The results show a generally improved performance of the present model relative to that of literature models which have generally been constructed based on similarity to alkane oxidation reaction kinetics. Chemical path flux analyses of all available methyl decanoate models are analyzed and the results reveal that the fuel oxidation pathways exhibit completely different chemical mechanisms depending on the modeling prescriptions of the kinetic and thermochemical parameters. In particular, there is a wide degree of variability in the fate prescribed to the methyl ester functionality. In addition, experimental analysis of diffusion flame extinctions for methyl butanoate and methyl decanoate reveals that the high temperature reactivity of methyl butanoate is similar to that of methyl decanoate by introducing a concept of transport-weighted enthalpy. Consequently, the present modeling work and experimental analysis suggest that further studies of small methyl ester systems, such as methyl butanoate are required in order to improve the model fidelity of large biodiesel like methyl esters.