In chemistry, radicals (often referred to as free radicals) are atoms, molecules or ions with unpaired electrons on an otherwise open shell configuration. These unpaired electrons are usually highly reactive, so radicals are likely to take part in chemical reactions. Radicals play an important role in combustion, atmospheric chemistry, polymerization, plasma chemistry, biochemistry, and many other chemical processes, including human physiology. For example, superoxide and nitric oxide regulate many biological processes, such as controlling vascular tone. "Radical" and "free radical" are frequently used interchangeably, although a radical may be trapped within a solvent cage or be otherwise bound. The first organic free radical identified was triphenylmethyl radical, by Moses Gomberg in 1900 at the University of Michigan.

Historically, the term radical has also been used for bound parts of the molecule, especially when they remain unchanged in reactions. These are now called functional groups. For example, methyl alcohol was described as consisting of a methyl "radical" and a hydroxyl "radical". Neither are radicals in the modern chemical sense, as they are permanently bound to each other, and have no unpaired, reactive electrons. They can, however, be observed as radicals in mass spectrometry after breaking down the substance with a hail of energetic electrons.

Depicting radicals in chemical reactions

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

$\backslash mathrm\{Cl\}\_2\; \backslash ;\; \backslash xrightarrow\{u.v.\}\; \backslash ;\; \{\backslash mathrm\{Cl\}\; \backslash cdot\}\; +\; \{\backslash mathrm\{Cl\}\; \backslash cdot\}$

Chlorine gas can be broken down by ultraviolet light to form atomic chlorine radicals.

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. It should be noted that the second electron of the breaking bond also moves to pair up with the attacking radical electron; this is not explicitly indicated in this case.

In chemistry, free radicals take part in radical addition and radical substitution as reactive intermediates. Chain reactions involving free radicals can usually be divided into three distinct processes: initiation, propagation, and termination.

• Initiation reactions are those which result in a net increase in the number of free radicals. They may involve the formation of free radicals from stable species as in Reaction 1 above or they may involve reactions of free radicals with stable species to form more free radicals.
• Propagation reactions are those reactions involving free radicals in which the total number of free radicals remains the same.
• Termination reactions are those reactions resulting in a net decrease in the number of free radicals. Typically two free radicals combine to form a more stable species, for example: 2Cl·→ Cl₂