Thermochemical stability: A comparison between experimental and predicted data C. Pasturenzi a, * , M. Dellavedova a , L. Gigante a , A. Lunghi a , M. Canavese a , C. Sala Cattaneo b , S. Copelli c a INNOVHUB, Divisione Stazione Sperimentale per i Combustibili, viale A. De Gasperi, 3, 20097 S. Donato M.se, Italy b Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria Chimica “G. Natta”, via Mancinelli 7, 20131 Milano, Italy c Università degli Studi dell’Insubria, Dipartimento di Scienza e Alta Tecnologia, via G.B. Vico 46, 21100 Varese, Italy article info Article history: Received 11 January 2013 Received in revised form 29 March 2013 Accepted 30 March 2013 Keywords: CHETAH DSC ARC Energy release potential Classification Risk database abstract The first step to be performed during the development of a new industrial process should be the assessment of all hazards associated to the involved compounds. Particularly, the knowledge of all substances thermochemical parameters is a primary feature for such a hazard evaluation. CHETAH (CHEmical Thermodynamic And Hazard evaluation) is a prediction software suitable for calculating potential hazards of chemicals, mixtures or a single reaction that, using only the structure of the involved molecules and Benson’s group contribution method, is able to calculate heats of formation, entropies, Gibbs free energies and reaction enthalpies. Because of its ability to predict the potential hazards of a material or mixture, CHETAH is part of the so-called “desktop methods” for early stage chemical safety analysis. In this work, CHETAH software has been used to compile a complete risk database reporting heats of decomposition and Energy Release Potential (ERP) for 342 common use chemicals. These compounds have been gathered into classes depending on their functional groups and similarities in their thermal behavior. Calculated decomposition enthalpies for each of the compounds have also been compared with experimental data obtained with either thermoanalytic or calorimetric techniques (Differential Scanning Calorimeter e DSC e and Accelerating Rate Calorimeter e ARC). Ó 2013 Elsevier Ltd. All rights reserved. 1. Introduction Systematic search for hazards, risk assessment and identifica- tion of possible remedies are the basic steps of risk analysis (Stoessel, 2008). Chemical industry, more than any others, is perceived as a potential threat for mankind and environment. Nevertheless, all the benefits arising from its activities cannot be disregarded: drugs for human health, crop protection, new mate- rials, colors, textiles and so on. One of the reason contributing to this negative perception is the occurrence of major accidents, such as those ones which took place in Seveso and Bhopal, that, even if are rare, unavoidably retain public attention. Therefore, in order to minimize and, if possible, eliminate such catastrophic events, a number of studies about the chemical risk associated to the thermal stability of compounds or reacting mixtures has been carried out throughout the last 35 years (Barontini, Cozzani, & Petarca, 2001; Cardillo, 2001; Cardillo & Cattaneo, 1991; Cardillo, Gigante, Lunghi, Fraleoni Morgera, & Zanirato, 2008; Cardillo, Gigante, Lunghi, & Zanirato, 2010; Cardillo & Girelli, 1980; Copelli et al., 2011a, 2011b; Di Somma et al., 2010; Dien, Fierz, Stoessel, & Kille, 1994; Fayet, Rotureau, Joubert, & Adamo, 2011; Frurip et al., 1995; Lunghi et al., 2004; Maestri et al., 2009; Roduit et al., 2005; Sato & Sugawara, 1985; Sempere, Nomen, Serra, & Cardillo, 1997). Chemical risk associated with thermally unstable materials or systems is sometimes predictable from both complete thermody- namic knowledge and correct interpretations of the fundamental laws of physical chemistry. The first step in the identification of thermal dangers consists in evaluating the thermodynamic po- tential of the system: that is, determining whether the reaction is thermodynamically favored and, subsequently, how much thermal energy releases. The amount of heat evolved can be related to the adiabatic temperature rise and, then, to the instability of reactants, products or reaction mass. Therefore, if it is possible to know or calculate in advance all the thermal effects of an undesired reaction, it is possible, at least as a first approximation, to predict the hazard. Basing on these features, it is very important to posses suitable tools aimed to determine the thermodynamic potential associated to a chemical compound or a mixture with a quite high level of * Corresponding author. Fax: þ39 02514286. E-mail address: pasturenzi@ssc.it (C. Pasturenzi). Contents lists available at SciVerse ScienceDirect Journal of Loss Prevention in the Process Industries journal homepage: www.elsevier.com/locate/jlp 0950-4230/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jlp.2013.03.011 Journal of Loss Prevention in the Process Industries xxx (2013) 1e13 Please cite this article in press as: Pasturenzi, C., et al., Thermochemical stability: A comparison between experimental and predicted data, Journal of Loss Prevention in the Process Industries (2013), http://dx.doi.org/10.1016/j.jlp.2013.03.011