A new approach was used to monitor the autocatalytic reaction of benzoyl peroxide (BPO) by non-isothermal and isothermal kinetic models constructed using differential scanning calorimetry and thermal activity monitor III analyses, respectively. Autocatalytic reactions generally start slowly and then accelerate as the reactant is consumed and the autocatalyst is produced. Consequently, an autocatalytic reaction may require special design considerations to avoid certain upset conditions, such as runaway exothermic reactions. We conducted a thermal hazard analysis of various products, including benzoic acid, benzene, and phenol, which were deliberately selected and individually mixed with BPO to investigate their thermal hazards. Model fitting can be applied to predict the amount of time required to achieve the maximum rate under isothermal conditions at any temperature of interest. The proposed procedure was effective and accurate for evaluating the autocatalytic reaction of BPO. (C) 2015 Elsevier B.V. All rights reserved.