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Article Dans Une Revue Journal of Physical Chemistry A Année : 2018

Thermal Decomposition of Phosgene and Diphosgene

Résumé

Phosgene (COCl2) is a toxic compound used or formed in a wide range of applications. The understanding of its thermal decomposition for destruction processes or in the event of accidental fire of stored reserves is a major safety issue. In this study, a detailed chemical kinetic model for the thermal decomposition and combustion of phosgene and diphosgene is proposed for the first time. A large number of thermo-kinetic parameters were calculated using quantum chemistry and reaction rate theory. The model was validated against experimental pyrolysis data from the literature. It is predicted that the degradation of diphosgene is mainly ruled by a pericyclic reaction producing two molecules of phosgene, and, to a lesser extent, by a roaming radical reaction yielding CO2 and CCl4. Phosgene is much more stable than diphosgene under high-temperature conditions and its decomposition starts at higher temperatures. Decomposition products are CO and Cl2. An equimolar mixture of these latter can be considered as a surrogate of phosgene from the kinetic point of view, but the important endothermic effect of the decomposition reaction can lead to different behaviors, for instance in case of auto-ignition under high pressure and high temperature.
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Dates et versions

hal-01708227 , version 1 (13-02-2018)

Identifiants

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Juan-Carlos Lizardo-Huerta, Baptiste Sirjean, Laurent Verdier, René Fournet, Pierre-Alexandre Glaude. Thermal Decomposition of Phosgene and Diphosgene. Journal of Physical Chemistry A, 2018, 122 (1), pp.249-257. ⟨10.1021/acs.jpca.7b09554⟩. ⟨hal-01708227⟩
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