Density functional theory for the thermodynamic gas-phase investigation of butanol biofuel and its isomers mixed with gasoline and ethanol

Herein, we present the results of our study on the thermodynamic properties of the isomers of butanol ( n -butanol, 2-butanol, i-butanol, and t -butanol) to evaluate their thermodynamic potential as a complementary biofuel and/or substitute for ethanol and gasoline. The Gaussian09W software was used to perform molecular geometry optimization calculations using density functional theory with the B3lyp hybrid function using the base set 6–311++g(d,p) and the compound methods G3, G4, and CBS-QB3. Calculations of the fundamental frequency of the molecules were performed to obtain the molecular vibration modes for the respective frequencies. These calculations provided thermodynamic parameters such as the entropy, enthalpy, and specific molar heat at constant pressure, all as a function of the temperature. The parameter values obtained by each method were compared to the experimental values available in the literature. The results showed good accuracy, especially those obtained at the B3lyp/6–311++g(d,p) level for n -butanol. The error between the theoretical and experimental values for the combustion enthalpy of n -butanol was less than 4% at 298.15 K; due to the good prediction of its thermodynamic properties, we used n -butanol as a model for the prediction of other thermodynamic properties. We started a molecular docking study of four ligands, namely, n-butanol, ethanol, propanol, heptane, isooctane, and methanol interacting with butanol isomers. The highest values of affinity energy found were for N-butanol. The possible formation of hydrogen bonds, associations by means of London forces, hydrogen, and alkyl interactions were analyzed. n -Butanol was added to ethanol–gasoline mixtures in the temperature range of 298.15 to 600 K and the results suggest that n -butanol has a higher calorific value than gasoline–ethanol mixtures in G30E, G40E, G50E, G60E, G70E, G80E, G90E, and E100 blends. As such, n -butanol releases greater amounts of heat during combustion and is thus a viable alternative to biofuels.