Relative reactivity of methyl anisole isomers: An experimental and kinetic modelling study

Abstract

Due to the current interest in biomass derived carbon neutral fuels and fuel additives for gasoline engines and to the growing need of understanding the fundamentals of gas phase combustion in the context of wildfires, this study investigates the combustion behavior of key components of biomass pyrolysis oils, namely the three methylanisole isomers (ortho-, meta- and para-methylanisole). Specifically, this study presents the first experimental ignition delay time measurements for such fuels using a shock tube and a rapid compression machine. Ignition experiments were carried out for stoichiometric fuel/air mixtures (φ = 1) at compressed pressure p_c = 10 and 20 bar, covering a temperature range T_c = 880–1220 K. A kinetic model based on previous efforts in the area of oxygenated aromatic hydrocarbon fuels is proposed to reproduce and interpret the experimental findings, specifically focusing on capturing the observed different reactivity of the three isomers. To this aim, thermodynamic properties of primary intermediates and bond dissociation energies were calculated highlighting relevant differences originated from the relative position of the O–CH₃ and –CH₃ substituents. In addition, an isomerization pathway specific to the ortho isomer was theoretically investigated and found to motivate the observed higher reactivity with respect to the meta and para isomers