The Energetics of Organofluorine Compounds: Aliphatic Fluorocarbons and Hydrofluorocarbons

Abstract In the current chapter, we discuss the thermochemistry of compounds with CF bonds. In the name of brevity, we limit our attention to the understanding of the enthalpies of formation of aliphatic fluorocarbons and hydrofluorocarbons. Discussions of alkanes, alkenes, and alkynes alike compose our study—there is scant mention of any species with a ring, or with unpaired electrons or a charge, or the presence of any other element other than carbon, fluorine, and usually hydrogen. Results from diverse calorimetric measurements and high‐level quantum chemical calculations are inseparably intermingled. How could it be otherwise when there are no classical calorimetric measurements reported for the determination of the enthalpy of formation of methyl fluoride, plausibly, the simplest organofluorine compound, nor any such study of the likewise simple ethyl fluoride? The chapter closes with the chemistry of perfluoro‐2‐butyne and thus unavoidably discusses trimeric derivative of alkynes, substituted benzenes. A plausible sequel to the current study, a possible new chapter entitled “The energetics of organofluorine compounds: Aromatic fluorocarbons and hydrofluorocarbons,” is casually pondered upon.