• adiabatic onset temperature;
  • adiabatic time to maximum rate;
  • differential scanning calorimetry;
  • kinetic model;
  • dicumyl peroxide

The article investigates the possibility of obtaining reliable information on the adiabatic behavior of thermally unstable substances based on the thermokinetic data collected by differential scanning calorimetric experiments. In particular, it is developed a novel numerical algorithm which allows the estimation of the adiabatic onset temperature. Theoretical results are verified considering the thermal decomposition of dicumyl peroxide carried out under different calorimetric conditions. Encouraging results point out that the procedures developed allow the assessment of adiabatic critical parameters that are very close to the values determined during the experiments. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3806–3815, 2013