Hammett equation in the context of Free-energy relationship


Hammett equation in the context of Free-energy relationship

⭐ Core Definition: Hammett equation

In organic chemistry, the Hammett equation describes a linear free-energy relationship relating reaction rates and equilibrium constants for many reactions involving benzoic acid derivatives with meta- and para-substituents to each other with just two parameters: a substituent constant and a reaction constant. This equation was developed and published by Louis Plack Hammett in 1937 as a follow-up to qualitative observations in his 1935 publication.

The basic idea is that for any two reactions with two aromatic reactants only differing in the type of substituent, the change in free energy of activation is proportional to the change in Gibbs free energy. It is important to understand, that the equilibrium constants in this relationship come from thermodynamics but the reaction rate constants come from chemical kinetics , and neither discipline predicts such relationship. Instead, it was introduced by Hammett empirically. Hammett equation belongs to a larger set of correlations between the rate of a chemical reaction and its driving force.

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Hammett equation in the context of Methoxy

In organic chemistry, a methoxy group is the functional group consisting of a methyl group bound to oxygen. This alkoxy group has the formula R−O−CH3.

On a benzene ring, the Hammett equation classifies a methoxy substituent at the para position as an electron-donating group, but as an electron-withdrawing group if at the meta position. At the ortho position, steric effects are likely to cause a significant alteration in the Hammett equation prediction, which otherwise follows the same trend as that of the para position.

View the full Wikipedia page for Methoxy
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