Abstract
The determination of ion enthalpies of formation from mass spectrometry measurements is discussed, as well as the availability of enthalpy of formation data for neutral molecules. Molecular and free radical enthalpies derived from the measurement of ionization and appearance energies are described. The empirical determination of ionization energies for homologous series is also outlined. The physicochemical difficulties associated with the measurement of enthalpies of formation of fragment ions are described. Electron and proton affinities, ion charge densities and ion enthalpies are discussed, particularly with respect to homologous series. The importance of the location of the charge site in an ion is emphasized.
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