Bell–Evans–Polanyi principle

In physical chemistry, the Evans–Polanyi principle (also referred to as the Bell–Evans–Polanyi principle, Brønsted–Evans–Polanyi principle, or Evans–Polanyi-Semenov principle) observes that the difference in activation energy between two reactions of the same family is proportional to the difference of their enthalpy of reaction.

This relationship can be expressed as:

where:

The Evans-Polanyi model is a linear energy relationship that serves as an efficient way to calculate activation energy of many reactions within a distinct family. The activation energy may be used to characterize the kinetic rate parameter of a given reaction through application of the Arrhenius equation.

The Evans-Polanyi model assumes the pre-exponential factor of the Arrhenius equation and the position of the transition state along the reaction coordinate are the same for all reactions belonging to a particular reaction family.

The Bell–Evans–Polanyi model was developed independently by Ronald Percy Bell and by Meredith Gwynne Evans and Michael Polanyi to explain the apparent linear relationship between activation energy and free energy in acid disassociation, as described in the Brønsted catalysis equation which was the original linear free energy relationship published in 1924.

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