Activation energy

In chemistry, activation energy is a term introduced in 1889 by the Swedish scientist Svante Arrhenius to describe the minimum energy which must be available to a chemical system with potential reactants to result in a chemical reaction. Activation energy may also be defined as the minimum energy required to start a chemical reaction. The activation energy of a reaction is usually denoted by E_a and given in units of kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol).

Activation energy can be thought of as the height of the potential barrier (sometimes called the energy barrier) separating two minima of potential energy (of the reactants and products of a reaction). For a chemical reaction to proceed at a reasonable rate, there should exist an appreciable number of molecules with translational energy equal to or greater than the activation energy.

The Arrhenius equation gives the quantitative basis of the relationship between the activation energy and the rate at which a reaction proceeds. From the equation, the activation energy can be found through the relation

where A is the frequency factor for the reaction, R is the universal gas constant, T is the absolute temperature (usually in kelvins), and k is the reaction rate coefficient. Even without knowing A, E_a can be evaluated from the variation in reaction rate coefficients as a function of temperature (within the validity of the Arrhenius equation).

At a more advanced level, the net Arrhenius activation energy term from the Arrhenius equation is best regarded as an experimentally determined parameter that indicates the sensitivity of the reaction rate to temperature. There are two objections to associating this activation energy with the threshold barrier for an elementary reaction. First, it is often unclear as to whether or not reaction does proceed in one step; threshold barriers that are averaged out over all elementary steps have little theoretical value. Second, even if the reaction being studied is elementary, a spectrum of individual collisions contributes to rate constants obtained from bulk ('bulb') experiments involving billions of molecules, with many different reactant collision geometries and angles, different translational and (possibly) vibrational energies—all of which may lead to different microscopic reaction rates.

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