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54-571: It was established in 1938 in place of the village of Horodyshche, which contained a manganese mine ( mining town ) and was called Komintern from 1926 to 1938. It is considered that next to the modern city was located the Cossack Fort "Tomakivka Sich" in the 16th century that was destroyed by Tatars soon after the Kosiński Uprising . During World War II , Marhanets was under German occupation from 17 August 1941 until 5 February 1944. It

108-467: A half-life of 3.7 million years, Mn with a half-life of 312.2 days, and Mn with a half-life of 5.591 days. All of the remaining radioactive isotopes have half-lives of less than three hours, and the majority of less than one minute. The primary decay mode in isotopes lighter than the most abundant stable isotope, Mn, is electron capture and the primary mode in heavier isotopes is beta decay . Manganese also has three meta states . Manganese

162-409: A magnesia nigra (the black ore) from magnesia alba (a white ore, also from Magnesia, also useful in glassmaking). Michele Mercati called magnesia nigra manganesa , and finally the metal isolated from it became known as manganese ( German : Mangan ). The name magnesia eventually was then used to refer only to the white magnesia alba (magnesium oxide), which provided the name magnesium for

216-607: A lesser extent as rhodochrosite ( MnCO 3 ). The most important manganese ore is pyrolusite ( MnO 2 ). Other economically important manganese ores usually show a close spatial relation to the iron ores, such as sphalerite . Land-based resources are large but irregularly distributed. About 80% of the known world manganese resources are in South Africa; other important manganese deposits are in Ukraine, Australia, India, China, Gabon and Brazil. According to 1978 estimate,

270-442: A primitive cubic structure with 20 atoms per unit cell at two types of sites, which is as complex as that of any other elemental metal. It is easily obtained as a metastable phase at room temperature by rapid quenching. It does not show magnetic ordering , remaining paramagnetic down to the lowest temperature measured (1.1 K). Gamma manganese (γ-Mn) forms when heated above 1,370 K (1,100 °C; 2,010 °F). It has

324-447: A simple face-centered cubic structure (four atoms per unit cell). When quenched to room temperature it converts to β-Mn, but it can be stabilized at room temperature by alloying it with at least 5 percent of other elements (such as C, Fe, Ni, Cu, Pd or Au), and these solute-stabilized alloys distort into a face-centered tetragonal structure. Delta manganese (δ-Mn) forms when heated above 1,406 K (1,130 °C; 2,070 °F) and

378-436: Is MnO 2 . It is the dark brown pigment of many cave drawings but is also a common ingredient in dry cell batteries. Complexes of Mn(IV) are well known, but they require elaborate ligands . Mn(IV)-OH complexes are an intermediate in some enzymes , including the oxygen evolving center (OEC) in plants. Simple derivatives Mn are rarely encountered but can be stabilized by suitably basic ligands. Manganese(III) acetate

432-466: Is a brown pigment for paint and is a constituent of natural umber . Tetravalent manganese is used as an activator in red-emitting phosphors . While many compounds are known which show luminescence , the majority are not used in commercial application due to low efficiency or deep red emission. However, several Mn activated fluorides were reported as potential red-emitting phosphors for warm-white LEDs. But to this day, only K 2 SiF 6 :Mn

486-552: Is a commonly used laboratory reagent because of its oxidizing properties; it is used as a topical medicine (for example, in the treatment of fish diseases). Solutions of potassium permanganate were among the first stains and fixatives to be used in the preparation of biological cells and tissues for electron microscopy. Aside from various permanganate salts, Mn(VII) is represented by the unstable, volatile derivative Mn 2 O 7 . Oxyhalides (MnO 3 F and MnO 3 Cl) are powerful oxidizing agents . The most prominent example of Mn in

540-494: Is a silvery-gray metal that resembles iron. It is hard and very brittle, difficult to fuse, but easy to oxidize. Manganese and its common ions are paramagnetic . Manganese tarnishes slowly in air and oxidizes ("rusts") like iron in water containing dissolved oxygen. Naturally occurring manganese is composed of one stable isotope , Mn. Several radioisotopes have been isolated and described, ranging in atomic weight from 46 u ( Mn) to 72 u ( Mn). The most stable are Mn with

