = constant, P = constant or Helmholtz free energy F at T = constant, V = constant), whilst the heat given out is usually a measure of the diminution of the total energy of the system (internal energy).
All thermodynamic data is a non-linear function of temperature (and pressure), but there is no universal equation format for expressing the various functions. Here we describe a commonly used polynomial equation to express the temperature dependence of the heat content. A common six-term equation for the isobaric heat content is:
Thus, in traditional use, the term "free" was attached to Gibbs free energy for systems at constant pressure and temperature, or to Helmholtz free energy for systems at constant temperature, to mean ‘available in the form of useful work.’ [8] With reference to the Gibbs free energy, we need to add the qualification that it is the energy ...
where ln denotes the natural logarithm, is the thermodynamic equilibrium constant, and R is the ideal gas constant.This equation is exact at any one temperature and all pressures, derived from the requirement that the Gibbs free energy of reaction be stationary in a state of chemical equilibrium.
In contrast, the Gibbs free energy or free enthalpy is most commonly used as a measure of thermodynamic potential (especially in chemistry) when it is convenient for applications that occur at constant pressure. For example, in explosives research Helmholtz free energy is often used, since explosive reactions by their nature induce pressure ...
In the history of thermodynamics, "On the Equilibrium of Heterogeneous Substances" is a 300-page paper written by American chemical physicist Willard Gibbs.It is one of the founding papers in thermodynamics, along with German physicist Hermann von Helmholtz's 1882 paper "Thermodynamik chemischer Vorgänge."
Only one equation of state will not be sufficient to reconstitute the fundamental equation. All equations of state will be needed to fully characterize the thermodynamic system. Note that what is commonly called "the equation of state" is just the "mechanical" equation of state involving the Helmholtz potential and the volume: