Prediction of the Thermodynamic Properties of Key Products and Intermediates from Biomass. II

Abstract

The thermodynamic properties of a wide range of chemical compounds relevant to the conversion of biomass-derived oxygenated feedstocks into fuels or chemical feedstocks were predicted using the correlated G3MP2 computational chemistry approach. The energetics of a range of reactions starting from 2,5-furandicarboxylic acid, 3-hydroxypropionic acid, aspartic acid, glucaric acid, glutamic acid, itaconic acid, malic acid, lactic acid, 3-hydroxybutyrolactone, furfural, and xylitol/arabinitol were calculated. The calculated G3MP2 gas phase heats of formation are mostly within ±2 kcal/mol of the available experimental values. Heats of formation of the liquid were obtained from calculations of the boiling point combined with the rule of Pictet and Trouton using modified values for Δ<i>S</i>_vap. Reaction energies in the aqueous phase at 298 K were estimated from self-consistent reaction field calculations of the solvation energy using the COSMO parametrization. Most of the reactions are exothermic, and the reaction products are stabilized by aqueous solvation. Endothermic processes include dehydrogenation, deamination, and dehydration reactions