The characterization of thermal decomposition of cumene hydroperoxide (CHP) in cumene from kinetic point of view is of great interest for industrial applications. However, the efforts done so far by the researchers lead only to the availability of single kinetic laws (first order, autocatalytic, etc.) whose usefulness is strongly limited by the presence in the starting solutions of some impurities. A detailed model aiming at simulating both, thermal and kinetic behavior of the system, is now presented. In other words, the proposed model tries to simulate CHP thermal decomposition process at varying reaction conditions (different initial temperature, in the range 120-160 degrees C, different initial CHP concentrations, addition of a-methylstyrene to CHP solutions in cumene) and during isothermal, scanning and adiabatic runs. A good capability of the model is observed to simulate the system behavior by using data collected under isothermal and adiabatic conditions and during scanning calorimetric runs. It is important to stress that the use of the model proposed in the present investigation does not require the adoption of adjustable parameters. (C) 2012 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.