Radical chain reaction 2026-10-13
A radical chain reaction regenerates a radical during propagation. Initiation supplies free radicals; propagation consumes one and produces another; termination removes chain-carrying free radicals. This explains why one initiating event can lead to many product-forming chemical reactions. The chain-growth polymerization article develops the corresponding growth of polymers.
Radical (chemistry) 2026-10-13
A radical has one or more unpaired Electrons. In a simple atomic orbital or molecular orbital occupancy picture, an unpaired Electron occupies a spatial orbital without an opposite-spin partner in that orbital. A dot such as marks this electronic property; it does not mean a missing Electron or positive electric charge. Free radicals can be neutral or charged. Terminology also has a boundary: metal ions exhibiting paramagnetism are not normally called free radicals just because they have unpaired Electrons.[ref]
Compare three species containing the same single proton. The hydrogen atom has one Electron in its atomic orbital, and is a neutral radical. The hydrogen cation has no Electrons, so no unpaired Electron. The hydrogen anion has two Electrons paired in its atomic orbital. It is charged but is not a radical in its ground state. With protons, Electrons, and positive elementary charge , the independent electric charge count is
The electron pair and electric charge questions require different information. An odd ensures that not all Electrons can be paired; an even alone does not ensure pairing, as the molecular orbital description of molecular oxygen illustrates.
Figure 1.
Electric charge and unpaired Electrons are different properties
. Left: actual ground state occupancies of , , and . Right: stipulated two-orbital models with fixed illustrate neutral, positive, and negative free radicals; those boxes are not assignments for particular chemical substances. Arrows label spin occupancy, not particle trajectories. Details.
The distinction matters whenever a chemical reaction mechanism uses dots and charge signs together. Homolysis gives one bonding Electron to each fragment, while heterolysis assigns both to one fragment. A radical chain reaction can pass an unpaired Electron from one species to another without generating net electric charge. Detection then exploits the unpaired Electron's spin and magnetic moment, rather than merely measuring whether the sample carries an electric charge.