Ab initio and kinetics study of the thermal unimolecular decomposition of 2-furfuryl alcohol

Abstract To uncover the fundamental chemistry of thermal unimolecular decomposition of 2-furfuryl alcohol, the quantum chemical calculations and reaction kinetics analysis are performed. The temperature and pressure-dependent rate constants of 2-furfuryl alcohol pyrolysis were calculated using Rice–Ramsperger–Kassel–Marcus/Master Equation method. Our calculations reveal that the preliminarily main reaction pathway occurs via 1,2 hydrogen shift to form a carbine intermediate (labelled as INT2) at high pressure limit. The temperature- and pressure- dependent rate constants for these main reaction pathways were discussed in details. The reaction pathway to produce bimolecular products (3-butyn-1-ol plus CO) has a main contribution at high temperatures and at P ≤ 1 atm. Morever, the thermodynamics and kinetics data determined in the present work would be useful for chemical kinetics modelers.