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Free-Radical Substitution in Alkanes

Ultraviolet light splits a halogen molecule into radicals, and those radicals attack an alkane in a chain that keeps itself going. The mechanism is why the product is always a mixture.

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What a learner can do afterwards

  • Writes initiation, propagation and termination steps with the radical dots in the right places
  • Explains how one photon can lead to many product molecules
  • Explains why further substitution, and so a mixture, cannot be avoided
  • Connects the same radical chemistry to chlorine radicals breaking down ozone

1 · Read

Alkanes are usually unreactive, but a burst of ultraviolet light changes that. The light splits a halogen molecule into two radicals, and each radical carries an unpaired electron looking for a partner. That split is called initiation, and it takes only one flash to begin.

Try it together

For methane with chlorine, the two propagation steps run as follows. A chlorine radical grabs a hydrogen from methane, giving hydrogen chloride plus a methyl radical. The methyl radical then attacks a chlorine molecule, giving chloromethane plus a fresh chlorine radical. Write every radical dot in the right place, because the dots show where the unpaired electron sits.

Each propagation turn regenerates a chlorine radical, so the chain repeats itself many times from a single photon. One flash can therefore lead to hundreds of product molecules before anything stops. The chain stops in termination, when two radicals meet and pair up: two methyl radicals join to ethane, or two chlorine radicals reform chlorine.

Good to know

You never get one clean product from this reaction. Chloromethane can meet another radical and substitute again, so dichloromethane, trichloromethane and tetrachloromethane build up alongside unreacted methane. The same radical chain chemistry matters in the sky: chlorine radicals from older refrigerants attack ozone the same way, with each radical destroying many ozone molecules in a chain.

Light splits the halogen, the chain feeds itself, and the mixture is unavoidable.

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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Free-Radical Substitution in Alkanes · Science, ages 16 to 17 · LightMySky