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Chemistry · Ch 5 — Chemical Bonding

Ionic solids and Lattice Enthalpy

5.2.2

Ionic solids and Lattice Enthalpy

Ionic solids are crystalline arrays of cations and anions held together purely by coulombic (electrostatic) attraction, with every cation surrounded by a fixed number of anions and vice versa in a regular, repeating three-dimensional lattice. Forming an ionic solid from separate gaseous atoms happens in stages: first ionisation, M(g)→M⊕(g)+e−M(g)\rightarrow M^{\oplus}(g)+e^- (always an ENDOTHERMIC step, since removing an electron from a neutral atom always costs energy), then electron gain, X(g)+e−→X−(g)X(g)+e^-\rightarrow X^-(g) (which can be exothermic or endothermic depending on the element), and finally condensation of the gaseous ion pair into the ordered solid lattice — a strongly exothermic step. For NaCl, ionising Na costs 495.8495.8 kJ mol⁻¹ and chlorine's electron gain releases 348.7348.7 kJ mol⁻¹, so forming gaseous Na⊕Cl⊖ ion pairs from separate gaseous atoms already releases a net 147.7147.7 kJ mol⁻¹ — but condensing those gaseous ion pairs further into the solid NaCl lattice releases a much larger 788788 kJ mol⁻¹. This shows that an ionic compound's real stability comes overwhelmingly from the energy released on forming its crystal lattice, not merely from each ion completing its octet. Lattice Enthalpy is accordingly DEFINED as the energy required to completely separate one mole of a solid ionic compound into its gaseous ions — e.g. NaCl's lattice enthalpy of 788788 kJ mol⁻¹ is the energy needed to pull one mole of solid NaCl apart into gaseous Na⊕(g) and Cl⊖(g) ions at infinite separation. Comparing compounds (Table 5.1), lattice entha …

Table 5.1Lattice enthalpy values of some ionic compounds

Table 5.1 — lattice enthalpy in kJ mol⁻¹: LiCl 853; NaCl 788; BeF2 3020; CaCl2 2258; AlCl3 5492.

From this data the text draws two trends for the SAME anion with different cations: (1) a higher cationic charge gives a larger lattice enthalpy, e.g. AlCl3 (3+ cation) > CaCl2 (2+ cation) > NaCl (1+ cation); (2) a smaller cation size gives a larger lattice enthalpy, …

Figure 5.2.2NaCl crystal lattice

What this figure shows. A schematic of the NaCl rock-salt crystal structure showing alternating Na⊕ and Cl⊖ ions in a regular, repeating three-dimensional array. In the real NaCl structure (standard chemistry fact used here since the book's own sketch is only indicative) each Na⊕ ion is octahedrally surrounded by 6 nearest-neighbour Cl⊖ ions and each Cl⊖ ion is likewise surrounded by 6 Na⊕ ions, giving a 6:6 coordination lattice; the ions are held in place purely by the cumulative coulombic attraction of every ion to every oppositely charged neighbour, which is what Lattice Enthalpy (defined in the body text as the energy needed to completely separate one mole of the solid ionic compound into its gaseous ions, e.g. 788 kJ to …