Disproportionation

Disproportionation is a specific type of redox reaction in which a species is simultaneously reduced and oxidised to form two different products.

Overview

For example, the UV photolysis of mercury(I) chloride Hg2Cl2 → Hg + HgCl2 is a disproportionation. Mercury(I) is a diatomic dication Hg2+
2
. In this reaction, the chemical bond in the molecular ion is broken, and one mercury atom is reduced to mercury(0), and the other is oxidized to mercury(II).

A similar type of reaction, but in which no element changes oxidation number, is the acid-base disproportionation reaction observed when an amphiprotic species reacts with itself. Two common examples for conjugated bases of polyprotic acids such as bicarbonate and dihydrogenophosphate are respectively:

2 HCO
3
CO2−
3
+ H2CO3
2 H
2
PO
4
HPO2−
4
+ H3PO4

The oxidation numbers remain constant in these acid-base reactions: O = −2, H = +1, C = +4, P = +5. This is also called autoionization.

Another variant on disproportionation is radical disproportionation, in which two radicals form an alkane and alkene.

Reverse reaction

The reverse of disproportionation, when a compound in an intermediate oxidation state is formed from compounds in lower and higher oxidation states, is called comproportionation, also known as symproportionation.

History

The first disproportionation reaction to be studied in detail was:

2 Sn2+ → Sn4+ + Sn

This was examined using tartrates by Johan Gadolin in 1788. In the Swedish version of his paper he called it 'söndring'.[1][2]

Examples

3 Cl2 + 6 OH → 5 Cl + ClO3 + 3 H2O
The chlorine gas reactant is in oxidation state 0. In the products, the chlorine in the Cl ion has an oxidation number of −1, having been reduced, whereas the oxidation number of the chlorine in the ClO3 ion is +5, indicating that it has been oxidized.
2 O2 + 2 H+ → H2O2 + O2
The oxidation state of oxygen is −1/2 in the superoxide free radical anion, −1 in hydrogen peroxide and 0 in dioxygen.
2 H2O2 → 2 H2O + O2
2 CO → C + CO2

Biochemistry

In 1937, Hans Adolf Krebs, who discovered the citric acid cycle bearing his name, confirmed the anaerobic dismutation of pyruvic acid in lactic acid, acetic acid and CO2 by certain bacteria according to the global reaction:[4]

2 pyruvic acid + H2O → lactic acid + acetic acid + CO2

The dismutation of pyruvic acid in other small organic molecules (ethanol + CO2, or lactate and acetate, depending on the environmental conditions) is also an important step in fermentation reactions. Fermentation reactions can also be considered as disproportionation or dismutation biochemical reactions. Indeed, the donor and acceptor of electrons in the redox reactions supplying the chemical energy in these complex biochemical systems are the same organic molecules simultaneously acting as reductant or oxidant.

Another example of biochemical dismutation reaction is the disproportionation of acetaldehyde into ethanol and acetic acid.[5]

While in respiration electrons are transferred from substrate (electron donor) to an electron acceptor, in fermentation part of the substrate molecule itself accepts the electrons. Fermentation is therefore a type of disproportionation, and does not involve an overall change in oxidation state of the substrate. Most of the fermentative substrates are organic molecules. However, a rare type of fermentation may also involve the disproportionation of inorganic sulfur compounds in certain sulfate-reducing bacteria.[6]

See also

References

  1. Gadolin Johan (1788) K. Sv. Vet. Acad. Handl. 1788, 186-197.
  2. Gadolin Johan (1790) Crells Chem. Annalen 1790, I, 260-273.
  3. Charlie Harding, David Arthur Johnson, Rob Janes, (2002), Elements of the P Block, Published by Royal Society of Chemistry, ISBN 0-85404-690-9
  4. Krebs, H.A. (1937). "LXXXVIII - Dismutation of pyruvic acid in gonoccus and staphylococcus" (PDF). Biochem J. 31 (4): 661–671. PMC 1266985. PMID 16746383.
  5. Biochemical basis of mitochondrial acetaldehyde dismutation in Saccharomyces cerevisiae
  6. A novel type of energy metabolism involving fermentation of inorganic sulfur compounds.
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