Disproportionation, also known as dismutation is used to describe a specific type of redox reaction in which a species is simultaneously reduced and oxidized so as to form two different products.
For example: the UV photolysis of mercury(I) chloride Hg2Cl2 → Hg + HgCl2 is a disproportionation since mercury (I) is both reduced to mercury (0) and 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:
- HCO3- + HCO3- → CO32- + H2CO3
- H2PO4- + H2PO4- → HPO42- + H3PO4
(the oxidation numbers remain constant in these acid-base reactions: O = 2-, H = 1+, C = 4+, P = 5+). This is also called autoionization.
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.
The first disproportionation reaction to be studied in detail was:
- 2 Sn2+ → Sn4+ + Sn
- Chlorine gas reacts with dilute sodium hydroxide to form sodium chloride, sodium chlorate and water. The ionic equation for this reaction is as follows :
- 3Cl2 + 6OH− → 5Cl− + ClO3− + 3H2O
- 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.
- The dismutation of superoxide free radical to hydrogen peroxide and oxygen, catalysed in living systems by the enzyme superoxide dismutase:
- 2O2− + 2H+ → H2O2 + O2
- The oxidation state of oxygen is -1/2 in the superoxide free radical anion, -1 in hydrogen peroxide and 0 in dioxygen.
- In the Cannizzaro reaction, an aldehyde is converted into an alcohol and a carboxylic acid. In the related Tishchenko reaction, the organic redox reaction product is the corresponding ester. In the Kornblum–DeLaMare rearrangement, a peroxide is converted to a ketone and an alcohol.
- The disproportionation of hydrogen peroxide into water and oxygen catalysed by either potassium iodide or the enzyme catalase:
- 2H2O2 → 2H2O + O2
- The Boudouard reaction is for example used in the HiPco method for producing carbon nanotubes, high pressure carbon monoxide disproportionates when catalysed on the surface of an iron particle:
- 2CO → C + CO2
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:
- 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.
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 sulphur compounds in certain sulphate-reducing bacteria.
- ^ Gadolin Johan (1788) K. Sv. Vet. Acad. Handl. 1788, 186-197.
- ^ Gadolin Johan (1790) Crells Chem. Annalen 1790, I, 260-273.
- ^ Charlie Harding, David Arthur Johnson, Rob Janes, (2002), Elements of the P Block, Published by Royal Society of Chemistry, ISBN 0854046909
- ^ Krebs, H.A. (1937). "LXXXVIII - Dismutation of pyruvic acid in gonoccus and staphylococcus". Biochem J. 31 (4): 661–671. http://www.ncbi.nlm.nih.gov/pmc/articles/PMC1266985/pdf/biochemj01050-0180.pdf.
- ^ [http://jb.asm.org/cgi/reprint/173/21/7012.pdf | Biochemical basis of mitochondrial acetaldehyde dismutation in Saccharomyces cerevisiae]
- ^ A novel type of energy metabolism involving fermentation of inorganic sulphur compounds.
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disproportionation — disproporcionavimasis statusas T sritis chemija apibrėžtis Atomų arba grupių persiskirstymas tarp dviejų vienodų molekulių, radikalų, grupių. atitikmenys: angl. dismutation; disproportionation rus. дисмутация; диспропорционирование ryšiai:… … Chemijos terminų aiškinamasis žodynas
disproportionation — disproporcionavimasis statusas T sritis chemija apibrėžtis Elemento oksidacijos laipsnio padidėjimas ir sumažėjimas vienodų molekulių reakcijos metu. atitikmenys: angl. dismutation; disproportionation rus. дисмутация; диспропорционирование ryšiai … Chemijos terminų aiškinamasis žodynas
disproportionation — |disprəˌpōrshə|nāshən, pȯr noun : the transformation of a substance into two or more dissimilar substances usually by a process involving simultaneous oxidation and reduction : dismutation disproportionation of hydrogen peroxide to water and… … Useful english dictionary
disproportionation — noun Date: circa 1929 the transformation of a substance into two or more dissimilar substances usually by simultaneous oxidation and reduction • disproportionate intransitive verb … New Collegiate Dictionary
disproportionation — /dis preuh pawr sheuh nay sheuhn, pohr /, n. Chem. the simultaneous oxidation and reduction of a substance reacting with itself, thereby forming two dissimilar molecules, as 2C2H4 > C2H6+C2H2. [1925 30; DISPROPORTION + ATION] * * * … Universalium
disproportionation — noun a) A form of redox reaction in which part of a reactant is oxidized and part of it is reduced simultaneously b) A reaction wherein a single reactant generates two chemical species which are different from each other and the initial reactant … Wiktionary
disproportionation — noun Chemistry a reaction in which a substance is simultaneously oxidized and reduced, giving two different products … English new terms dictionary
disproportionation — dis·pro·por·tion·a·tion … English syllables
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