In chemistry, activation energy is a term introduced in 1889 by the Swedish scientist Svante Arrhenius, that is defined as the energy that must be overcome in order for a chemical reaction to occur. 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 Ea, and given in units of kilojoules per mole.
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 energy equal to or greater than the activation energy.
In some cases rates of reaction decrease with increasing temperature. When following an approximately exponential relationship so the rate constant can still be fit to an Arrhenius expression, this results in a negative value of Ea. Reactions exhibiting these negative activation energies are typically barrierless reactions, in which the reaction proceeding relies on the capture of the molecules in a potential well. Increasing the temperature leads to a reduced probability of the colliding molecules capturing one another (with more glancing collisions not leading to reaction as the higher momentum carries the colliding particles out of the potential well), expressed as a reaction cross section that decreases with increasing temperature. Such a situation no longer leads itself to direct interpretations as the height of a potential barrier.
A substance that modifies the transition state to lower the activation energy is termed a catalyst; a biological catalyst is termed an enzyme. It is important to note that a catalyst increases the rate of reaction without being consumed by it. In addition, while the catalyst lowers the activation energy, it does not change the energies of the original reactants nor products. Rather, the reactant energy and the product energy remain the same and only the activation energy is altered (lowered).
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