Learn · Organic Chemistry

Initiation, Propagation, and Termination

The three phases of a free-radical halogenation chain reaction — and why one flash of light makes many product molecules.

Quick answer Free-radical halogenation runs as a chain in three phases: initiation splits X₂ into radicals, two propagation steps repeat to consume reactants and regenerate a carrier, and termination combines any two radicals to stop the chain. Because each propagation cycle makes product while handing off a new radical, a single initiation event can yield thousands of product molecules.

1. Initiation splits X₂ into two radicals.

Light or heat breaks the halogen bond homolytically, making two chain-carrying radicals; this step is slow and happens rarely.

Cl2 absorbs UV light (hν).
Two chlorine radicals form — the chain carriers (initiation).

2. Propagation step 1 abstracts a hydrogen.

A chlorine radical pulls an H off the alkane, producing HCl and a carbon radical that carries the chain forward.

Ethyl radical, R•
H–Cl by-product

3. Propagation step 2 regenerates the carrier.

The carbon radical grabs a chlorine from Cl₂, forming the R–Cl product and releasing a fresh chlorine radical to repeat the cycle.

Chloroethane product
New Cl• continues the chain

4. Termination combines radicals and ends the chain.

When any two radicals meet they pair up — removing carriers so the chain stops, sometimes making a side product.

Cl• + Cl•
R• + Cl•
R• + R• (butane)

5. Overall: the two propagation steps add up to the reaction.

Summed, the cycle converts alkane plus Cl₂ into the chloroalkane plus HCl — one initiation feeds many product-making cycles.

Ethane + Cl₂, under light, gives chloroethane + HCl.

Summary

Initiation makes radicals · propagation step 1 abstracts H · propagation step 2 regenerates the carrier · termination pairs radicals to stop the chain · one flash of light yields many products.

Quiz yourself

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Initiation — light or heat homolytically splits X₂ into two X• radicals. It is slow and accounts for very few events.

Each propagation cycle consumes reactants and regenerates a radical carrier, so the same chain repeats thousands of times before it terminates.

(1) Cl• + CH₃CH₃ → •CH₂CH₃ + HCl. (2) •CH₂CH₃ + Cl₂ → CH₃CH₂Cl + Cl•.

Propagation regenerates a carrier and keeps the chain going; termination combines two radicals, destroying carriers and ending the chain.

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