The effects of formaldehyde and hemiformal equilibria on the rates of the base‐catalyzed and hydroxymethylations of phenol by aqueous formaldehyde have been treated quantitatively. A kinetic model treating all seven simultaneous, parallel, consecutive, and competing reactions, as well as the equilibria, has been shown to apply to a wide variety of the conditions and to data from other works. Concentration‐induced solvent effects on the rates and on the ortho/para‐substitution patters have been studied. The temperature dependence of the rate constants, both for dilute systems and systems composed primarily of phenol and aqueous formaldehyde, has been determined.

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