Elementary Reactions

A reaction mechanism consists of a series of elementary reaction steps, the sum of which is the stoichiometric chemical equation. An elementary reaction is a precise statement of the molecules which react or are formed in a single step of a mechanism. When we write a mechanism with its elementary reaction steps, we are forming a hypothesis that we hope to test with experimental rate data. The first step in such a test is to derive the rate law expected from the postulated mechanism.

The molecularity specifies the number of molecules involved as reactants in an elementary step. A unimolecular reaction is a step in which a single A molecule undergoes a reaction; the rate of such a step is first-order, k1[A]. A bimolecular reaction is a step in which two molecules react, A + B or 2 A; the rate of such a step is first-order in each reacting species, k₂[A][B] or k₂[A]². A termolecular reaction is a step in which three molecules react, A + B + C or 2 A + B or 3 A; the rate of such a step is first-order in each reacting species and third-order overall.