Comproportionation or synproportionation is a chemical reaction where two reactants containing the same element but with different oxidation numbers, form a compound having an intermediate oxidation number. It is the opposite of disproportionation. [1]
In electrochemistry, the tendency of two redox species to disproportionate, or comproportionate, can be determined by examining their Frost diagram. It is a graphical plot of nE° = −ΔG°/F as a function of the oxidation number for the different redox species of a given element.
The Gibbs free energy ΔG° is related to the reduction potential E° by the formula: ΔG° = −nFE° or nE° = −ΔG°/F, where n is the number of transferred electrons, and F is the Faraday constant (F = 96,485 J/(V·mol)= 96,485 Coulomb). [1]
If the value of nE° = −ΔG°/F for a species is lower than the line joining two adjacent, or more generally, neighboring species, having thus a lower and a higher oxidation number, then this species is more stable than its neighbors, and the two surrounding species will undergo comproportionation to minimize the Gibbs free energy of the system. Example: a mixture of Mn(III) and Mn(VI) will comproportionate towards Mn(IV) as illustrated in the Frost diagram for manganese. Non-adjacent neighboring species of Mn obeying the same general rule will also react together as, e.g., Mn2+ and MnO−4 to form MnO2. So, the more distant Mn(II) and Mn(VII) can also react together to form Mn(IV). The reacting redox species do not have to be necessarily adjacent on a Frost diagram.
The comproportionation reaction cannot easily occur in solids in which the potentially reactive species are immobile and thus cannot react together, or the reaction will be extremely slow and will also require high temperature close to the melting point of the solid to render the reactive species more mobile. However, if these species are soluble, and thus highly mobile in an aqueous solution, they will much more easily encounter, react and undergo comproportionation. In the case of heterogeneous systems involving a solution and one or more solid phases, as in a lead–acid battery, a comproportionation reaction is possible thanks to the mobile dissolved Pb2+ ions released into solution at the surface of the battery solid electrodes (Pb and PbO2). In the gas phase, the comproportionation reaction is much faster because of the much higher mobility of the reacting species as illustrated, e.g., in the Claus reaction where H2S and SO2 react together to form elemental sulfur. Various classical comproportionation reactions are detailed in the series of examples here below.
Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.
Aqua regia is a mixture of nitric acid and hydrochloric acid, optimally in a molar ratio of 1:3. Aqua regia is a fuming liquid. Freshly prepared aqua regia is colorless, but it turns yellow, orange or red within seconds from the formation of nitrosyl chloride and nitrogen dioxide. It was named by alchemists because it can dissolve the noble metals gold and platinum, though not all metals.
In chemistry, iron(III) refers to the element iron in its +3 oxidation state. In ionic compounds (salts), such an atom may occur as a separate cation (positive ion) denoted by Fe3+.
Manganese dioxide is the inorganic compound with the formula MnO
2. This blackish or brown solid occurs naturally as the mineral pyrolusite, which is the main ore of manganese and a component of manganese nodules. The principal use for MnO
2 is for dry-cell batteries, such as the alkaline battery and the zinc–carbon battery. MnO
2 is also used as a pigment and as a precursor to other manganese compounds, such as KMnO
4. It is used as a reagent in organic synthesis, for example, for the oxidation of allylic alcohols. MnO
2 has an α-polymorph that can incorporate a variety of atoms in the "tunnels" or "channels" between the manganese oxide octahedra. There is considerable interest in α-MnO
2 as a possible cathode for lithium-ion batteries.
Iron(III) chloride describes the inorganic compounds with the formula FeCl3(H2O)x. Also called ferric chloride, these compounds are some of the most important and commonplace compounds of iron. They are available both in anhydrous and in hydrated forms which are both hygroscopic. They feature iron in its +3 oxidation state. The anhydrous derivative is a Lewis acid, while all forms are mild oxidizing agents. It is used as a water cleaner and as an etchant for metals.
Group 7, numbered by IUPAC nomenclature, is a group of elements in the periodic table. It contains manganese (Mn), technetium (Tc), rhenium (Re) and bohrium (Bh). This group lies in the d-block of the periodic table, and are hence transition metals. This group is sometimes called the manganese group or manganese family after its lightest member; however, the group itself has not acquired a trivial name because it belongs to the broader grouping of the transition metals.
Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as “tickle” or “tickle 4”, as a phonetic representation of the symbols of its molecular formula.
