Theoretical Studies on the Reaction Kinetic of 2-Acetylfuran with Hydroxyl Radicals

Abstract

With the development of synthetic methods, 2acetylfuran (AF2) has become a potential biomass fuel. The potential energy surfaces of AF2 and OH including OH-addition reactions and H-abstraction reactions were constructed by theoretical calculations at the CCSDT/CBS/M06-2x/cc-pVTZ level. The temperature-and pressure-dependent rate constants of the relevant reaction pathways were solved based on transition state theory and Rice−Ramsperger−Kassel−Marcus theory, as well as Eckart tunneling effect correction. The results showed that the H-abstraction reaction on CH 3 on the branched chain and the OH-addition reaction at the C (2) and C (5) sites on the furan ring were the main reaction channels in the reaction system. At low temperatures, the AF2 and OH-addition reactions dominate, and the percentage decreases gradually to zero with increasing temperature, and at high temperatures, the H-abstraction reactions on the branched chains become the most dominant reaction channel. The rate coefficients calculated in the current work improve the combustion mechanism of AF2 and provide theoretical guidance for the practical application of AF2.

Theoretical Study of the Decomposition Reactions of 2-Vinylfuran

“…The energy barrier of TS24 is lower than that of the initial reactants, probably due to the weak van der Waals (vdW) complexes of V2F formed with H through hydrogen bonding. The rate constants of this barrier-free reaction cannot be calculated using the conventional transition state theory; therefore, the rate constants of the process are calculated using the phase space theory . The interaction of the reactants with the weak vdW complexes is estimated by the formula V ( R ) = C 6 / R 6 , where R is the distance between the reactants.…”

“…The rate constants of this barrier-free reaction cannot be calculated using the conventional transition state theory; therefore, the rate constants of the process are calculated using the phase space theory. 34 The interaction of the reactants with the weak vdW complexes is estimated by the formula V ( R ) = C 6 / R 6 , where R is the distance between the reactants. C 6 is estimated by the equation C 6 = α 1 ·α 2 · E 1 · E 2 /( E 1 + E 2 ), where α i and E i ( i = 1,2) are the polarizabilities and ionization energies of the two reactants, respectively.…”

“…With the development of methods to convert biomass into furan-based biofuels, furan-based fuels have received increasing attention, and their combustion reaction kinetics is one of the current hot spots of research in the field of combustion. , Furan-based biofuels, including furan, 2-methylfuran, 3-methylfuran, 2-ethylfuran (EF2), 2,5-dimethylfuran, 2-acetylfuran, furfural, 2-furfuryl alcohol and methyl 2-furoate, have attracted much attention. − …”

“…The calculation results show that the total rate constant of the H-addition reaction channel is 3.3–10 times higher than that of the H-abstraction reaction channel. He et al . constructed the PESs of 2-acetylfuran and OH at the CCSDT/CBS/M06–2x/cc-pVTZ level and solved the temperature and pressure rate constants.…”

“…He et al. 25 constructed the PESs of 2-acetylfuran and OH at the CCSDT/CBS/M06–2x/cc-pVTZ level and solved the temperature and pressure rate constants. The results showed that the OH-addition reaction dominated at low temperatures, and the proportion gradually decreased to zero with the increase of temperature; at high temperatures, the H-abstraction reaction on the branched chain became the most dominant reaction pathway.…”