Calorimetric and kinetic evaluation of thermal stability and process safety in tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxybenzoate

This study evaluated the thermal stability and process safety of tert-butyl peroxybenzoate (TBPB), tert-butyl peroxy-2-ethylhexanoate (TBPO), and their mixture. Thermogravimetric (TG) analysis, differential scanning calorimetry (DSC), and accelerated rate calorimetry were used to elucidate the thermal behavior and breakdown kinetics. The TG results indicated moderate to low breakdown temperatures for all samples, demonstrating their thermal stability. DSC revealed onset temperatures for exothermic disintegration between 66.66 °C and 104.23 °C. The mixture had two distinct exothermic peaks, signifying the thermal decomposition of the mixture was such that the characteristic temperature and heat of the reaction were between those of TBPB and TBPO. Using Heat–Wait–Search methodology, the study identified thermal runaway exothermically. Under pseudoadiabatic conditions, the mixture exhibited greater increases in temperature and pressure—of 115.06 °C and 28.77 bar, respectively—compared with the individual compounds. To elucidate the apparent activation energy (E_a) and reaction kinetics, the study applied models developed by Arrhenius, Flynn-Wall-Ozawa, Friedman, Kissinger, and Starink. The E_a values obtained based on the TG, DSC, and ARC experiments were approximately 50.47, 98.19, and 99.71 kJ/mol, respectively, and were lower than those of TBPB and TBPO pure substances. The self-accelerating decomposition temperature of TBPB/TBPO decreased from 34 to 32 °C as the packaging of TBPB/TBPO was increased from 25 to 100 kg and was more than 10 °C lower than that of the individual substance. These findings offer a framework for evaluating the thermal risks associated with TBPB and TBPO, particularly when mixed. They contribute to the safe transit, storage, and handling of industrial organic peroxides, enriching our collective understanding of the stability and safety of these compounds.