On the competition between hydrogen abstraction versus C-O bond fission in initiating dimethyl ether combustion
- Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry
There has been a growing interest in the potential use of dimethyl ether (DME) as a diesel fuel in compression ignition engines. There are two initiation steps involved in the combustion of DME, one involving C-O bond fission and the other involving hydrogen abstraction by molecular oxygen. The kinetics and thermodynamics of C-O bond fission were explored computationally in a previous paper. The present paper addresses the competing process--hydrogen abstraction by molecular oxygen. Ab initio molecular orbital calculations are used to study the structures and energetics of the reactants, products, and the transition state for the CH{sub 3}OCH{sub 3} + O{sub 2} reaction. The calculations predict a barrier for hydrogen abstraction from CH{sub 3}OCH{sub 3} by O{sub 2} of 47.4 kcal/mol. This is lower than the barrier height for C-O bond fission previously calculated to be 81.1 kcal/mol. The results support values used in current models for the combustion of DME. Moreover, an examination of rates for C-O bond fission versus hydrogen abstraction by O{sub 2} suggests that the bimolecular process is the dominant pathway.
- OSTI ID:
- 355729
- Journal Information:
- Combustion and Flame, Journal Name: Combustion and Flame Journal Issue: 1-2 Vol. 118; ISSN CBFMAO; ISSN 0010-2180
- Country of Publication:
- United States
- Language:
- English
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