IB ChemistryStructure 22.22.2.12
2.2.12HL

Benzene

Evidence against the Kekulé model – how delocalised π electrons create extraordinary stability.

🟣 This is Higher Level (HL) content.

Kekulé Model vs Reality

Kekulé proposed benzene as a cyclohexatriene with alternating C–C and C=C bonds. However, three lines of evidence utterly refute this model:

Evidence Type What Kekulé Predicts What We Observe
Physical (X-ray) Alternating bond lengths (154 pm / 134 pm) All 6 C–C bonds identical at 140 pm – intermediate between single and double
Thermodynamic ΔH hydrogenation ≈ 3× cyclohexene ΔH hydrogenation is significantly less exothermic – benzene is more stable than predicted (resonance energy)
Chemical Should readily undergo addition reactions (like alkenes) Overwhelmingly favours substitution – preserves the stable aromatic ring

🔑 The Delocalised Model

Each carbon is sp² hybridised. The unhybridised p-orbital on each carbon overlaps laterally with its neighbours, creating a continuous ring of delocalised π electrons above and below the plane. This is represented as a circle inside the hexagon.

The delocalisation lowers the potential energy of the molecule, giving benzene its remarkable thermodynamic stability and its resistance to addition reactions.

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