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Radical (chemistry)

In chemistry, a radical, also known as a free radical, is an atom, molecule, or ion that has at least one unpaired valence electron.[1][2] With some exceptions, these unpaired electrons make radicals highly chemically reactive. Many radicals spontaneously dimerize. Most organic radicals have short lifetimes.

"Free radical" redirects here. For the aging theory, see Free-radical theory of aging. For other uses, see Free radical (disambiguation).

A notable example of a 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.


Radicals may be generated in a number of ways, but typical methods involve redox reactions, Ionizing radiation, heat, electrical discharges, and electrolysis are known to produce radicals. Radicals are intermediates in many chemical reactions, more so than is apparent from the balanced equations.


Radicals are important in combustion, atmospheric chemistry, polymerization, plasma chemistry, biochemistry, and many other chemical processes. A majority of natural products are generated by radical-generating enzymes. In living organisms, the 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.

Inorganic radicals[edit]

A large variety of inorganic radicals are stable and in fact isolable. Examples include most first-row transition metal complexes.


With regard to main group radicals, the most abundant radical in the universe is also the most abundant chemical in the universe, H. Most main group radicals are not however isolable, despite their intrinsic stability. Hydrogen radicals for example combine eagerly to form H2. Nitric oxide (NO) is well known example of an isolable inorganic radical. Fremy's salt (Potassium nitrosodisulfonate, (KSO3)2NO) is a related example. Many thiazyl radicals are known, despite limited extent of π resonance stabilization.[10][11]


Many radicals can be envisioned as the products of breaking of covalent bonds by homolysis. The homolytic bond dissociation energies, usually abbreviated as "ΔH °" are a measure of bond strength. Splitting H2 into 2 H, for example, requires a ΔH ° of +435 kJ/mol, while splitting Cl2 into two Cl requires a ΔH ° of +243 kJ/mol. For weak bonds, homolysis can be induced thermally. Strong bonds require high energy photons or even flames to induce homolysis.

Diradicals[edit]

Diradicals are molecules containing two radical centers. Dioxygen (O2) is an important example of a stable diradical. Singlet oxygen, the lowest-energy non-radical state of dioxygen, is less stable than the diradical due to Hund's rule of maximum multiplicity. The relative stability of the oxygen diradical is primarily due to the spin-forbidden nature of the triplet-singlet transition required for it to grab electrons, i.e., "oxidize". The diradical state of oxygen also results in its paramagnetic character, which is demonstrated by its attraction to an external magnet.[12] Diradicals can also occur in metal-oxo complexes, lending themselves for studies of spin forbidden reactions in transition metal chemistry.[13] Carbenes in their triplet state can be viewed as diradicals centred on the same atom, while these are usually highly reactive persistent carbenes are known, with N-heterocyclic carbenes being the most common example.


Triplet carbenes and nitrenes are diradicals. Their chemical properties are distinct from the properties of their singlet analogues.

Initiation reactions are those that result in a net increase in the number of radicals. They may involve the formation of radicals from stable species as in Reaction 1 above or they may involve reactions of radicals with stable species to form more radicals.

Propagation reactions are those reactions involving radicals in which the total number of radicals remains the same.

Termination reactions are those reactions resulting in a net decrease in the number of radicals. Typically two radicals combine to form a more stable species, for example:

2 Cl → Cl2

In chemical equations, radicals are frequently denoted by a dot placed immediately to the right of the atomic symbol or molecular formula as follows:


Radical reaction mechanisms use single-headed arrows to depict the movement of single electrons:


The homolytic cleavage of the breaking bond is drawn with a "fish-hook" arrow to distinguish from the usual movement of two electrons depicted by a standard curly arrow. The second electron of the breaking bond also moves to pair up with the attacking radical electron.


Radicals also take part in radical addition and radical substitution as reactive intermediates. Chain reactions involving radicals can usually be divided into three distinct processes. These are initiation, propagation, and termination.

Electron pair

Globally Harmonized System of Classification and Labelling of Chemicals

Hofmann–Löffler reaction