Kinetics of the degradation of methyl, ethyl and n-propyl 4-hydroxybenzoate esters in aqueous solution

Abstract

The kinetics of the hydrolysis of methyl, ethyl and n-propyl 4-hydroxybenzoate esters and a subsequent decarboxylation of 4-hydroxybenzoic acid have been studied at pH 1.26–10.59 and the sterilizing temperature of 130.5°C. Enthalpies (ΔH∗) and entropies (ΔS∗) of activation are reported for k obs and the derived rate constants. The decarboxylation reaction showed a maximum rate near the mid-pH region where the esters were more susceptible to hydrolysis. The overall pathway for the degradation of the esters was accounted for by a consecutive reaction sequence: ▪ where A represents ester, B, 4-hydroxybenzoic acid and C, phenol. Interference with the spectrophotometric assay by the subsequent oxidation of phenol, made necessary the exhaustive de-oxygenation of solutions for the kinetic runs where phenol was formed. The esters were found to be sufficiently stable to withstand a heat sterilization process within the pH range 3–6. The rate of phenol formation by decarboxylation of the acid was greater in the pH range where the esters are frequently used commercially, as preservatives.