Redox Chemistry

Oxidation-Reduction Reactions

Earth’s atmosphere contains about 20% molecular oxygen, O2, a chemically reactive gas that plays an essential role in the metabolism of aerobic organisms and in many environmental processes that shape the world. The term oxidation was originally used to describe chemical reactions involving O2, but its meaning has evolved to refer to a broad and important reaction class known asoxidation-reduction (redox) reactions. A few examples of such reactions will be used to develop a clear picture of this classification.

Some redox reactions involve the transfer of electrons between reactant species to yield ionic products, such as the reaction between sodium and chlorine to yield sodium chloride:

2Na(s) + Cl2(g) 2NaCl(s)

It is helpful to view the process with regard to each individual reactant, that is, to represent the fate of each reactant in the form of an equation called a half-reaction:

2Na(s) 2Na+(s) + 2e
Cl2(g) + 2e⟶  2Cl(s)

These equations show that Na atoms lose electrons while Cl atoms (in the Cl2 molecule) gain electrons, the “s” subscripts for the resulting ions signifying they are present in the form of a solid ionic compound. For redox reactions of this sort, the loss and gain of electrons define the complementary processes that occur:


oxidation = loss of electrons
reduction = gain of electrons

In this reaction, then, sodium is oxidized and chlorine undergoes reduction. Viewed from a more active perspective, sodium functions as a reducing agent (reductant), since it provides electrons to (or reduces) chlorine. Likewise, chlorine functions as an oxidizing agent (oxidant), as it effectively removes electrons from (oxidizes) sodium.


reducing agent = species that is oxidized
oxidizing agent = species that is reduced

Some redox processes, however, do not involve the transfer of electrons. Consider, for example, a reaction similar to the one yielding NaCl:


H2(g) + Cl2(g) ⟶  2HCl(g)

The product of this reaction is a covalent compound, so transfer of electrons in the explicit sense is not involved. To clarify the similarity of this reaction to the previous one and permit an unambiguous definition of redox reactions, a property called oxidation number has been defined. The oxidation number (or oxidation state) of an element in a compound is the charge its atoms would possess if the compound was ionic. The following guidelines are used to assign oxidation numbers to each element in a molecule or ion.


  1. The oxidation number of an atom in an elemental substance is zero.
  2. The oxidation number of a monatomic ion is equal to the ion’s charge.
  3. Oxidation numbers for common nonmetals are usually assigned as follows:
    • Hydrogen: +1 when combined with nonmetals, −1 when combined with metals
    • Oxygen: −2 in most compounds, sometimes −1 (so-called peroxides, O22−), very rarely 1/2 (so-called superoxides, O2), positive values when combined with F (values vary)
    • Halogens: −1 for F always, −1 for other halogens except when combined with oxygen or other halogens (positive oxidation numbers in these cases, varying values)
  4. The sum of oxidation numbers for all atoms in a molecule or polyatomic ion equals the charge on the molecule or ion.


Using the oxidation number concept, an all-inclusive definition of redox reaction has been established. Oxidation-reduction (redox) reactions are those in which one or more elements involved undergo a change in oxidation number. (While the vast majority of redox reactions involve changes in oxidation number for two or more elements, a few interesting exceptions to this rule do exist Example.) Definitions for the complementary processes of this reaction class are correspondingly revised as shown here:


oxidation = increase in oxidation number
reduction = decrease in oxidation number

Returning to the reactions used to introduce this topic, they may now both be identified as redox processes. In the reaction between sodium and chlorine to yield sodium chloride, sodium is oxidized (its oxidation number increases from 0 in Na to +1 in NaCl) and chlorine is reduced (its oxidation number decreases from 0 in Cl2 to −1 in NaCl). In the reaction between molecular hydrogen and chlorine, hydrogen is oxidized (its oxidation number increases from 0 in H2 to +1 in HCl) and chlorine is reduced (its oxidation number decreases from 0 in Cl2 to −1 in HCl).


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Organic redox reaction

Organic reductions or organic oxidations or organic redox reactions are redox reactionsthat take place with organic compounds. In organic chemistry oxidations and reductions are different from ordinary redox reactions because many reactions carry the name but do not actually involve electron transfer in the electrochemical sense of the word.[1] Instead the relevant criterion for organic oxidation is gain of oxygen and/or loss of hydrogen [2]


Simple functional groups can be arranged in order of increasing oxidation state. The oxidation numbers are only an approximation:[1]


oxidation number compounds
-4 alkanes
-2 alkenes, alcohols, alkyl halides, amines
0 alkynes, ketones, aldehydes, geminal diols,
+2 carboxylic acids, amides, chloroform
+4 carbon dioxide, tetrachloromethane


When methane is oxidized to carbon dioxide its oxidation number changes from -4 to +4. Classical reductions include alkene reduction toalkanes and classical oxidations include oxidation of alcohols to aldehydes. In oxidations electrons are removed and the electron density of a molecule is reduced. In reductions electron density increases when electrons are added to the molecule. This terminology is always centered on the organic compound. For example, it is usual to refer to the reduction of a ketone by lithium aluminium hydride, but not to the oxidation of lithium aluminium hydride by a ketone. Many oxidations involve removal of hydrogen atoms from the organic molecule, and the reverse reduction adds hydrogens to an organic molecule.


Many reactions classified as reductions also appear in other classes. For instance conversion of the ketone to an alcohol by lithium aluminium hydride can be considered a reduction but the hydride is also a good nucleophile in nucleophilic substitution. Many redox reactions in organic chemistry have coupling reaction reaction mechanism involving free radical intermediates. True organic redox chemistry can be found in electrochemical organic synthesis or electrosynthesis. Examples of organic reactions that can take place in an electrochemical cell are theKolbe electrolysis.[3]


In disproportionation reactions the reactant is both oxidised and reduced in the same chemical reaction forming two separate compounds.


Asymmetric catalytic reductions and asymmetric catalytic oxidations are important in asymmetric synthesis.


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Redox Ladder