594-549: Is also seen in the mineral rhodochrosite ( manganese(II) carbonate ). Manganese(II) commonly exists with a high spin, S = 5/2 ground state because of the high pairing energy for manganese(II). There are no spin-allowed d–d transitions in manganese(II), which explain its faint color. Manganese forms a large variety of organometallic derivatives, i.e., compounds with Mn-C bonds. The organometallic derivatives include numerous examples of Mn in its lower oxidation states, i.e. Mn(−III) up through Mn(I). This area of organometallic chemistry

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648-574: Is an oxidant useful in organic synthesis . Solid compounds of manganese(III) are characterized by its strong purple-red color and a preference for distorted octahedral coordination resulting from the Jahn-Teller effect . A particularly common oxidation state for manganese in aqueous solution is +2, which has a pale pink color. Many manganese(II) compounds are known, such as the aquo complexes derived from manganese(II) sulfate (MnSO 4 ) and manganese(II) chloride (MnCl 2 ). This oxidation state

702-464: Is attractive because Mn is inexpensive and of relatively low toxicity. Of greatest commercial interest is "MMT", methylcyclopentadienyl manganese tricarbonyl , which is used as an anti-knock compound added to gasoline (petrol) in some countries. It features Mn(I). Consistent with other aspects of Mn(II) chemistry, manganocene ( Mn(C 5 H 5 ) 2 ) is high-spin. In contrast, its neighboring metal iron forms an air-stable, low-spin derivative in

756-421: Is dominant in a given soil. At pH values less than 6 or under anaerobic conditions, Mn(II) dominates, while under more alkaline and aerobic conditions, Mn(III,IV) oxides and hydroxides predominate. These effects of soil acidity and aeration state on the form of Mn can be modified or controlled by microbial activity. Microbial respiration can cause both the oxidation of Mn to the oxides, and it can cause reduction of

810-545: Is found throughout the world's oceans, 90% of which originates from hydrothermal vents. Particulate Mn develops in buoyant plumes over an active vent source, while the dMn behaves conservatively. Mn concentrations vary between the water columns of the ocean. At the surface, dMn is elevated due to input from external sources such as rivers, dust, and shelf sediments. Coastal sediments normally have lower Mn concentrations, but can increase due to anthropogenic discharges from industries such as mining and steel manufacturing, which enter

864-458: Is low spin, which contrasts with the high spin character of its precursor, MnBr 2 (dmpe) 2 ( dmpe = (CH 3 ) 2 PCH 2 CH 2 P(CH 3 ) 2 ). Polyalkyl and polyaryl derivatives of manganese often exist in higher oxidation states, reflecting the electron-releasing properties of alkyl and aryl ligands. One example is [Mn(CH 3 ) 6 ] . The origin of the name manganese is complex. In ancient times, two black minerals were identified from

918-408: Is mainly mined in South Africa, Australia, China, Gabon, Brazil, India, Kazakhstan, Ghana, Ukraine and Malaysia. For the production of ferromanganese , the manganese ore is mixed with iron ore and carbon, and then reduced either in a blast furnace or in an electric arc furnace. The resulting ferromanganese has a manganese content of 30–80%. Pure manganese used for the production of iron-free alloys

972-501: Is part of the iron group of elements, which are thought to be synthesized in large stars shortly before the supernova explosion. Mn decays to Cr with a half-life of 3.7 million years. Because of its relatively short half-life, Mn is relatively rare, produced by cosmic rays impact on iron . Manganese isotopic contents are typically combined with chromium isotopic contents and have found application in isotope geology and radiometric dating . Mn–Cr isotopic ratios reinforce

1026-424: Is produced by leaching manganese ore with sulfuric acid and a subsequent electrowinning process. A more progressive extraction process involves directly reducing (a low grade) manganese ore by heap leaching . This is done by percolating natural gas through the bottom of the heap; the natural gas provides the heat (needs to be at least 850 °C) and the reducing agent (carbon monoxide). This reduces all of

