Journal of Loss Prevention in the Process Industries 21 (2008) 407–422 Experimental strategies for the identification of substances formed in the loss of control of chemical industrial processes Federica Barontini a , Severino Zanelli a , Valerio Cozzani b,Ã , Lucia Gigante c , Angelo Lunghi c , Renato Rota d , Paolo Cardillo c a Dipartimento di Ingegneria Chimica, Chimica Industriale e Scienza dei Materiali, Universita` degli Studi di Pisa, via Diotisalvi n.2, 56126 Pisa, Italy b Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie Ambientali, Alma Mater Studiorum, Universita` di Bologna, via Terracini 28, 40131 Bologna, Italy c Stazione Sperimentale Combustibili, v.le De Gasperi 3, 20097 S. Donato Milanese, Italy d Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘‘G. Natta’’, Politecnico di Milano, Via Mancinelli 7, 20131 Milano, Italy Received 5 October 2007; received in revised form 13 October 2007; accepted 6 February 2008 Abstract 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. r 2008 Elsevier Ltd. All rights reserved. Keywords: Major accident hazards; Runaway reactions; Hazardous substances; Experimental protocols; Analysis of decomposition products; Hyphenated techniques 1. Introduction The high number of severe accidents that took place in chemical plants during the past years have raised serious concerns on their reliability, their safety, and their environmental impact, calling for the further development of safety assessment and risk management tools. Handling and processing of chemical substances may directly cause important hazards due to the substance characteristics. However, another important hazard factor comes from the possible formation of dangerous compounds by unwanted or unforeseen reactions. These events are usually associated to a loss of containment, thus resulting in a toxic release. As a matter of fact, the formation 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 (Cozzani, Amendola, & Zanelli, 1997; Cozzani & Zanelli, 1997; Cozzani, Zanelli, Amendola, & Smeder, 1997), the more important being that of Seveso, in 1976, that gave the name to the European Directives on the control of major industrial hazards (Council Directive 82/501/EEC, 1982; Council Directive 96/82/EC, 1996). Although the dangerous characteristics of chemical sub- stances involved in industrial processes are extensively investigated, less attention is paid to the chemical hazards posed by unwanted reactions. This is probably caused by the complexity of the problem. The chemical effects of ARTICLE IN PRESS www.elsevier.com/locate/jlp 0950-4230/$ - see front matter r 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.jlp.2008.02.001 Ã Corresponding author. Tel.: +39 051 2090240; fax: +39 051 2090247. E-mail address: valerio.cozzani@unibo.it (V. Cozzani).