Molecular dynamics investigations on the thermophysical property of fatty acid ethyl esters

Abstract

To develop innovative fuel additives or substitutes and design spray-assisted internal combustion engines, it is important to have a comprehensive understanding of the thermophysical characteristics of biodiesels. Rooted in statistical mechanics, the molecular simulation method can predict the thermophysical properties over a wide range of temperatures and pressures, which overcomes the challenges of experimental measurements and facility restrictions. This work focused on the evaluation of three classical force fields (FFs) in terms of their ability to predict the thermophysical properties of ethyl-caprylate (EtC8:0), ethyl-caprate (EtC10:0), ethyl-laurate (EtC12:0), ethyl-myristate (EtC14:0), ethyl-palmitate (EtC16:0), and ethyl-stearate (EtC18:0) within a temperature range of (303.15 to 403.15) K and pressures up to 100 MPa. The Optimized Potential for Liquid Simulations–All atom and its modification (OPLS and L–OPLS) and Transferable Potential for Phase Equilibria–United Atom (TraPPE–UA) FFs were evaluated. These findings demonstrated that the L–OPLS FF, when applied in the isobaric-isothermal (NPT) and canonical ensembles (NVT), effectively replicated the experimental data and semi-empirical models for density, viscosity, diffusivity coefficient, and interfacial behavior at elevated temperatures and pressures. Moreover, the utilization of the radial distribution function, radius of gyration, and end-to-end distance distribution in the analysis of liquid conformations allowed for a comprehensive investigation of the microscopic structure. This work provides the theoretical methodologies and empirical evidence for the advancement of biodiesel and other petrochemicals.