Pyrolusite Dendritic On Felsite
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Pyrolusite is a
mineral In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid chemical compound with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. ( ...
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-cell ...
( Mn O2) and is important as an
ore Ore is natural rock or sediment that contains one or more valuable minerals, typically containing metals, that can be mined, treated and sold at a profit.Encyclopædia Britannica. "Ore". Encyclopædia Britannica Online. Retrieved 7 Apr ...
of manganese.. It is a black,
amorphous In condensed matter physics and materials science, an amorphous solid (or non-crystalline solid, glassy solid) is a solid that lacks the long-range order that is characteristic of a crystal. Etymology The term comes from the Greek ''a'' ("wi ...
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, or specific gravity, is the ratio of the density (mass of a unit volume) of a substance to the density of a given reference material. Specific gravity for liquids is nearly always measured with respect to water (molecule), wa ...
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 Manganite is a mineral composed of manganese oxide-hydroxide, MnO(OH), crystallizing in the monoclinic system (pseudo-orthorhombic). Crystals of manganite are prismatic and deeply striated parallel to their length; they are often grouped togethe ...
,
hollandite Hollandite (chemical formula: Ba(Mn4+6Mn3+2)O16) is an oxide mineral. It is the barium-manganese (III) endmember of the coronadite group. A mineral, with the chemical composition BaMn4+6Fe3+2O16, that was first found in the Kajlidongri mine in ...
,
hausmannite Hausmannite is a complex oxide of manganese containing both di- and tri-valent manganese. The formula can be represented as Mn2+Mn3+2O4. It belongs to the spinel group and forms tetragonal crystals. Hausmannite is a brown to black metallic minera ...
,
braunite Braunite is a silicate mineral containing both di- and tri- valent manganese with the chemical formula: Mn2+Mn3+6 SiO4 Common impurities include iron, calcium, boron, barium, titanium, aluminium, and magnesium. Braunite forms grey/black tetragon ...
, 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, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
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 bogs and often results from alteration of manganite.


Use

The metal is obtained by reduction of the oxide with
sodium Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable iso ...
,
magnesium Magnesium is a chemical element with the 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 of the periodic ta ...
,
aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
, or by
electrolysis In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from n ...
. Pyrolusite is extensively used for the manufacture of
spiegeleisen Spiegeleisen (literally "mirror-iron", —mirror or specular; —iron) is a ferromanganese alloy containing approximately 15% manganese and small quantities of carbon and silicon. Spiegeleisen is sometimes also referred to as ''specular pig iron' ...
and
ferromanganese Ferromanganese is a ferroalloy with high manganese content (high-carbon ferromanganese can contain as much as 80% Mn by weight). It is made by heating a mixture of the oxides MnO2 and Fe2O3, with carbon (usually as coal and coke) in either a bla ...
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 metalloids such ...
. As an oxidizing agent it is used in the preparation of
chlorine Chlorine is a chemical element with the 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 betwee ...
; indeed, chlorine gas itself was first described by
Karl Scheele Carl Wilhelm Scheele (, ; 9 December 1742 – 21 May 1786) was a Swedish German pharmaceutical chemist. Scheele discovered oxygen (although Joseph Priestley published his findings first), and identified molybdenum, tungsten, barium, hydro ...
in 1774 from the reaction products of pyrolusite and
hydrochloric acid Hydrochloric acid, also known as muriatic acid, is an aqueous solution of hydrogen chloride. It is a colorless solution with a distinctive pungent smell. It is classified as a strong acid Acid strength is the tendency of an acid, symbol ...
. 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 containing the manganate(VII) ion, , the conjugate base of permanganic acid. Because the manganese atom is in the +7 oxidation state, the permanganate(VII) ion is a strong oxidizing agent. The ion is a tra ...
s) and for decolorizing glass. When mixed with molten glass it oxidizes the ferrous
iron Iron () is a chemical element with symbol Fe (from la, ferrum) 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, right in f ...
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 that has been appreciated for its color and natural beauty since Neolithic times. Much valued from antiquity to the present as a gemstone, amber is made into a variety of decorative objects."Amber" (2004). In Ma ...
, 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 Dendrite derives from the Greek word "dendron" meaning ( "tree-like"), and may refer to: Biology *Dendrite, a branched projection of a neuron *Dendrite (non-neuronal), branching projections of certain skin cells and immune cells Physical * Dendr ...
crystal habit In mineralogy, crystal habit is the characteristic external shape of an individual crystal or crystal group. The habit of a crystal is dependent on its crystallographic form and growth conditions, which generally creates irregularities due to l ...
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 (, also ''Homo neanderthalensis'' and erroneously ''Homo sapiens neanderthalensis''), also written as Neandertals, are an extinct species or subspecies of archaic humans who lived in Eurasia until about 40,000 years ago. While th ...
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 origin, and the oldest known are more than 40,000 ye ...
s, but it has also been suggested that it was powdered and mixed with
tinder fungus ''Fomes fomentarius'' (commonly known as the tinder fungus, false tinder fungus, hoof fungus, tinder conk, tinder polypore or ice man fungus) is a species of fungal plant pathogen found in Europe, Asia, Africa and North America. The species prod ...
for lighting fires. Manganese dioxide, in the form of
umber Umber is a natural brown earth pigment that contains iron oxide and manganese oxide. In its natural form, it is called raw umber. When Calcination, calcined, the color becomes warmer and it becomes known as burnt umber. Its name derives from '' ...
, was one of the earliest natural substances used by human ancestors. It was used as a
pigment A pigment is a colored material that is completely or nearly insoluble in water. In contrast, dyes are typically soluble, at least at some stage in their use. Generally dyes are often organic compounds whereas pigments are often inorganic compo ...
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 Paleoli ...
. It may have been also used by the
Neanderthals Neanderthals (, also ''Homo neanderthalensis'' and erroneously ''Homo sapiens neanderthalensis''), also written as Neandertals, are an Extinction, extinct species or subspecies of archaic humans who lived in Eurasia until about 40,000 years ag ...
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, tr, Anadolu Yarımadası), and the Anatolian plateau, also known as Asia Minor, is a large peninsula in Western Asia and the westernmost protrusion of the Asian continent. It constitutes the major part of modern-day Turkey. The re ...
with that name. Two minerals are called μάγνης, namely
lodestone Lodestones are naturally magnetized pieces of the mineral magnetite. They are naturally occurring magnets, which can attract iron. The property of magnetism was first discovered in antiquity through lodestones. Pieces of lodestone, suspen ...
and pyrolusite (manganese dioxide). Later the term μαγνησία was used for manganese dioxide. In the sixteenth century it was called "manganesum". It also was called Alabandicus (from the
Alabanda Alabanda ( grc, Ἀλάβανδα) or Antiochia of the Chrysaorians was a city of ancient Caria, Anatolia, the site of which is near Doğanyurt, Çine, Aydın Province, Turkey. The city is located in the saddle between two heights. The area is ...
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 with the 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 of the periodic ta ...
.


See also

Other manganese oxides: *
Birnessite Birnessite (nominally MnO2.''n''H2O) is a hydrous manganese dioxide mineral with a chemical formula of Na0.7Ca0.3Mn7O14·2.8H2O. It is the main manganese mineral species at the Earth's surface, and commonly occurs as fine-grained, poorly crystall ...
*
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