Détermination directe des constantes cinétiques d'une réaction chimique par microcalorimétrie à conduction application à la saponification des diesters

The kinetic study of competitive consecutive reactions presents difficulties owing to the complexity of the mathematical integration of differential equation systems. Many investigators adopted methods using graphs of experimental data to determine the kinetic constants of a reaction. We propose, in this work, a direct determination of these constants based on thermograms recorded with a Calvet conduction microcalorimeter using a computing program which includes numerical integration of differential equation systems, signal convolution with an experimental function of apparatus (to get rid of the inertness of the detector—recorder system) and the optimization of the adopted model parameters. We applied this exploitation process to the alkaline hydrolysis of some diester of diols or dicarboxylic acids in aqueous solution.