Unimolecular Elementary Reactions


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OpenStax Chemistry 2e

The molecularity of an elementary reaction is the number of (atoms, molecules, or ions). For example, a unimolecular reaction involves the reaction of a single reactant species to produce one or more molecules of product:

A ⟶ products

The rate law for a unimolecular reaction is first order:

rate = k[A]

A unimolecular reaction may be one of several elementary reactions in a complex mechanism. For example, the reaction:

O3 ⟶ O2 + O

illustrates a unimolecular elementary reaction that occurs as one part of a two-step reaction mechanism as described above. However, some unimolecular reactions may be the only step of a single-step reaction mechanism. (In other words, an “overall” reaction may also be an elementary reaction in some cases.) For example, the gas-phase decomposition of cyclobutane, C4H8, to ethylene, C2H4 , is represented by the following chemical equation:

This equation represents the overall reaction observed, and it might also represent legitimate elementary reaction. The rate law predicted from this equation, assuming it elementary reaction, turns out to the same as the rate law derived experimentally for the overall reaction, namely, one showing first-order behavior:

This agreement between observed and predicted rate laws is interpreted to mean that the proposed unimolecular, single-step process is a reasonable mechanism for the butadiene reaction.