Diffusion-controlled reaction

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Diffusion-controlled (or diffusion-limited) reactions are reactions in which the reaction rate is equal to the rate of transport of the reactants through the reaction medium (usually a solution).[1] The process of chemical reaction can be considered as involving the diffusion of reactants until they encounter each other in the right stoichiometry and form an activated complex which can form the product species. The observed rate of chemical reactions is, generally speaking, the rate of the slowest or "rate determining" step. In diffusion controlled reactions the formation of products from the activated complex is much faster than the diffusion of reactants and thus the rate is governed by collision frequency.

Diffusion control is rare in the gas phase, where rates of diffusion of molecules are generally very high. Diffusion control is more likely in solution where diffusion of reactants is slower due to the greater number of collisions with solvent molecules. Reactions where the activated complex forms easily and the products form rapidly are most likely to be limited by diffusion control. Examples are those involving catalysis and enzymatic reactions. Heterogeneous reactions where reactants are in different phases are also candidates for diffusion control.

One classical test for diffusion control of a heterogeneous reaction is to observe whether the rate of reaction is affected by stirring or agitation; if so then the reaction is almost certainly diffusion controlled under those conditions.