CRITICAL THERMODYNAMIC ANALYSIS OF DIFFERENTIAL SCANNING CALORIMETRY FOR STUDYING CHEMICAL-KINETICS

A critical thermodynamic analysis of differential thermal calorimetry is reported herein to gain further insight into the phenomena leading to the reported differences between kinetic parameters extracted from isothermal DSC methods and those from dynamic DSC methods. The sources have been identified for the variations observed in the total heat of reaction as a function of the heating rate in dynamic DSC experiments . The analysis clearly indicates that these variations are, in fact, t o be anticipated. The relationships necessary for extracting kinetic d ata from both isothermal and dynamic experiments are derived rigorousl y by resorting to classical thermodynamics.