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oxidation and reduction

oxidation and reduction, complementary chemical reactions characterized by the loss or gain, respectively, of one or more electrons by an atom or molecule. Originally the term oxidation was used to refer to a reaction in which oxygen combined with an element or compound, e.g., the reaction of magnesium with oxygen to form magnesium oxide or the combination of carbon monoxide with oxygen to form carbon dioxide. Similarly, reduction referred to a decrease in the amount of oxygen in a substance or its complete removal, e.g., the reaction of cupric oxide and hydrogen to form copper and water.

When an atom or molecule combines with oxygen, it tends to give up electrons to the oxygen in forming a chemical bond. Similarly, when it loses oxygen, it tends to gain electrons. Such changes are now described in terms of changes in the oxidation number, or oxidation state, of the atom or molecule (see valence). Thus oxidation has come to be defined as a loss of electrons or an increase in oxidation number, while reduction is defined as a gain of electrons or a decrease in oxidation number, whether or not oxygen itself is actually involved in the reaction.

In the formation of magnesium oxide from magnesium and oxygen, the magnesium atoms have lost two electrons, or the oxidation number has increased from zero to +2. This is also true when magnesium reacts with chlorine to form magnesium chloride. In solution, ferrous iron (oxidation number +2) may be oxidized to ferric iron (oxidation number +3) by the loss of an electron. In the reduction of cupric oxide the oxidation number of copper has changed from +2 to zero by the gain of two electrons. The two processes, oxidation and reduction, occur simultaneously and in chemically equivalent quantities. In the formation of magnesium chloride, for every magnesium atom oxidized by a loss of two electrons, two chlorine atoms are reduced by a gain of one electron each.

Oxidation-reduction reactions, called also redox reactions, are most simply balanced in the form of chemical equations by arranging the quantities of the substances involved so that the number of electrons lost by one substance is equaled by the number gained by another substance. In such reactions, the substance losing electrons (undergoing oxidation) is said to be an electron donor, or reductant, since its lost electrons are given to and reduce the other substance. Conversely, the substance that is gaining electrons (undergoing reduction) is said to be an electron acceptor, or oxidant.

Common reductants (substances readily oxidized) are the active metals, hydrogen, hydrogen sulfide, carbon, carbon monoxide, and sulfurous acid. Common oxidants (substances readily reduced) include the halogens (especially fluorine and chlorine), oxygen, ozone, potassium permanganate, potassium dichromate, nitric acid, and concentrated sulfuric acid. Some substances are capable of acting either as reductants or as oxidants, e.g., hydrogen peroxide and nitrous acid.

The corrosion of metals is a naturally occurring redox reaction. Industrially, many redox reactions are of great importance: combustion of fuels; electrolysis (oxidation occurs at the anode and reduction at the cathode); and metallurgical processes in which free metals are obtained from their ores.

The Columbia Electronic Encyclopedia, 6th ed. Copyright © 2012, Columbia University Press. All rights reserved.

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