Computational Studies on the Thermodynamic and Kinetic Parameters of Oxidation of 2-Methoxyethanol Biofuel via H-Atom Abstraction by Methyl Radical

Abstract In this work, a theoretical investigation of thermochemistry and kinetics of the oxidation of bifunctional 2-Methoxyethanol (2ME) biofuel using methyl radical was introduced. Potential-energy surface for various channels for the oxidation of 2ME was studied at density function theory (M06-2X) andab initioCBS-QB3 levels of theory. H-atom abstraction reactions, which are essential processes occurring in the initial stages of the combustion or oxidation of organic compounds, from different sites of 2ME were examined. A similar study was conducted for the isoelectronicn-butanol to highlight the consequences of replacing the ϒ CH2group by an oxygen atom on the thermodynamic and kinetic parameters of the oxidation processes. Rate coefficients were calculated from the transition state theory. Our calculations show that energy barriers forn-butanol oxidation increase in the order of α ‹ O ‹ ϒ ‹ β ‹ ξ, which are consistent with previous data. However, for 2ME the energy barriers increase in the order α ‹ β ‹ ξ ‹ O. At elevated temperatures, a slightly high total abstraction rate is observed for the bifunctional 2ME (4 abstraction positions) overn-butanol (5 abstraction positions).