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Concept
Manganese dioxide
Summary
Manganese dioxide is the inorganic compound with the formula MnO2. 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 MnO2 is for dry-cell batteries, such as the alkaline battery and the zinc–carbon battery. MnO2 is also used as a pigment and as a precursor to other manganese compounds, such as potassium permanganateKMnO4. It is used as a reagent in organic synthesis, for example, for the oxidation of allylic alcohols. MnO2 has an α-polymorph that can incorporate a variety of atoms (as well as water molecules) in the "tunnels" or "channels" between the manganese oxide octahedra. There is considerable interest in α-MnO2 as a possible cathode for lithium-ion batteries.
Several polymorphs of MnO2 are claimed, as well as a hydrated form. Like many other dioxides, MnO2 crystallizes in the rutile crystal structure (this polymorph is called pyrolusite or β-MnO2), with three-coordinate oxide and octahedral metal centres. MnO2 is characteristically nonstoichiometric, being deficient in oxygen. The complicated solid-state chemistry of this material is relevant to the lore of "freshly prepared" MnO2 in organic synthesis. The α-polymorph of MnO2 has a very open structure with "channels" which can accommodate metal atoms such as silver or barium. α-MnO2 is often called hollandite, after a closely related mineral.
Naturally occurring manganese dioxide contains impurities and a considerable amount of manganese(III) oxide. Production of batteries and ferrite (two of the primary uses of manganese dioxide) requires high purity manganese dioxide. Batteries require "electrolytic manganese dioxide" while ferrites require "chemical manganese dioxide".
One method starts with natural manganese dioxide and converts it using dinitrogen tetroxide and water to a manganese(II) nitrate solution. Evaporation of the water leaves the crystalline nitrate salt. At temperatures of 400 °C, the salt decomposes, releasing N2O4 and leaving a residue of purified manganese dioxide.
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