A theoretical study on reaction mechanism of thermal decomposition of furyl radicals

Abstract

This study presents the reaction mechanism of furyl decomposition, which plays an important role in the production of the second-generation biofuels from lignocellulosic feedstock. The reaction mechanism was explored using the highly accurate ab initio composite method CBS-QB3. It was found that (i) the conversion of 2-furyl  3-furyl was unfavorable due to its high energy barrier (63.9 kcal∙mol-1 at 0 K); (ii) 2-furyl could be decomposed in to three product channels in the increasing thermodynamically favorable order as C2 H2 & •HC=C=O (P1) > CO & c-C3 H3 • (P2) > CO & HC≡C‒CH2 • (P3); and (iii) 3-furyl only decomposed to P3 products. The calculated thermodynamic properties (such as heat of formation, entropy, heat capacity) for the temperature range of 298-2,000 K were in good agreement with the limited and scattered literature data; therefore, the calculated data could be used for further study in modelling and simulation of furyl-related system as well as the lignocellulosic bioconversion technology