Radical (chemistry)

In chemistry, a radical (more precisely, a free radical) is an atom, molecule, or ion that has an unpaired valence electron. With some exceptions, these unpaired electrons make free radicals highly chemically reactive towards other substances, or even towards themselves: their molecules will often spontaneously dimerize or polymerize if they come in contact with each other. Most radicals are reasonably stable only at very low concentrations in inert media or in a vacuum.

A notable example of a free radical is the hydroxyl radical (HO•), a molecule that has one unpaired electron on the oxygen atom. Two other examples are triplet oxygen and triplet carbene (:CH
2) which have two unpaired electrons. In contrast, the hydroxyl anion (HO−
) is not a radical, since the unpaired electron is resolved by the addition of an electron; singlet oxygen and singlet carbene are not radicals as the two electrons are paired.

Free radicals may be created in a number of ways, including synthesis with very dilute or rarefied reagents, reactions at very low temperatures, or breakup of larger molecules. The latter can be affected by any process that puts enough energy into the parent molecule, such as ionizing radiation, heat, electrical discharges, electrolysis, and chemical reactions. Radicals are intermediate stages in many chemical reactions.

Free radicals play an important role in combustion, atmospheric chemistry, polymerization, plasma chemistry, biochemistry, and many other chemical processes. In living organisms, the free radicals superoxide and nitric oxide and their reaction products regulate many processes, such as control of vascular tone and thus blood pressure. They also play a key role in the intermediary metabolism of various biological compounds. Such radicals can even be messengers in a process dubbed redox signaling. A radical may be trapped within a solvent cage or be otherwise bound.

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