Kinetic Modeling of Methyl Butanoate in Shock Tube

• DOI: 10.1021/jp804358r
• Publication Date: 2008-12-01T19:55:42Z
• Authors: Lam K. Huynh; Kuang C. Lin; Angela Violi
• Keywords: Butyrates; Kinetics; Hot Temperature; Isomerism; Models, Chemical; 13. Climate action; 0211 other engineering and technologies; 0202 electrical engineering, electronic engineering, information engineering; Quantum Theory; Computer Simulation; 02 engineering and technology; 7. Clean energy; Algorithms

An increased necessity for energy independence and heightened concern about the effects of rising carbon dioxide levels have intensified search renewable fuels that could reduce our current consumption petrol diesel. One such fuel is biodiesel, which consists methyl esters fatty acids. Methyl butanoate (MB) contains essential chemical structure long-chain acids a shorter, but similar, alkyl chain. This paper reports on detailed kinetic mechanism MB assembled using theoretical approaches. Thirteen pathways include decomposition, isomerization, propagation steps were computed ab initio calculations [J. Org. Chem. 2008, 73, 94]. Rate constants from first principles important reactions in CO2 formation, namely CH3OCO═CH3 + (R1) CH3OCO═CH3O CO (R2) reactions, are at high theory implemented mechanism. Using G3B3 potential surface together with B3LYP/6-31G(d) gradient, Hessian geometries, rate R1 R2 calculated Rice−Ramsperger−Kassel−Marcus corrections treatments tunneling, hindered rotation, variational effects. The reaction differ data present literature by most 20%, while those factor 4 lower than available values. new model derived simulations combined presented Fisher et al. [Proc. Combust. Inst. 2000, 28, 1579] addition newly found six-centered unimolecular elimination yields ethylene acetate, = C2H4 CH3COOCH3. latter pathway requires inclusion CH3COOCH3 decomposition suggested Westbrook accepted]. composed used to study formation during pyrolysis as well investigate autoignition shock tube reactor different temperatures pressures. results agree very experimental literature. Sensitivity flux (rate-of-production) analyses carried out mechanism, mechanisms, assess importance various each regime. With C2H species, one species ignition delay time, also conditions. In giving better insight pyrolysis/oxidation MB, suggest ways improve mechanism's capability predict times oxidation