Disproportionation

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In chemistry, disproportionation, sometimes called dismutation, is a redox reaction in which one compound of intermediate oxidation state converts to two compounds, one of higher and one of lower oxidation states. [1] [2] The reverse of disproportionation, such as when a compound in an intermediate oxidation state is formed from precursors of lower and higher oxidation states, is called comproportionation , also known as synproportionation.

Contents

More generally, the term can be applied to any desymmetrizing reaction where two molecules of one type react to give one each of two different types: [3]

This expanded definition is not limited to redox reactions, but also includes some molecular autoionization reactions, such as the self-ionization of water. In contrast, some authors use the term redistribution to refer to reactions of this type (in either direction) when only ligand exchange but no redox is involved and distinguish such processes from disproportionation and comproportionation.
For example, the Schlenk equilibrium

is an example of a redistribution reaction.

History

The first disproportionation reaction to be studied in detail was:

This was examined using tartrates by Johan Gadolin in 1788. In the Swedish version of his paper he called it söndring. [4] [5]

Examples

The oxidation numbers remain constant in this acid-base reaction.
The chlorine 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 oxidation state of oxygen is −1/2 in the superoxide free radical anion, −1 in hydrogen peroxide and 0 in dioxygen.

Polymer chemistry

In free-radical chain-growth polymerization, chain termination can occur by a disproportionation step in which a hydrogen atom is transferred from one growing chain molecule to another one, which produces two dead (non-growing) chains. [14]

Chain—CH2–CHX + Chain—CH2–CHX → Chain—CH=CHX + Chain—CH2–CH2X

in which, Chain— represents the already formed polymer chain, and indicates a reactive free radical.

Biochemistry

In 1937, Hans Adolf Krebs, who discovered the citric acid cycle bearing his name, confirmed the anaerobic dismutation of pyruvic acid into lactic acid, acetic acid and CO2 by certain bacteria according to the global reaction: [15]

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. [16]

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. [17]

Disproportionation of sulfur intermediates

Sulfur isotopes of sediments are often measured for studying environments in the Earth's past (Paleoenvironment). Disproportionation of sulfur intermediates, being one of the processes affecting sulfur isotopes of sediments, has drawn attention from geoscientists for studying the redox conditions in the oceans in the past.

Sulfate-reducing bacteria fractionate sulfur isotopes as they take in sulfate and produce sulfide. Prior to 2010s, it was thought that sulfate reduction could fractionate sulfur isotopes up to 46 permil [18] and fractionation larger than 46 permil recorded in sediments must be due to disproportionation of sulfur intermediates in the sediment. This view has changed since the 2010s. [19] As substrates for disproportionation are limited by the product of sulfate reduction, the isotopic effect of disproportionation should be less than 16 permil in most sedimentary settings. [9]

Disproportionation can be carried out by microorganisms obligated to disproportionation or microorganisms that can carry out sulfate reduction as well. Common substrates for disproportionation include elemental sulfur, thiosulfate and sulfite. [9]

Claus reaction: a comproportionation reaction

The Claus reaction is an example of comproportionation reaction (the inverse of disproportionation) involving hydrogen sulfide (H2S) and sulfur dioxide (SO2) to produce elemental sulfur and water as follows:

The Claus reaction is one of the chemical reactions involved in the Claus process used for the desulfurization of gases in the oil refinery plants and leading to the formation of solid elemental sulfur, more easy to store, transport and dispose off.

See also

Related Research Articles

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<span class="mw-page-title-main">Sulfur</span> Chemical element, symbol S and atomic number 16

Sulfur (also spelled sulphur in British English) is a chemical element; it has symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with the chemical formula S8. Elemental sulfur is a bright yellow, crystalline solid at room temperature.

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Sulfuric acid or sulphuric acid, known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, and hydrogen, with the molecular formula H2SO4. It is a colorless, odorless, and viscous liquid that is miscible with water.

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<span class="mw-page-title-main">Redox</span> Chemical reaction in which oxidation states of atoms are changed

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<span class="mw-page-title-main">Cerium(IV) sulfate</span> Chemical compound

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<span class="mw-page-title-main">Single displacement reaction</span> Type of chemical reaction

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<span class="mw-page-title-main">Sulfur-reducing bacteria</span> Microorganisms able to reduce elemental sulfur to hydrogen sulfide

Sulfur-reducing bacteria are microorganisms able to reduce elemental sulfur (S0) to hydrogen sulfide (H2S). These microbes use inorganic sulfur compounds as electron acceptors to sustain several activities such as respiration, conserving energy and growth, in absence of oxygen. The final product of these processes, sulfide, has a considerable influence on the chemistry of the environment and, in addition, is used as electron donor for a large variety of microbial metabolisms. Several types of bacteria and many non-methanogenic archaea can reduce sulfur. Microbial sulfur reduction was already shown in early studies, which highlighted the first proof of S0 reduction in a vibrioid bacterium from mud, with sulfur as electron acceptor and H
2
as electron donor. The first pure cultured species of sulfur-reducing bacteria, Desulfuromonas acetoxidans, was discovered in 1976 and described by Pfennig Norbert and Biebel Hanno as an anaerobic sulfur-reducing and acetate-oxidizing bacterium, not able to reduce sulfate. Only few taxa are true sulfur-reducing bacteria, using sulfur reduction as the only or main catabolic reaction. Normally, they couple this reaction with the oxidation of acetate, succinate or other organic compounds. In general, sulfate-reducing bacteria are able to use both sulfate and elemental sulfur as electron acceptors. Thanks to its abundancy and thermodynamic stability, sulfate is the most studied electron acceptor for anaerobic respiration that involves sulfur compounds. Elemental sulfur, however, is very abundant and important, especially in deep-sea hydrothermal vents, hot springs and other extreme environments, making its isolation more difficult. Some bacteria – such as Proteus, Campylobacter, Pseudomonas and Salmonella – have the ability to reduce sulfur, but can also use oxygen and other terminal electron acceptors.

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Sulfur is metabolized by all organisms, from bacteria and archaea to plants and animals. Sulfur can have an oxidation state from -2 to +6 and is reduced or oxidized by a diverse range of organisms. The element is present in proteins, sulfate esters of polysaccharides, steroids, phenols, and sulfur-containing coenzymes.

<span class="mw-page-title-main">Microbial oxidation of sulfur</span>

Microbial oxidation of sulfur is the oxidation of sulfur by microorganisms to build their structural components. The oxidation of inorganic compounds is the strategy primarily used by chemolithotrophic microorganisms to obtain energy to survive, grow and reproduce. Some inorganic forms of reduced sulfur, mainly sulfide (H2S/HS) and elemental sulfur (S0), can be oxidized by chemolithotrophic sulfur-oxidizing prokaryotes, usually coupled to the reduction of oxygen (O2) or nitrate (NO3). Anaerobic sulfur oxidizers include photolithoautotrophs that obtain their energy from sunlight, hydrogen from sulfide, and carbon from carbon dioxide (CO2).

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