The formation and release of dangerous substances as a consequence of the deviation of a process from the normal operating conditions was found to be the cause of severe accidents, the more important being that of Seveso, that took place in 1976. The present study was dedicated to the definition of specific experimental protocols for the identification of the possible products formed in the loss of control of a chemical industrial process. A set of reference experimental techniques was defined to obtain experimental data on the products formed in "out of control" conditions. The application to several case studies provided useful information on the decomposition products that may be formed in accidental scenarios. The comparison of the experimental data obtained by the application of the reference protocols with information reported in MSDS evidenced that detailed experimental information is of fundamental importance to correctly evaluate the hazard due to the unwanted formation and release of hazardous substances in "out of control" conditions. The analysis of the case studies also evidenced the severity that scenarios due to the formation and release of hazardous products in "out of control" conditions may have for some industrial processes. (C) 2008 Elsevier Ltd. All rights reserved.