Ab initio kinetics of OH-initiated reactions of 2-furfuryl alcohol. (15th April 2023)

• Record Type: Journal Article
• Authors: Xing, Lili; Cui, Jintao; Lian, Liuchao; Wang, Jinglan; Wang, Huanhuan; He, Yunrui; Wang, Shaowei; Wang, Xuetao; Xu, Liyou; Cheng, Zhanjun
• Is Part Of: Fuel. Volume 338(2023)
• Publication Date: 2023-04-15
• Subjects: 2-Furfuryl alcohol -- H-abstraction and OH-addition -- Quantum chemical calculations -- Thermodynamics -- Reaction kinetics; Fuel -- Periodicals; Coal -- Periodicals; Coal; Fuel; Periodicals; 662.6
• DOI: 10.1016/j.fuel.2022.127325
• Languages: English
• ISSNs: 0016-2361

Abstract

Highlights: High precision schematic energetics calculation. Site-specific reactivity. Revealing the competing relationship between OH-addition and H-abstraction pathways. Providing valuable kinetic data in a wide temperature and pressure condition. Abstract: Oxidation of furan-based biofuels in the atmosphere and combustion are mainly initiated by reactions with small radicals (e.g. OH radical), the kinetics of which are crucial to obtain a comprehensive understanding of combustion processes, especially in engine operation. However, the structure- and site-dependent chemistry for OH-initiated reactions of furans with oxygenated substituents is unknown. In the present study, 2-furfuryl alcohol (2FFOH) was selected as a model fuel, and a full schematic energy diagram for 2FFOH with OH was calculated by a high-level quantum chemical method (CCSD(T)/CBS//M06-2X/def2-TZVP). The temperature- and pressure-dependent behavior of the rate coefficients k ( T, P ) for 2FFOH with OH was calculated at 298–2500 K and 0.01–10 atm by using the Rice–Ramsperger–Kassel–Marcus/Master equation method. Our calculations reveal that the rate coefficients of H-abstraction from the side chain are faster than those from the ring at T ≤ 2300 K. The observed temperature dependence behaviors of the total rate coefficients are consistent with prior experimental studies of other furans (e.g., furan, 25DMF and 2MF) with OH. The total rate coefficients of 2FFOH with OH exhibit a slightly positive pressure dependence only in the temperature range of 500–1000 K. We also found that the OH-addition pathways for 2FFOH with OH system dominate at T ≤ 1300 K. Moreover, the thermodynamic and kinetic data determined in the present work would be valuable for the future development of the fundamental chemical reaction mechanism of furan-based fuels in the atmosphere and combustion.