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Manganate

physical science Maturity 11-13 Next article →

In the field of inorganic nomenclature, a manganate is a negatively charged molecular entity. It features manganese as its central atom.

Manganate
Manganate

While the term can describe several different ions, it usually refers to the tetraoxidomanganate(2−) anion. This specific ion is also called manganate(VI). This name comes from its +6 oxidation state. Manganates are unique because they are the only known manganese(VI) compounds. They are essential for understanding how transition metal oxyanions behave in chemistry.

The structure of the manganate(VI) ion is a tetrahedron. This means it forms a shape like a pyramid with four triangular sides.

Manganate
Manganate

This shape is isostructural with sulfates and chromates. This term means they share the same geometric arrangement. The manganese–oxygen distance in this structure is 165.9 pm. This distance is about 3 pm longer than the distance found in permanganate. Because it is a d1 ion, it is paramagnetic. This means it is attracted to magnetic fields. Although it should show Jahn–Teller distortion, the deviation from its tetrahedral shape is too small to detect with X-ray crystallography.

Scientists have identified several different types of manganate ions. These are distinguished by their oxidation states. There is hypomanganate, also known as manganate(V). There is also permanganate, which is manganate(VII). Another type is the dimanganate(III) ion. Scientists have even prepared a manganate(IV) anion. They did this through the radiolysis of dilute permanganate solutions.

Manganate
Manganate

In dilute solutions, the manganate(VI) ion appears as a dark green liquid. It shows a strong absorption in the ultraviolet spectrum. It also shows a weaker absorption at 650 nm. Its visible absorption maximum is at 606 nm.

Research into these structures began in the early 19th century. In 1831, the scientist Eilhard Mitscherlich noted that manganates share structures with sulfates and chromates. This discovery helped chemists understand how different elements can form similar shapes. Since then, scientists have used advanced tools like Raman spectroscopy to study them. They have also used pulse radiolysis techniques to estimate chemical constants. For example, they estimated the second acid dissociation constant for the hypothetical manganic acid. This constant, known as pKa, is 7.4 ± 0.1.

Manganates are often prepared through specific chemical processes. In a laboratory, scientists can make sodium and potassium manganates. They do this by stirring permanganate in a concentrated solution of hydroxide. This solution is usually 5–10 M. The stirring process can take 24 hours or involve heating.

Manganate
Manganate

On an industrial scale, potassium manganate is produced as an intermediate. It is made to create potassium permanganate. To do this, manganese dioxide is dissolved in molten potassium hydroxide. An oxidizing agent, such as air or potassium nitrate, is added to the mixture.

These compounds are very useful as oxidizing agents in organic synthesis. An oxidizing agent is a substance that causes other chemicals to lose electrons.

Manganate
Manganate

Barium manganate, BaMnO4, is particularly useful because it is insoluble. It can oxidize primary alcohols into aldehydes. These aldehydes can then be turned into carboxylic acids. It can also turn secondary alcohols into ketones. Additionally, barium manganate can oxidize hydrazones into diazo compounds.

Despite their uses, manganates are not always stable. They are prone to a process called disproportionation. This happens when a single substance breaks down into different products. This occurs in all aqueous solutions unless they are very alkaline. The ultimate products of this breakdown are permanganate and manganese dioxide. The exact mechanism is complex. It may involve species that are protonated or involve manganese(V). Finally, the term "manganite" is sometimes used for related compounds. These were once thought to contain the Mn(III) anion. However, most are actually mixed oxides with structures like perovskite, spinel, or sodium chloride.

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