The alcoholysis of acetyl chloride under various reaction conditions has been investigated by isoperibolic calorimetry and HPLC-analysis. Non-linear kinetic evaluation has been realized by the program TA-kin 3.3 on the basis of temperature and concentration data, Depending on the excess of alcohol, different partial reaction orders are found. The reaction rate also depends on the basicity of the solvent, This could be caused by H-bonding with the alcohol increasing the activation energy. It was possible to distinguish between the kinetic parameters of the ethanolysis and the i-propanolysis of acetyl chloride in the evaluation of the alcoholysis of acetyl chloride by alcoholic mixtures at stoichiometric concentrations of the reagents. A partial order of n = 0.5 far the alcohol, as determined in the evaluation of the single alcoholysis under these conditions, has been confirmed. The results show that heat accumulations are an important feature for the kinetic evaluation of reactions under the concentration conditions described.:(C) 2000 Elsevier Science B.V. All rights reserved.