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9701 · 23.1

Lattice energy and Born-Haber cycles

A Born-Haber cycle is a clever energy diagram that breaks down the formation of an ionic solid into a series of simpler, measurable steps. By applying Hess's Law, we can calculate the lattice energy, which is too difficult to measure directly.

Need to know

What you need to know

  • **Standard Lattice Energy (ΔH°_latt)**: Formation of 1 mole of solid ionic lattice from its gaseous ions. E.g., Na⁺(g) + Cl⁻(g) → NaCl(s). This is always **exothermic**.
  • **Standard Enthalpy of Formation (ΔH°_f)**: Formation of 1 mole of a compound from its elements in their standard states. E.g., Na(s) + ½Cl₂(g) → NaCl(s). Can be exothermic or endothermic.
  • **Standard Enthalpy of Atomisation (ΔH°_at)**: Formation of 1 mole of gaseous atoms from an element in its standard state. E.g., Na(s) → Na(g). This is always **endothermic**.
  • **First Ionisation Energy (IE₁)**: Removal of 1 mole of electrons from 1 mole of gaseous atoms. E.g., Na(g) → Na⁺(g) + e⁻. This is always **endothermic**.
  • **First Electron Affinity (EA₁)**: Addition of 1 mole of electrons to 1 mole of gaseous atoms. E.g., Cl(g) + e⁻ → Cl⁻(g). This is usually **exothermic** for non-metals.

Explanation

Building Ionic Crystals, Step by Step

  1. Lattice energy (ΔH°_latt) is the exothermic enthalpy change when one mole of a solid ionic lattice is formed from its gaseous ions. It's more exothermic for smaller ions with higher charges.
  2. A Born-Haber cycle applies Hess's law, stating the total enthalpy change is independent of the route taken. It equates the standard enthalpy of formation (ΔH°_f) with the sum of all steps in an alternative pathway.
  3. The magnitude of lattice energy is determined by the strength of electrostatic attraction. It becomes more exothermic (stronger) as ionic charges increase and ionic radii decrease.
  4. Comparing the experimental ΔH°_latt (from a Born-Haber cycle) with a theoretical value (from a pure ionic model) reveals covalent character. A large discrepancy suggests significant orbital overlap, often due to a highly polarising cation and a polarisable anion.