Kinetics of homogeneous catalytic chlorination of acetic acid

The kinetics of the chlorination of acetic acid (HAc) to monochloroacetic acid (MCA) and the physical solubility of chlorine in HAc and its mixtures with MCA were investigated in a laboratory scale semibatch reactor. The temperature dependence of the Henry's constant was determined from solubility data obtained at temperatures between 70°C and 110°C. The kinetic experiments were performed at 75–100°C with 3–13 mol % acetyl chloride (AcCl) and 0–5 weight % H₂SO₄ added as catalysts. Gas chromatography was used to determine the concentrations of HAc, MCA, dichloroacetic acid and AcCl during the experiments. The results indicate that the reaction rate is independent of the concentrations of HAc and Cl₂ whereas the reaction is significantly enhanced by MCA and H₂SO₄. The effects are explained by a reaction mechanism involving the acid catalyzed enolization of AcCl as the rate-determining step. A rate equation based on this mechanism was derived. Kinetic constants included in the equation were determined by regression analysis.