Model-free kinetic determination of pre-exponential factor and reaction mechanism in accelerating rate calorimetry

Abstract

Abstract Accelerating rate calorimetry (ARC) is an essential tool in thermal hazard assessment of self-reactive chemicals. Compared to the thermal analysis, the kinetic approaches for ARC are relatively less. To enrich the kinetic approaches for ARC, the feasibility of a model-free based pre-exponential factor and reaction model determining method in ARC data process is investigated in this article. By using the compensation effect in association with Friedman s isoconversional method, the Eα, lnAα and f(α) dependency with α are obtained from several experiments under different thermal inertia. Then, the apparent reaction mechanism function is determined based on non-linear regression method. For effective verification, the numerical simulations are carried out based on a Sestak-Berggren decomposition model. In addition, the applicability of this kinetic approach is investigated by studying the effect of NaOH on the thermal decomposition of cumene hydroperoxide/cumene solutions. Both the simulative and experimental results show the value of this kinetic approach.