Renewable Platform Chemicals: Evaluation of Experimental Data for Alkyl Benzoates with Complementary Measurements, Structure–Property Correlations, and Quantum Chemical Calculations

Alkyl benzoates (or esters of benzoic acid) are important preservatives in the food and beverage industry. The development of new and effective synthesis pathways from renewable sources opens a window of opportunity for their large-scale production. Consequently, new areas of application for alkyl benzoates, e.g., conversion to platform chemicals or hydrogen storage, can be considered. The production and conversion of alkyl benzoates usually involve several steps, so controlling selectivity and yield is a challenge for these new pathways. Success depends on fine-tuning the distribution between thermodynamic and kinetic products. The latter is possible if reliable thermochemical and thermophysical data on the reactants are available. The thermochemical properties of a homological series of alkyl benzoates, including vapor pressures, enthalpies of vaporization, enthalpies of solution, and enthalpies of formation, were the focus of this study. The data sets for each thermodynamic property were evaluated using structure–property correlations and quantum chemical calculations and recommended for thermochemical calculations. The energetics of chemical reactions based on alkyl benzoates relevant to hydrogen storage were calculated and compared to the reaction enthalpies of common liquid organic hydrogen carriers.