Kinetics of Enol Formation from Reaction of OH with Propene
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- 作者：Lam K. Huynh† ; ‡ ; ; Hongzhi R. Zhang§ ; ; Shaowen Zhang ; Eric Eddings§ ; ; Adel Sarofim§ ; ; Matthew E. Law
- 刊名：Journal of Physical Chemistry A
- 出版年：2009
- 出版时间：April 2, 2009
- 年：2009
- 卷：113
- 期：13
- 页码：3177-3185
- 全文大小：336K
- 年卷期：v.113,no.13(April 2, 2009)
- ISSN：1520-5215
文摘
Kinetics of enol generation from propene has been predicted in an effort to understand the presence of enols in flames. A potential energy surface for reaction of OH with propene was computed by CCSD(T)/cc-pVDZ//B3LYP/cc-pVTZ calculations. Rate constants of different product channels and branching ratios were then calculated using the Master Equation formulation (J. Phys. Chem. A 2006, 110, 10528). Of the two enol products, ethenol is dominant over propenol, and its pathway is also the dominant pathway for the OH + propene addition reactions to form bimolecular products. In the temperature range considered, hydrogen abstraction dominated propene + OH consumption by a branching ratio of more than 90%. Calculated rate constants of enol formation were included in the Utah Surrogate Mechanism to model the enol profile in a cyclohexane premixed flame. The extended model shows consistency with experimental data and gives 5% contribution of ethenol formation from OH + propene reaction, the rest coming from ethene + OH.