Activation energy

1 Formula
Temp in kelvin R=8.314j/k/mol

( )
k2 energy activation 1 1
log = · −
k1 2.303R t1 t2
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 con-
stants obtained from bulk ('bulb') experiments involving
billions of molecules, with many different reactant col-
lision geometries and angles, different translational and
(possibly) vibrational energies—all of which may lead to
different microscopic reaction rates.

2 Temperature independence and

The sparks generated by striking steel against a flint provide the the relation to the Arrhenius
activation energy to initiate combustion in this Bunsen burner. equation
The blue flame sustains itself after the sparks stop because the
continued combustion of the flame is now energetically favorable.
The Arrhenius equation gives the quantitative basis of the
relationship between the activation energy and the rate at
which a reaction proceeds. From the Arrhenius equation,
In chemistry, activation energy is a term introduced in the activation energy can be found through the relation
1889 by the Swedish scientist Svante Arrhenius to de-
scribe the minimum energy which must be available to
k = Ae−Ea /(RT )
a chemical system with potential reactants to result in
a chemical reaction. Activation energy may also be de- where A is the frequency factor for the reaction, R is the
fined as the maximum energy required to start a chemical universal gas constant, T is the temperature (in kelvin),
reaction. The activation energy of a reaction is usually and k is the reaction rate coefficient. Even without know-
denoted by Ea and given in units of kilojoules per mole ing A, Ea can be evaluated from the variation in reaction
(kJ/mol) or kilocalories per mole (kcal/mol). rate coefficients as a function of temperature (within the
validity of the Arrhenius equation).
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 reac-
tants and products of a reaction). For a chemical reaction 3 Negative activation energy
to proceed at a reasonable rate, there should exist an ap-
preciable number of molecules with translational energy In some cases, rates of reaction decrease with increas-
equal to or greater than the activation energy. ing temperature. When following an approximately ex-

1
2 7 EXTERNAL LINKS

ponential relationship so the rate constant can still be fit
to an Arrhenius expression, this results in a negative value
of Ea. Elementary 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 di-
rect interpretations as the height of a potential spot.
stead of also using Eₐ, however, the Eyring equation uses
the concept of Gibbs energy and the symbol * ∆G‡ to
denote the energy of the transition state. This implies that
the equation is similar but not identical to the Arrhenius
one, because the Gibbs energy contains an entropic term
in addition to the enthalpic one.
6 See also
• Fire point
• Arrhenius equation

• Chemical kinetics
4 Catalysis • Mean kinetic temperature

• Quantum tunnelling
Main article: Catalysis
A substance that modifies the transition state to lower the
Reaction without catalyst 7 External links
Reaction with catalyst

Ea (Y→X)
Ea (X→Y)
Energy

∆H
X

Reaction path

The relationship between activation energy ( Ea ) and enthalpy

of formation (ΔH) with and without a catalyst, plotted against
the reaction coordinate. The highest energy position (peak posi-
tion) represents the transition state. With the catalyst, the energy
required to enter transition state decreases, thereby decreasing the
energy required to initiate the reaction.

activation energy is termed a catalyst; a biological catalyst

is termed an enzyme. It is important to note that a cata-
lyst 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 re-
actants or products. Rather, the reactant energy and the
product energy remain the same and only the activation
energy is altered (lowered).

5 Relationship with Gibbs energy

In the Arrhenius equation, the term activation energy
(Eₐ) is used to describe the energy required to reach the
transition state. Likewise, the Eyring equation is a simi-
lar equation that also describes the rate of a reaction. In-
 3

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