A mechanistic and experimental study of the diethyl ether oxidation

Carlo Adamo (1) , Patricia Rotureau (2) , Stefania Di Tommaso (1) , Wassila Benaissa (2) , Peggy Gruez (2)

1 LECIME - Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575)
2 INERIS - Institut National de l'Environnement Industriel et des Risques

This work presents the results of the theoretical investigations on autoxidation process of diethyl ether (DEE), a chemical largely used as solvent in laboratories and considered to be responsible for various accidents. Based on Density Functional Theory (DFT) calculations, the aims of this study were the identification of all the most probable reaction paths involved in DEE oxidation (at ambient temperature and under conditions that reflect normal storage conditions) and the characterization of products and all potential hazardous intermediates, such as peroxides. Results indicate that industrial hazards could be related to hydroperoxide formation and accumulation during the chain propagation step. A detailed kinetics model of DEE oxidation in the gas phase was then developed from all energetic and kinetics parameters collected during the mechanistic study. Outputs of the kinetics model, in terms of time of evolution of product concentrations, have been then compared with the experimentally measured concentration of products (notably hydroperoxides) issued from tests on DEE oxidation conducted under accelerated conditions with autoclaves.

Mots clés: DIETHYL ETHER (DEE); DFT; KINETICS MODEL; OXIDATION AT ACCELERATED CONDITIONS

Domaines: Sciences de l'ingénieur [physics]

Carlo Adamo, Patricia Rotureau, Stefania Di Tommaso, Wassila Benaissa, Peggy Gruez. A mechanistic and experimental study of the diethyl ether oxidation. AIChE Spring Meeting 2012 & 8. Global Congress on Process Safety (GCPS), Apr 2012, Houston, United States. pp.NC. ⟨ineris-00976232⟩