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NCERT Exemplar · Q26

Q.Use the following data to calculate ΔlatticeH° for NaBr.
ΔsubH° for sodium metal = 108.4 kJ mol^-1
Ionization enthalpy of sodium = 496 kJ mol^-1
Electron gain enthalpy of bromine = -325 kJ mol^-1
Bond dissociation enthalpy of bromine = 192 kJ mol^-1
ΔfH° for NaBr(s) = -360.1 kJ mol^-1

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Applying Hess's law around the Born–Haber cycle for NaBr gives ΔlatticeH∘=+735.5 kJ mol−1\Delta_{\text{lattice}}H^\circ = +735.5\ \text{kJ mol}^{-1} (for the dissociation NaBr(s) → Na⁺(g) + Br⁻(g), the convention used in this chapter).

The Born–Haber cycle

Because enthalpy is a state function, the direct formation of NaBr(s) from its elements must have the same enthalpy change as the stepwise route through gaseous atoms and ions. Equating the two routes lets us solve for the lattice enthalpy, which cannot be measured directly.

Na(s)+12Br2(g)⟶NaBr(s),ΔfH∘=−360.1 kJ mol−1\text{Na(s)} + \tfrac{1}{2}\text{Br}_2(g) \longrightarrow \text{NaBr(s)}, \qquad \Delta_f H^\circ = -360.1\ \text{kJ mol}^{-1}

The individual steps

StepProcessΔH (kJ mol−1)\Delta H\ (\text{kJ mol}^{-1})
Sublimation of NaNa(s)→Na(g)\text{Na(s)} \to \text{Na(g)}+108.4+108.4
Dissociation of 12Br2\tfrac{1}{2}\text{Br}_212Br2(g)→Br(g)\tfrac{1}{2}\text{Br}_2(g) \to \text{Br(g)}12×192=+96.0\tfrac{1}{2}\times 192 = +96.0
Ionisation of NaNa(g)→Na+(g)+e−\text{Na(g)} \to \text{Na}^+(g) + e^-+496+496
Electron gain by BrBr(g)+e−→Br−(g)\text{Br(g)} + e^- \to \text{Br}^-(g)−325-325
Lattice formationNa+(g)+Br−(g)→NaBr(s)\text{Na}^+(g) + \text{Br}^-(g) \to \text{NaBr(s)}−ΔlatticeH∘-\Delta_{\text{lattice}}H^\circ

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