free energy

Measure of the total combined energies within a system, derived from heats of transformation, disorder, and other forms of internal energy (e.g., electrostatic charges). A system will change spontaneously to achieve a lower total free energy. Thus, free energy is the driving force toward equilibrium conditions. The change in free energy between an initial and a final state is useful in evaluating certain thermodynamic processes and can be used to judge whether transformations will occur spontaneously. There are two forms of free energy, with different definitions and applications: the Helmholtz (see Hermann von Helmholtz) free energy, sometimes called the work function, and the Gibbs (see J. Willard Gibbs) free energy.

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In physical organic chemistry, a free-energy relationship or linear Gibbs energy relation relates the logarithm of a reaction rate constant or equilibrium constant for one series of reactions with the logarithm of the rate or equilibrium constant for a related series of reactions. Establishing free-energy relationships helps understanding the reaction mechanism for a chemical reaction and makes it possible to predict reaction rates and equilibrium constants.

The Brønsted catalysis equation describes the relationship between the ionization constant of a series of catalysts and the reaction rate constant for a reaction on which the catalyst operates. The Hammett equation predicts the equilibrium constant or reaction rate of a reaction from a substituent constant and a reaction type constant. The Edwards equation relates the nucleophilic power to polarisability and basicity.

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