§ DICTIONARY · CONCEPT

Arrhenius equation

k = A exp(−E_a/k_BT) — the law that ties a reaction's rate to temperature through the Boltzmann tail of molecules energetic enough to react.

§ 01

Definition

The Arrhenius equation expresses the rate constant of a chemical reaction as k = A exp(−E_a/RT), with E_a the activation energy, A a pre-exponential frequency factor, and RT (or k_BT per molecule) the thermal energy. The exponential is a Boltzmann factor: it is the fraction of molecular collisions energetic enough to clear the activation barrier. A modest rise in temperature can multiply the reacting fraction many times over, which is why reaction rates are so sharply temperature-sensitive.

The form is the direct fingerprint of the MaxwellBoltzmann tail. Only molecules in the high-energy tail of the distribution carry enough energy to react, and that tail grows exponentially with temperature. A common rule of thumb — that many reactions roughly double in rate for every 10 °C — is just the Arrhenius factor evaluated for typical activation energies.

Plotting ln k against 1/T gives a straight line whose slope is −E_a/R, the standard experimental route to measuring activation energies. The same exponential governs diffusion in solids, viscous flow, and the temperature dependence of biological processes.

§ 02

History

Proposed by Svante Arrhenius in 1889, building on earlier work by van 't Hoff; later given a microscopic basis by collision theory and transition-state theory, both resting on the Boltzmann factor.

Arrhenius equation — Physics.explained