The termination step of the free-radical chlorination of methane is the most stable one among all three steps.
The free-radical substitution reaction between chlorine and methane features three major steps:
Initiation, during which chlorine molecules undergo homolytic fission to produce chlorine free radicals. Ultraviolet radiations are typically applied to supply the energy required for breaking the chlorine-chlorine single bonds. The initiation step is thus <em>endothermic</em>.
Propagation, a process in which chlorine free radicals react with methane molecules and remove a hydrogen atom from the alkane to produce hydrogen chloride and an alkyl radical e.g., . The carbon-containing free radical would react with chlorine molecules to produce chloromethane and yet another chlorine free radical. This process can well repeat itself to chlorinate a significant number of methane molecules.
Termination. Free radicals combine to produce molecules. For example, two chlorine free radicals would combine to produce a chlorine molecule, whereas two alkyl free radicals would combine to produce an alkane with two-carbon atoms in its backbone.
Chemical processes that increase the stability of a substance reduces its chemical potential energy. Energy conserves, thus such processes would also release energy equal to the potential energy lost in quantity. Free radicals are unstable and- as seen in the propagation step- compete readily with neutral molecules for their electrons. The propagation step keeps the number of free radicals constant and is therefore more exothermic than the initiation step. The termination step reduces the number of free radicals, increase the stability of the system by the greatest extent, and is therefore the most exothermic step among the three.