Thermal Decomposition of Methyl Butanoate: Ab Initio Study of a Biodiesel Fuel Surrogate

详细信息    查看全文

• 作者：Lam K. Huynh ; Angela Violi
• 刊名：Journal of Organic Chemistry
• 出版年：2008
• 出版时间：January 4, 2008
• 年：2008
• 卷：73
• 期：1
• 页码：94 - 101
• 全文大小：191K
• 年卷期：v.73,no.1(January 4, 2008)
• ISSN：1520-6904

文摘

In this paper, we report a detailed analysis of the breakdown kinetic mechanism for methyl butanoate(MB) using theoretical approaches. Electronic structures and structure-related molecular properties ofreactants, intermediates, products, and transition states were explored at the BH&HLYP/cc-pVTZ levelof theory. Rate constants for the unimolecular and bimolecular reactions in the temperature range of300-2500 K were calculated using Rice-Ramsperger-Kassel-Marcus and transition state theories,respectively. Thirteen pathways were identified leading to the formation of small compounds such asCH₃, C₂H₃, CO, CO₂, and H₂CO. For the initial formation of MB radicals, H, CH₃, and OH were consideredas reactive radicals participating in hydrogen abstraction reactions. Kinetic simulation results for a hightemperature pyrolysis environment show that MB radicals are mainly produced through hydrogenabstraction reactions by H atoms. In addition, the C(O)OCH₃ = CO + CH₃O reaction is found to be themain source of CO formation. The newly computed kinetic sub-model for MB breakdown is recommendedas a core component to study the combustion of oxygenated species.