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

• DOI: 10.1016/j.tca.2021.178983
• Publication Date: 2021-06-26T03:09:33Z
• Authors: Jiong Ding; Xingci Zhang; Dongfang Hu; Shuliang Ye; Juncheng Jiang
• Keywords: Cumene hydroperoxide; Thermal inertia; Cumene

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.