Pyrolusite is a
mineral
In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid substance with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. (2011): Mi ...
consisting essentially of
manganese dioxide
Manganese dioxide is the inorganic compound with the formula . 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 is for dry-cel ...
(
Mn O2) and is important as an
ore of manganese.
[.] It is a black,
amorphous
In condensed matter physics and materials science, an amorphous solid (or non-crystalline solid) is a solid that lacks the long-range order that is a characteristic of a crystal. The terms "glass" and "glassy solid" are sometimes used synonymousl ...
appearing mineral, often with a granular, fibrous, or columnar structure, sometimes forming
reniform crusts. It has a metallic
luster, a black or bluish-black streak, and readily soils the fingers. The
specific gravity
Relative density, also called specific gravity, is a dimensionless quantity defined as the ratio of the density (mass of a unit volume) of a substance to the density of a given reference material. Specific gravity for solids and liquids is nea ...
is about 4.8. Its name is from the Greek for ''fire'' and to ''wash'', in reference to its use as a way to remove tints from glass.
[
]
Occurrence
Pyrolusite and romanechite are among the most common manganese minerals.
Pyrolusite occurs associated with manganite, hollandite, hausmannite, braunite, cryptomelane, chalcophanite, goethite
Goethite (, ) is a mineral of the diaspore group, consisting of iron(III) oxide-hydroxide, specifically the α- polymorph. It is found in soil and other low-temperature environments such as sediment. Goethite has been well known since ancient t ...
, and hematite
Hematite (), also spelled as haematite, is a common iron oxide compound with the formula, Fe2O3 and is widely found in rocks and soils. Hematite crystals belong to the rhombohedral lattice system which is designated the alpha polymorph of . ...
under oxidizing
Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
conditions in hydrothermal
Hydrothermal circulation in its most general sense is the circulation of hot water (Ancient Greek ὕδωρ, ''water'',Liddell, H.G. & Scott, R. (1940). ''A Greek-English Lexicon. revised and augmented throughout by Sir Henry Stuart Jones. with th ...
deposits. It also occurs in bog
A bog or bogland is a wetland that accumulates peat as a deposit of dead plant materials often mosses, typically sphagnum moss. It is one of the four main types of wetlands. Other names for bogs include mire, mosses, quagmire, and musk ...
s and often results from alteration of manganite.[
]
Use
The metal is obtained by reduction of the oxide with sodium
Sodium is a chemical element; it has Symbol (chemistry), symbol Na (from Neo-Latin ) and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the peri ...
, magnesium
Magnesium is a chemical element; it has Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 ...
, aluminium
Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
, or by electrolysis
In chemistry and manufacturing, electrolysis is a technique that uses Direct current, direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of c ...
. Pyrolusite is extensively used for the manufacture of spiegeleisen and ferromanganese and of various alloys such as manganese-bronze
Bronze is an alloy consisting primarily of copper, commonly with about 12–12.5% tin and often with the addition of other metals (including aluminium, manganese, nickel, or zinc) and sometimes non-metals (such as phosphorus) or metalloid ...
. As an oxidizing agent it is used in the preparation of chlorine
Chlorine is a chemical element; it has Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between ...
; indeed, chlorine gas itself was first described by Karl Scheele in 1774 from the reaction products of pyrolusite and hydrochloric acid
Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...
. Natural pyrolusite has been used in batteries, but high-quality batteries require synthetic products. Pyrolusite is also used to prepare disinfectants (permanganate
A permanganate () is a chemical compound with the manganate(VII) ion, , the conjugate base of permanganic acid. Because the manganese atom has a +7 oxidation state, the permanganate(VII) ion is a strong oxidising agent. The ion is a transition ...
s) and for decolorizing glass. When mixed with molten glass it oxidizes the ferrous iron
Iron is a chemical element; it has symbol Fe () and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, forming much of Earth's o ...
to ferric iron, and so discharges the green and brown tints (making it classically useful to glassmakers as a decolorizer). As a coloring material, it is used in calico printing and dyeing; for imparting violet, amber
Amber is fossilized tree resin. Examples of it have been appreciated for its color and natural beauty since the Neolithic times, and worked as a gemstone since antiquity."Amber" (2004). In Maxine N. Lurie and Marc Mappen (eds.) ''Encyclopedia ...
