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Prelude on the energetics of compound formation

Let us consider the enthalpy of formation of an ionic compound like NaCl, or in general terms MX  [Pg.199]

The lattice enthalpy, Aiatt//m, is the molar enthalpy change accompanying the formation of a gas of ions from the solid. Since the reaction involves lattice disruption the lattice enthalpy is always large and positive. Aatom//m and Adiss//m are the enthalpies of atomization (or sublimation) of the solid, M(s), and the enthalpy of dissociation (or atomization) of the gaseous element, X2(g). The enthalpy of ionization is termed electron gain enthalpy, Aeg//m, for the anion and ionization enthalpy, Ajon//m, for the cation. [Pg.200]

The enthalpy of formation of the compound MX is now the sum of these five contributions  [Pg.200]

While the enthalpy of formation is the property of interest in chemical thermodynamics of materials, many books focus on the lattice enthalpy when considering trends in stability. The static non-vibrational part of the lattice enthalpy can be deconvoluted into contributions of electrostatic nature, due to electron-electron repulsion, dispersion or van der Waals attraction, polarization and crystal field effects. The lattice enthalpy is in the 0 K approximation given as a sum of the potential energies of the different contributions  [Pg.200]

The next nearest neighbours to the central M+ are 12 M+ at distance V2r. The repulsive cation-cation interaction term is given as [Pg.201]


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