Screening Stability, Thermochemistry, and Chemical Kinetics of 3-Hydroxybutanoic Acid as a Bifunctional Biodiesel Additive.

Abstract

The thermo-kinetic aspects of 3-hydroxybutyric acid (3-HBA) pyrolysis in the gas phase were investigated using density functional theory (DFT), specifically the M06-2X theoretical level in conjunction with the cc-pVTZ basis set. The obtained data were compared with benchmark CBS-QB3 results. The degradation mechanism was divided into 16 pathways, comprising 6 complex fissions and 10 barrierless reactions. Energy profiles were calculated and supplemented with computations of rate coefficients and branching ratios over the temperature range of 600-1700 K at a pressure of 1 bar using transition state theory (TST) and Rice-Ramsperger-Kassel-Marcus (RRKM) methods. Thermodynamics results indicated the presence of six stable conformers within a 4 kcal mol-1 energy range. The estimated chemical kinetics results suggested that TST and RRKM approaches are comparable, providing confidence in our calculations. The branching ratio analysis reveals that the dehydration reaction pathway leading to the formation of H2O and CH3CH═CHCO2H dominates entirely at T ≤ 650 K. At these temperatures, there is a minor contribution from the simple homolytic bond fission reaction, yielding related radicals [CH3•CHOH + •CH2CO2H]. However, at T ≥ 700 K, this reaction becomes the primary decomposition route. At T = 1700 K, there is a minor involvement of a reaction pathway resulting in the formation of CH3CH(OH)•CH2 + •CHO(OH) with an approximate contribution of 16%, and a reaction leading to [•CH3 + •CH2OHCH2CO2H] with around 9%.