A new mechanism for initiation of free-radical chain reactions during high-temperature, homogeneous oxidation of unsaturated hydrocarbons: Ethylene, propyne, and allene
✍ Scribed by Hai Wang
- Publisher
- John Wiley and Sons
- Year
- 2001
- Tongue
- English
- Weight
- 165 KB
- Volume
- 33
- Category
- Article
- ISSN
- 0538-8066
- DOI
- 10.1002/kin.1066
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✦ Synopsis
Abstract
The initiation of free radical chain reactions by singlet carbene biradicals is proposed for homogeneous oxidation of typical unsaturated hydrocarbons, including ethylene, allene, and propyne. The mechanism features the production of singlet vinylidene and methylvinylidene by 1,1‐H~2~ elimination and 1,2‐H shift, respectively, from ethylene and propyne. The singlet biradicals then react with molecular oxygen to initiate a free‐radical chain process. The analysis used quantum chemistry calculations and detailed modeling of ignition delay times. In all cases tested the carbene pathway was found to dominate the initial radical‐pool production. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 698–706, 2001