Kinetic Parameters at High-Pressure-Limit for Unimolecular Alkene Elimination Reaction Class of Fatty Acid Alkyl Esters (FAAEs)

The unimolecular alkene elimination reaction class of fatty acid alkyl esters (FAAEs) is a crucial component in the low-temperature combustion mechanism for biodiesel fuels. However, thermo-kinetic parameters for this reaction class are scarce, particularly for the large-size molecules over four carbon atoms and intricate branched-chain configurations. Thermo-kinetic parameters are essential for constructing a reaction mechanism, which can be used to clarify the chemical nature of combustion for biodiesel fuels. In this paper, the B3LYP method, in conjunction with the 6-311G(d,p) basis set, is used to carry out geometry optimization of the species participating in the reactions. Frequency calculations are further executed at the same level of theory. Additionally, coupled with the 6-311G(d,p) basis set, the B3LYP method acts as the low-level ab initio approach, while the Gaussian-4 (G4) composite method serves as the high-level ab initio approach within the isodesmic reaction correction scheme. The CCSD(T) approach is employed to verify the consistency of the electronic energy ascertained through the G4 method. The isodesmic reaction method (IRM) is used to obtain the energy barriers and reaction enthalpies for unimolecular alkene elimination reaction class of FAAEs. Based on the reaction class transition state theory (RC-TST), high-pressure-limit rate coefficients were computed, with asymmetric Eckart tunneling corrections applied across 500~2000 K temperature range. Rate rules at the high-pressure-limit are obtained through the averaging of rate coefficients from a representative collection of reactions, which incorporate substituent groups and carbon chains with different sizes and lengths. Ultimately, the energy barriers, reaction enthalpies, and rate rules at the high-pressure-limit and kinetic parameters expressed as (A, n, E) are supplied for developing the low-temperature combustion mechanism of biodiesel fuels.