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Propagation Step 1:
One of the chlorine atoms abstracts a hydrogen atom from a
methane molecule:
Propagation Step 2:
The methyl radical abstracts a chlorine atom from another Cl 2
molecule yielding chloromethane and a new chlorine atom.
This step is exothermic and supplies the driving force for the
overall reaction.
Chain Termination
When two radicals find each other and combine to form a
covalent bond they are no longer available to participate in
propagating the reaction.
3-5
The enthalpies for the first and second propagation steps for the
four halogens are:
In the first propagation step, the very strong H-F bond results in a
strong exothermic reaction for fluorine. The remaining values for
Cl, Br, and I reflect the decreasing bond strengths of the HCl, HBr,
and HI molecules.
Iodine does not react with methane to form methyl iodide and
hydrogen iodide.