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Free Radical Substitution

The halogenation of alkanes takes place by a mechanism called free radical substitution and can be considered to take place in three steps:
  • initiation
  • propagation
  • termination
Initiation involves the homolytic fission of a Cl-Cl bond by ultraviolet radiation (photodissociation). The Cl radicals formed are very reactive and remove a hydrogen when they collide with an alkane molecule. This gives an alkyl radical which breaks a Cl-Cl bond releasing a Cl radical i.e. a chain reaction. Termination occurs when two radicals react together to form a molecule, removing radicals from the chain.

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