Theoretical study on thermochemical parameters and pKa values for fluorinated isomers of toluene

Despite the prominent importance of fluorinated isomers of toluene in environmental and industrial applications, robust data pertinent to their thermochemistry is rather scarce. Thermochemical properties, in terms of standard entropies, heat capacities, standard enthalpies of formation, Gibbs free energies of formation and solvation energies are calculated herein for all fluorinated isomers of toluene. Estimated barriers for the internal rotation of the methyl group are in accord with experimental measurements available for a few congeners. Very exoergic values for Δf View the MathML source indicates a thermodynamic tendency toward the formation of highly fluorinated congeners. Solvation of all isomers in water at ambient conditions incurs a trivial exoergicity. Profiles for internal rotations obtained from partial optimisation reasonably match corresponding profiles obtained via automatic recognition for barriers of rotations based on Pitzer–Gwinn tables. Calculated pKa values reveal a very weak acidic character; especially for lower fluorinated congeners