A bond-dissociation enthalpy is the molar enthalpy change for the specified homolysis at temperature , with reactant and products in specified standard states. Its usual units are . The superscript specifies standard states; it does not fix to room temperature.[ref]
Write for each species' molar thermal enthalpy increment. With an energy per parent molecule,
Here is the Avogadro constant. The thermal increments include translational kinetic energy, molecular rotation, thermally excited molecular vibration and electronic states when populated, and the contribution to enthalpy. They are additional to the zero-point energies already included in . If values of standard enthalpy of formation at the same are available, Hess's law gives the same quantity as .
Units alone do not identify the convention. Multiplying either or by the Avogadro constant gives molar energy, but does not add thermal enthalpy. One electronvolt per dissociation corresponds to . A spectroscopic wavenumber represents energy , using the Planck constant and speed of light ; corresponds to .[ref]
The standard enthalpy of formation is the enthalpy change on forming exactly one mole of the specified compound in its stated standard state from its constituent chemical elements in their reference states at the same specified temperature. The reference states are normally the stable elemental forms at the standard pressure. A standard state does not itself mean 298 K; temperature must be stated separately.
Use the balanced aqueous-acid reaction
A Hess cycle first atomizes the metal, then ionizes its gas-phase atoms, then hydrates the triply charged gas ions:
Close the reference leg by combining the three electrons with to make . Calling that element-independent contribution gives
A single-ion standard enthalpy of formation uses the conventional hydrogen-ion reference; it must not be treated as a balanced creation of net charge from neutral metal without an electron/reference term. The constant hydrogen leg does not affect comparisons along the lanthanide series.
Figure 1.
Original Hess cycle separating atomization, three ionizations, hydration and the common aqueous hydrogen reference leg
. Details.
The standard enthalpy of formation is the enthalpy change for forming one mole of a specified chemical substance from its chemical elements in their reference states at the stated temperature. For sodium chloride at , those reactant states are solid sodium and diatomic gaseous chlorine. Standard state specifies conditions; it does not by itself select a temperature.