Although standard enthalpies of formation provide information about the net stability of molecules and their transformations, they do not always indicate stability of individual bonds. This analysis normally involves parameters, loosely called “bond energies,” that reflect the amount of energy required to cleave chemical bonds. Bond energies are essential for understanding the nature of chemical bonds. They can be used to assess the results from quantum chemistry calculations (or from other, less sophisticated theoretical models) and thus support or oppose the descriptions of those bonds. Moreover, bond energy values also enable us to estimate the driving forces of chemical reactions by considering the strengths of all the bonds that are cleaved and formed. In fact, there are many reactions for which the standard enthalpies of formation of all reactants and products are not available (and cannot be easily estimated) but whose energetics can be predicted from the appropriate bond energies. In the previous chapters, we attempted to review all the important parameters in molecular energetics, but to avoid unnecessary distraction, we deliberately omitted bond energies from the discussion. The literature is plagued with a variety of concepts that fall into that designation but are not always synonymous. We can find names like bond strengths, bond enthalpies, bond energies, bond dissociation enthalpies, bond dissociation energies, bond disruption enthalpies, bond enthalpy terms, intrinsic bond energies, and symbols like D, D̄, 〈D〉, E, BDE, and so on. The meaning of these concepts it not always obvious and, unfortunately, some are occasionally misused. Now we look into each one of them. Consider a molecule AB, where A and B can be atoms or groups of atoms.
Thermochemistry, Bond Energies and Internal Rotor Potentials of Acetic Acid Hydrazide, Acetamide, N-Methyl Acetamide (NMA) and Radicals