Although virtually all types of organic materials can undergo air oxidation, certain types are particularly prone to autoxidation, including unsaturated compounds that have allylic hydrogens or benzylic hydrogens; these materials are converted to hydroperoxides by autoxidation.
Autoxidation is a free radical chain process. Such reactions can be divided into three stages: chain initation, propagation, and termination. In the initiation process, some event causes free radicals to be formed. For example, free radicals can be produced purposefully by the decomposition of a radical initiator, such as benzoyl peroxide. In some cases, initiation occurs by a process that is not well understood but is thought to be the spontaneous reaction of oxygen with a material with a readily abstractable hydrogen. Destructive autoxidation processes also are initiated by pollutants such as those in smog.
Once free radicals are formed, they react in a chain to convert the material to a hydroperoxide. The chain is ended by termination reactions in which free radicals collide and combine their odd electrons to form a new bond.
Autoxidation is a process of enormous economic impact, since all foods, plastics, gasolines, oils, rubber, and other materials that must be exposed to air undergo continuous destructive reactions of this type. All plastics and rubber and most processed foods contain antioxidants to protect them against the attack of oxygen.