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Benzene: Delocalisation and Electrophilic Substitution

Benzene's six electrons spread around the ring instead of sitting in three double bonds, which makes it much more stable than the alternative structure. That stability is why it substitutes rather than adds.

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What a learner can do afterwards

  • Compares the enthalpy of hydrogenation of benzene with three times that of cyclohexene and says what the gap shows
  • Gives two further pieces of evidence against alternating double bonds, such as equal bond lengths and the failure to decolourise bromine water
  • Draws the mechanism for nitration, including how the electrophile is generated
  • Explains why the ring is restored at the end of the mechanism

1 · Read

Benzene spreads its six pi electrons around the whole ring instead of fixing them in three double bonds. Burning it with hydrogen releases clearly less energy than three cyclohexenes would, so the ring starts from a calmer, more stable place.

Two more clues agree. Every carbon to carbon bond in benzene shares one length, and benzene will not decolourise bromine water the way alkenes do.

Try it together

In nitration, concentrated nitric and sulfuric acids make the NO2+ electrophile, the ring offers its electrons to it, and then a proton drops off so the shared loop closes again as nitrobenzene.

Good to know

Adding would smash the shared ring and its bonus stability, so benzene substitutes instead and keeps the ring intact. Whenever you write the mechanism, end it by restoring the loop.

Shared electrons bring bonus stability, tests deny fixed double bonds, and substitution protects the ring.

2 · Watch

Take it off screen

Print a worksheetA4 with an answer key page for grown-ups. No screen, no internet.

Where it sits

Then practise

8 questions wait behind this lesson, each with its answer explained. Every answer feeds the sky: stars light as they are learned, and dim when it is time to come back.

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Benzene: Delocalisation and Electrophilic Substitution · Science, ages 17 to 18 · LightMySky