Evaluation of thermal stability and runaway behavior of any exothermic chemical system is of great importance for the design and operation of a chemical process. The evaluation process should be based on a thorough investigation of the reaction chemistry including reaction pathways, thermodynamic, and kinetic parameters. When addressing the reactivity hazards of any reacting system, the dominant pathway(s) should be identified. Identifying the main reaction pathway under specific conditions will lead to a better thermodynamic and kinetic characterization of the reacting system. In this article, the thermal stability and runaway behavior of styrene-acrylonitrile copolymerization reaction system in bulk is evaluated. Traditional thermal analysis techniques (calorimetric analysis) are combined with computational quantum chemistry methods and empirical thermodynamic-energy correlations. Reaction pathways are identified from the theoretical approach and verified by experimental measurements. The results of this analysis are compared to literature data for this system. (C) 2003 Elsevier B.V. All rights reserved.