Lead(II) chloride (PbCl2) is an inorganic compound which is a white solid under ambient conditions. It is poorly soluble in water. Lead(II) chloride is one of the most important lead-based reagents. It also occurs naturally in the form of the mineral cotunnite.
Manganese(II) chloride is the dichloride salt of manganese, MnCl2. This inorganic chemical exists in the anhydrous form, as well as the dihydrate (MnCl2·2H2O) and tetrahydrate (MnCl2·4H2O), with the tetrahydrate being the most common form. Like many Mn(II) species, these salts are pink, with the paleness of the color being characteristic of transition metal complexes with high spin d5 configurations.
Iron(II) chloride, also known as ferrous chloride, is the chemical compound of formula FeCl2. It is a paramagnetic solid with a high melting point. The compound is white, but typical samples are often off-white. FeCl2 crystallizes from water as the greenish tetrahydrate, which is the form that is most commonly encountered in commerce and the laboratory. There is also a dihydrate. The compound is highly soluble in water, giving pale green solutions.
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. 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.
Gold(III) chloride, traditionally called auric chloride, is an inorganic compound of gold and chlorine with the molecular formula Au2Cl6. The "III" in the name indicates that the gold has an oxidation state of +3, typical for many gold compounds. It has two forms, the monohydrate (AuCl3·H2O) and the anhydrous form, which are both hygroscopic and light-sensitive solids. This compound is a dimer of AuCl3. This compound has a few uses, such as an oxidizing agent and for catalyzing various organic reactions.
Tin(II) chloride, also known as stannous chloride, is a white crystalline solid with the formula SnCl2. It forms a stable dihydrate, but aqueous solutions tend to undergo hydrolysis, particularly if hot. SnCl2 is widely used as a reducing agent (in acid solution), and in electrolytic baths for tin-plating. Tin(II) chloride should not be confused with the other chloride of tin; tin(IV) chloride or stannic chloride (SnCl4).
A Frost diagram or Frost–Ebsworth diagram is a type of graph used by inorganic chemists in electrochemistry to illustrate the relative stability of a number of different oxidation states of a particular substance. The graph illustrates the free energy vs oxidation state of a chemical species. This effect is dependent on pH, so this parameter also must be included. The free energy is determined by the oxidation–reduction half-reactions. The Frost diagram allows easier comprehension of these reduction potentials than the earlier-designed Latimer diagram, because the “lack of additivity of potentials” was confusing. The free energy ΔG° is related to the reduction potential E shown in the graph by the formula: ΔG° = −nFE° or nE° = −ΔG°/F, where n is the number of transferred electrons, and F is the Faraday constant (F = 96,485 J/(V·mol)= 96,485 Coulomb). The Frost diagram is named after Arthur Atwater Frost, who originally invented it as a way to "show both free energy and oxidation potential data conveniently" in a 1951 paper.
Vanadium(III) chloride describes the inorganic compound with the formula VCl3 and its hydrates. It forms a purple anhydrous form and a green hexahydrate [VCl2(H2O)4]Cl·2H2O. These hygroscopic salts are common precursors to other vanadium(III) complexes and is used as a mild reducing agent.
Titanium(II) chloride is the chemical compound with the formula TiCl2. The black solid has been studied only moderately, probably because of its high reactivity. Ti(II) is a strong reducing agent: it has a high affinity for oxygen and reacts irreversibly with water to produce H2. The usual preparation is the thermal disproportionation of TiCl3 at 500 °C. The reaction is driven by the loss of volatile TiCl4:
Technetium compounds are chemical compounds containing the chemical element technetium. Technetium can form multiple oxidation states, but often forms in the +4 and +7 oxidation states. Because technetium is radioactive, technetium compounds are extremely rare on Earth.
Iron shows the characteristic chemical properties of the transition metals, namely the ability to form variable oxidation states differing by steps of one and a very large coordination and organometallic chemistry: indeed, it was the discovery of an iron compound, ferrocene, that revolutionalized the latter field in the 1950s. Iron is sometimes considered as a prototype for the entire block of transition metals, due to its abundance and the immense role it has played in the technological progress of humanity. Its 26 electrons are arranged in the configuration [Ar]3d64s2, of which the 3d and 4s electrons are relatively close in energy, and thus it can lose a variable number of electrons and there is no clear point where further ionization becomes unprofitable.
Germanium dichloride is a chemical compound of germanium and chlorine with the formula GeCl2. It is a yellow solid. Germanium dichloride is an example of a compound featuring germanium in the +2 oxidation state.