Redox Reactions

Redox (shorthand for oxidation-reduction) reactions describe all chemical reactions in which atoms have their oxidation number (oxidation state) changed. This can be either a simple redox process, such as the oxidation of carbon to yield carbon dioxide (CO₂) or the reduction of carbon by hydrogen to yield methane (CH₄), or a complex process such as the oxidation of sugar(C₆H₁₂O₆) in the human body through a series of complex electron transfer processes.

The term comes from the two concepts of reduction and oxidation. It can be explained in simple terms:

• Oxidation is the loss of electrons or an increase in oxidation state by a molecule, atom, or ion.
• Reduction is the gain of electrons or a decrease in oxidation state by a molecule, atom, or ion.

Though sufficient for many purposes, these descriptions are not precisely correct. Oxidation and reduction properly refer to a change in oxidation number — the actual transfer of electrons may never occur. Thus, oxidation is better defined as an increase in oxidation number, and reduction as a decrease in oxidation number. In practice, the transfer of electrons will always cause a change in oxidation number, but there are many reactions that are classed as "redox" even though no electron transfer occurs (such as those involving covalent bonds).
Non-redox reactions, which do not involve changes in formal charge, are known as metathesis reactions.

Examples of redox reactions

A good example is the reaction between hydrogen and fluorine in which hydrogen is being oxidized and fluorine is being reduced:

H₂ + F₂ → 2 HF

We can write this overall reaction as two half-reactions:
the oxidation reaction:

H₂ → 2 H⁺ + 2 e⁻

and the reduction reaction:

F₂ + 2 e⁻ → 2 F⁻

Analyzing each half-reaction in isolation can often make the overall chemical process clearer. Because there is no net change in charge during a redox reaction, the number of electrons in excess in the oxidation reaction must equal the number consumed by the reduction reaction (as shown above).
Elements, even in molecular form, always have an oxidation number of zero. In the first half-reaction, hydrogen is oxidized from an oxidation number of zero to an oxidation number of +1. In the second half-reaction, fluorine is reduced from an oxidation number of zero to an oxidation number of −1.
When adding the reactions together the electrons cancel:

H2	→	2 H+ + 2 e−
F2 + 2 e−	→	2 F−
H2 + F2	→	2 H+ + 2 F−

And the ions combine to form hydrogen fluoride:

H₂ + F₂ → 2 H⁺ + 2 F⁻ → 2 HF

Displacement reactions

Redox occurs in single displacement reactions or substitution reactions. The redox component of these types of reactions is the change of oxidation state (charge) on certain atoms, not the actual exchange of atoms in the compounds.
For example, in the reaction between iron and copper(II) sulfate solution:

Fe + CuSO₄ → FeSO₄ + Cu

The ionic equation for this reaction is:

Fe + Cu²⁺ → Fe²⁺ + Cu

As two half-equations, it is seen that the iron is oxidized:

Fe → Fe²⁺ + 2 e⁻

And the copper is reduced:

Cu²⁺ + 2 e⁻ → Cu

Other examples

• The oxidation of iron(II) to iron(III) by hydrogen peroxide in the presence of an acid:

Fe²⁺ → Fe³⁺ + e⁻

H₂O₂ + 2 e⁻ → 2 OH⁻

Overall equation:

2 Fe²⁺ + H₂O₂ + 2 H⁺ → 2 Fe³⁺ + 2 H₂O

• The reduction of nitrate to nitrogen in the presence of an acid (denitrification):

2 NO₃⁻ + 10 e⁻ + 12 H⁺ → N₂ + 6 H₂O

Iron rusting in pyrite cubes

• Oxidation of elemental iron to iron(III) oxide by oxygen (commonly known as rusting, which is similar to tarnishing):

4 Fe + 3 O₂ → 2 Fe₂O₃

• The combustion of hydrocarbons, such as in an internal combustion engine, which produces water, carbon dioxide, some partially oxidized forms such as carbon monoxide, and heat energy. Complete oxidation of materials containing carbon produces carbon dioxide.

• In organic chemistry, the stepwise oxidation of a hydrocarbon by oxygen produces water and, successively, an alcohol, an aldehyde or a ketone, a carboxylic acid, and then a peroxide.

[edit] Redox reactions in industry

The primary process of reducing ore to produce metals is discussed in the article on Smelting.
Oxidation is used in a wide variety of industries such as in the production of cleaning products and oxidising ammonia to produce nitric acid, which is used in most fertilizers.
Redox reactions are the foundation of electrochemical cells.
The process of electroplating uses redox reactions to coat objects with a thin layer of a material, as in chrome plated automotive parts, silver plated cutlery, and gold plated jewelry.
The production of compact discs depends on a redox reaction, which coats the disc with a thin layer of metal film.

Redox reactions in biology

Top: ascorbic acid (reduced form of Vitamin C)
Bottom: dehydroascorbic acid (oxidized form of Vitamin C)

Many important biological processes involve redox reactions.
Cellular respiration, for instance, is the oxidation of glucose (C₆H₁₂O₆) to CO₂ and the reduction of oxygen to water. The summary equation for cell respiration is:

C₆H₁₂O₆ + 6 O₂ → 6 CO₂ + 6 H₂O

The process of cell respiration also depends heavily on the reduction of NAD⁺ to NADH and the reverse reaction (the oxidation of NADH to NAD⁺). Photosynthesis is essentially the reverse of the redox reaction in cell respiration:

6 CO₂ + 6 H₂O + light energy → C₆H₁₂O₆ + 6 O₂

Biological energy is frequently stored and released by means of redox reactions. Photosynthesis involves the reduction of carbon dioxide into sugars and the oxidation of water into molecular oxygen. The reverse reaction, respiration, oxidizes sugars to produce carbon dioxide and water. As intermediate steps, the reduced carbon compounds are used to reduce nicotinamide adenine dinucleotide (NAD⁺), which then contributes to the creation of a proton gradient, which drives the synthesis of adenosine triphosphate (ATP) and is maintained by the reduction of oxygen. In animal cells, mitochondria perform similar functions. See Membrane potential article.
The term redox state is often used to describe the balance of NAD⁺/NADH and NADP⁺/NADPH in a biological system such as a cell or organ. The redox state is reflected in the balance of several sets of metabolites (e.g., lactate and pyruvate, beta-hydroxybutyrate and acetoacetate), whose interconversion is dependent on these ratios. An abnormal redox state can develop in a variety of deleterious situations, such as hypoxia, shock, and sepsis. Redox signaling involves the control of cellular processes by redox processes.
Redox proteins and their genes must be co-located for redox regulation according to the CoRR hypothesis for the function of DNA in mitochondria and chloroplasts.

Redox cycling

A wide variety of aromatic compounds are enzymatically reduced to form free radicals that contain one more electron than their parent compounds. In general, the electron donor is any of a wide variety of flavoenzymes and their coenzymes. Once formed, these anion free radicals reduce molecular oxygen to superoxide, and regenerate the unchanged parent compound. The net reaction is the oxidation of the flavoenzyme's coenzymes and the reduction of molecular oxygen to form superoxide. This catalytic behavior has been described as futile cycle or redox cycling.
Examples of redox cycling-inducing molecules are the herbicide paraquat and other viologens and quinones such as menadione.