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Kinetics of homogeneous catalytic chlorination of acetic acid
Author(s) -
Martikainen Päivi,
Salmi Tapio,
Paatero Erkki,
Hummelstedt Leif,
Klein Paul,
Damén Henrik,
Lindroos Torsten
Publication year - 1987
Publication title -
journal of chemical technology and biotechnology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.64
H-Index - 117
eISSN - 1097-4660
pISSN - 0268-2575
DOI - 10.1002/jctb.280400405
Subject(s) - chemistry , acetic acid , catalysis , reaction rate constant , chlorine , solubility , kinetics , dichloroacetic acid , chloride , reaction mechanism , chemical kinetics , inorganic chemistry , organic chemistry , physics , quantum mechanics
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 % H 2 SO 4 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 Cl 2 whereas the reaction is significantly enhanced by MCA and H 2 SO 4 . 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.