Kinetic Modeling of the Thermal Destruction of Lewisite - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Hazardous Materials Année : 2020

Kinetic Modeling of the Thermal Destruction of Lewisite

Résumé

Organoarsenic compounds have been widely used as pesticides and chemical agents. Lewisite (C2H2AsCl3), a blister agent, is a model of such compounds. A comprehensive detailed kinetic mechanism of combustion has been developed based on theoretical investigations. A benchmark allowed to select an appropriate methodology able to deal with such a heavy atom as As with precision and reasonable computational times. The density functional theory (DFT) method ωB97X-D was found to give the best results on target data. Core pseudo potentials were used for arsenic with the cc-pVTZ-PP basis set, whereas Def2-TZVP basis set was used for other atoms. The mechanism of the decomposition of lewisite includes all reactions involved in thermal decomposition and combustion mechanisms, including molecular and radical intermediates, and the decomposition reactions of small species containing arsenic. Simulation shows that lewisite decomposition starts around 700 K and is very little sensitive to the presence of oxygen since the radical reactions involve mainly very reactive Cl-atoms as chain carriers. The main reaction paths have been derived. As experimentally observed, AsCl3 is the main arsenic product produced almost in one-to-one yield, whereas acetylene is an important hydrocarbon product in pyrolysis. In combustion, several arsenic oxides, eventually chlorinated, are produced, which toxicity need to be assessed.
Fichier principal
Vignette du fichier
Paper-Lewisite_HAL.pdf (830.08 Ko) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)
Loading...

Dates et versions

hal-02908202 , version 1 (28-07-2020)

Identifiants

Citer

J.-C Lizardo-Huerta, B. Sirjean, Laurent Verdier, R. Fournet, Pierre-Alexandre Glaude. Kinetic Modeling of the Thermal Destruction of Lewisite. Journal of Hazardous Materials, 2020, 398, pp.123086. ⟨10.1016/j.jhazmat.2020.123086⟩. ⟨hal-02908202⟩
45 Consultations
145 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More