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Published on: August 17, 2019
Oxidation mechanism of diethyl ether: a complex process for a simple molecule.
Stefania Di Tommaso1, Patricia Rotureau, Orlando Crescenzi
1Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie, CNRS UMR 7575, Chimie ParisTech, 11, rue Pierre et Marie Curie, F-75231 Paris Cedex 05, France.
Diethyl ether (DEE) autoxidation involves complex mechanisms. Density Functional Theory (DFT) reveals direct decomposition and radical isomerization as key pathways, with hydroperoxide accumulation posing industrial risks.
Area of Science:
- Computational Chemistry
- Chemical Kinetics
- Organic Chemistry
Background:
- Organic compounds like ethers can form hazardous peroxides via autoxidation.
- Existing literature on ether oxidation mechanisms is often outdated and lacks detail.
Purpose of the Study:
- To investigate the autoxidation mechanism of diethyl ether (DEE) using Density Functional Theory (DFT).
- To identify potential hazardous intermediates, such as peroxides, in the DEE autoxidation process.
Main Methods:
- Extensive Density Functional Theory (DFT) calculations were employed.
- Analysis of reaction paths and kinetic evaluation of competing channels.
Main Results:
- Two primary reaction pathways were identified: direct decomposition (β-scission) of the DEE radical and isomerization of the peroxy radical (DEEOO˙).
- Radical isomerization appears to play a significant role in the overall DEE oxidation.
- Hydroperoxide formation and accumulation during chain propagation are linked to industrial hazards.
Conclusions:
- The study elucidates a complex oxidation mechanism for diethyl ether.
- Understanding these pathways, particularly radical isomerization and hydroperoxide accumulation, is crucial for mitigating risks associated with DEE usage.
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