, and black colors to glass, pottery, and bricks; and in the manufacture of green and violet paints.
Dendritic manganese oxides
Black, manganese oxides with a dendritic crystal habit
In mineralogy, crystal habit is the characteristic external shape of an individual crystal or aggregate of crystals. The habit of a crystal is dependent on its crystallographic form and growth conditions, which generally creates irregularities d ...
often found on fracture or rock surfaces are often assumed to be pyrolusite although careful analyses of numerous examples of these dendrites has shown that none of them are, in fact, pyrolusite. Instead, they are other forms of manganese oxide.
History
Some of the most famous early cave paintings in Europe were executed by means of manganese dioxide. Blocks of pyrolusite are found often at Neanderthal
Neanderthals ( ; ''Homo neanderthalensis'' or sometimes ''H. sapiens neanderthalensis'') are an extinction, extinct group of archaic humans who inhabited Europe and Western and Central Asia during the Middle Pleistocene, Middle to Late Plei ...
sites. It may have been kept as a pigment for cave painting
In archaeology, cave paintings are a type of parietal art (which category also includes petroglyphs, or engravings), found on the wall or ceilings of caves. The term usually implies prehistoric art, prehistoric origin. These paintings were often c ...
s, but it has also been suggested that it was powdered and mixed with tinder fungus for lighting fires. Manganese dioxide, in the form of umber
Umber is a natural earth pigment consisting of iron oxide and manganese oxide; it has a brownish color that can vary among shades of yellow, red, and green. Umber is considered one of the oldest pigments known to humans, first used in the Ajant ...
, was one of the earliest natural substances used by human ancestors. It was used as a pigment
A pigment is a powder used to add or alter color or change visual appearance. Pigments are completely or nearly solubility, insoluble and reactivity (chemistry), chemically unreactive in water or another medium; in contrast, dyes are colored sub ...
at least from the Middle Paleolithic
The Middle Paleolithic (or Middle Palaeolithic) is the second subdivision of the Paleolithic or Old Stone Age as it is understood in Europe, Africa and Asia. The term Middle Stone Age is used as an equivalent or a synonym for the Middle P ...
. It may have been also used by the Neanderthals
Neanderthals ( ; ''Homo neanderthalensis'' or sometimes ''H. sapiens neanderthalensis'') are an extinction, extinct group of archaic humans who inhabited Europe and Western and Central Asia during the Middle Pleistocene, Middle to Late Plei ...
in fire-making.
The ancient Greeks had a term μάγνης or Μάγνης λίθος ("Magnes lithos") meaning stone of the area called Μαγνησία (Magnesia), referring to Magnesia in Thessaly or to areas in Asia Minor
Anatolia (), also known as Asia Minor, is a peninsula in West Asia that makes up the majority of the land area of Turkey. It is the westernmost protrusion of Asia and is geographically bounded by the Mediterranean Sea to the south, the Aegean ...
with that name. Two minerals are called μάγνης, namely lodestone
Lodestones are naturally magnetization, magnetized pieces of the mineral magnetite. They are naturally occurring magnets, which can attract iron. The property of magnetism was first discovered in Ancient history, antiquity through lodeston ...
and pyrolusite (manganese dioxide).(not to be confused with the current mineral called Lodestone, which does not contain Manganese. Lodestone is a naturally magnetized form of the iron mineral Magnetite. FeFe2O4)
The term μαγνησία was used for manganese dioxide. In the sixteenth century it was called "manganesum". It also was called Alabandicus (from the Alabanda region of Asia Minor) and Braunstein. Eventually the name of the element manganese was derived from "manganesum", whereas "magnesia" came to mean the oxide of a different element, magnesium
Magnesium is a chemical element; it has Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group 2 ...
.
See also
Other manganese oxides:
* Birnessite
* Psilomelane
Psilomelane is a group name for hard black manganese oxides including hollandite and romanechite. Psilomelane consists of hydrous manganese oxide with variable amounts of barium and potassium. Psilomelane is erroneously, and uncommonly, known as ...
References
{{ores
Manganese(IV) minerals
Oxide minerals
Rutile group
Tetragonal minerals
Minerals in space group 136