Calorimetric Investigation of the Formation of Grignard Reagents

A novel technique for the determination of the thermodynamic and kinetic parameters of the Grignard reagent formation is described. Instead of operating under the spontaneous exothermic initiation of Grignard reactions, the calorimetric measurement was carried out in a closed reactor pressure vessel. In that way, the increase of the reactor temperature and the pressure can be used for detecting the initiation of the Grignard-reagent formation as shown by comparison with the on-line profiles of the concentration of the Grignard reagent measured by FTIR-spectroscopy simultaneously. Results showed that the molar reaction enthalpy of a Grignard reagent could be determined by a closed reactor vessel more accurately than under reflux conditions.