Bond Energies

Most heats of formation are negative, reflecting the strong covalent bonds and lower enthalpy that characterizes stable compounds relative to their elements. However, some stable compounds are found to have positive heats of formation, e.g. benzene and condensed ring aromatics, making it unwise to generalize from this data alone. As we have noted, heats of reaction reflect the bond dissociation energies of bonds that are broken and formed in the reaction, but the formalism of setting elemental heats of formation to zero obscures the covalent bond dissociation energies of diatomic elements such as H 2, O2, N2and Cl2. Elements that have solid standard states (e.g. carbon) present an even more complex bond dissociation energy challenge. Fortunately, it is possible to determine the bond dissociation energy of diatomic elements and compounds with precision by nonthermodynamic methods, and together with thermodynamic data such information permits a table of average bond energies to be assembled. These bond energies or bond dissociation enthalpies are always positive, since they represent the endothermic homolysis of a covalent bond. It must be emphasized that for the common covalent bonds found in polyatomic molecules (e.g. C-H and C-C) these are average dissociation enthalpies, in contrast to specific bond dissociation enthalpies determined for individual bonds in designated compounds. Factors such as hybridization, strain and conjugation may raise or lower these numbers substantially. Common sense suggests that molecules held together by strong covalent bonds will be more stable than molecules constructed from weaker bonds. Previously we defined bond dissociation energy as the energy required to break a bond into neutral fragments (radicals or atoms). The sum of all the bond energies of a molecule can therefore be considered its atomization energy, i.e. the energy required to break the molecule completely into its component atoms. If this concept is applied to the reactants and products of a reaction, it should be clear that a common atomization state exists, and that the total bond energies of the reactants compared with the bond energies of the products determines the enthalpy change of the reaction. Thus, if the products have a greater total bond energy than the reactants the reaction will be exothermic, and the opposite is true for an endothermic reaction. The following diagram illustrates this relationship for the combustion of methane. Always remember, a bond energy is energy that must be introduced to break a bond, and is not a component of a molecule's potential energy.

Bond energies may be used for rough calculations of enthalpies of reaction. To do so the total bond energies of the reactant molecules must be subtracted from the total bond energies of the product molecules, and the resulting sign must be changed. This operation is outlined above for the combustion of methane. To compare such a calculation with an experimental standard enthalpy of reaction, correction factors for heats of condensation (or fusion) must be added to achieve standard state conditions. In the above example, gaseous water must be condensed to the liquid state, releasing 10.5 kcal/mol of heat. Once this is done, a reasonably good estimate of the standard enthalpy change is obtained. It may be helpful to note that the potential energy of a given molecular system is inversely proportional to its total bond energies. In this sense the potential energy of the methane + oxygen reactants is greater than that of the carbon dioxide + water products. In this reaction, potential energy is lost by conversion to kinetic (heat) energy.