1080-442: Is stable up to the manganese melting point of 1,519 K (1,250 °C; 2,270 °F). It has a body-centered cubic structure (two atoms per cubic unit cell). Common oxidation states of manganese are +2, +3, +4, +6, and +7, although all oxidation states from −3 to +7 have been observed. Manganese in oxidation state +7 is represented by salts of the intensely purple permanganate anion MnO − 4 . Potassium permanganate

1134-405: Is unusual among elemental metals in having a very complex unit cell, with 58 atoms per cell (29 atoms per primitive unit cell) in four different types of site. It is paramagnetic at room temperature and antiferromagnetic at temperatures below 95 K (−178 °C). Beta manganese (β-Mn) forms when heated above the transition temperature of 973 K (700 °C; 1,290 °F). It has

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1188-412: Is used as a reagent in organic chemistry for the oxidation of benzylic alcohols (where the hydroxyl group is adjacent to an aromatic ring ). Manganese dioxide has been used since antiquity to oxidize and neutralize the greenish tinge in glass from trace amounts of iron contamination. MnO 2 is also used in the manufacture of oxygen and chlorine and in drying black paints. In some preparations, it

1242-433: Is used as an oxidising agent; as a rubber additive; and in glass making, fertilisers, and ceramics. Manganese sulfate can be used as a fungicide. Manganese is also an essential human dietary element, important in macronutrient metabolism, bone formation, and free radical defense systems. It is a critical component in dozens of proteins and enzymes. It is found mostly in the bones, but also the liver, kidneys, and brain. In

1296-496: The Middle Ages until modern times and is evident in 14th-century glass from Venice . Because it was used in glassmaking, manganese dioxide was available for experiments by alchemists, the first chemists. Ignatius Gottfried Kaim (1770) and Johann Glauber (17th century) discovered that manganese dioxide could be converted to permanganate , a useful laboratory reagent. Kaim also may have reduced manganese dioxide to isolate

1350-602: The Spartan steel exceptionally hard. Around the beginning of the 19th century, manganese was used in steelmaking and several patents were granted. In 1816, it was documented that iron alloyed with manganese was harder but not more brittle. In 1837, British academic James Couper noted an association between miners' heavy exposure to manganese and a form of Parkinson's disease . In 1912, United States patents were granted for protecting firearms against rust and corrosion with manganese phosphate electrochemical conversion coatings, and

1404-523: The ocean floor has 500 billion tons of manganese nodules . Attempts to find economically viable methods of harvesting manganese nodules were abandoned in the 1970s. In South Africa, most identified deposits are located near Hotazel in the Northern Cape Province , ( Kalahari manganese fields ), with a 2011 estimate of 15 billion tons. In 2011 South Africa produced 3.4 million tons, topping all other nations. Manganese

1458-476: The +6 oxidation state is the green anion manganate , [MnO 4 ] . Manganate salts are intermediates in the extraction of manganese from its ores. Compounds with oxidation states +5 are somewhat elusive, and often found associated to an oxide (O ) or nitride (N ) ligand. One example is the blue anion hypomanganate [MnO 4 ] . Mn(IV) is somewhat enigmatic because it is common in nature but far rarer in synthetic chemistry. The most common Mn ore, pyrolusite ,

1512-491: The 2020s. The real mission of Hughes Glomar Explorer was to raise a sunken Soviet submarine, the K-129 , with the goal of retrieving Soviet code books. An abundant resource of manganese in the form of manganese nodules found on the ocean floor. These nodules, which are composed of 29% manganese, are located along the ocean floor . The environmental impacts of nodule collection are of interest. Dissolved manganese (dMn)

1566-479: The 20th century, manganese dioxide was widely used as the cathodic for commercial disposable dry batteries of both the standard (zinc–carbon) and alkaline types. Manganese is essential to iron and steel production by virtue of its sulfur -fixing, deoxidizing , and alloying properties. This application was first recognized by the British metallurgist Robert Forester Mushet (1811–1891) who, in 1856, introduced

1620-471: The Solar System. Four allotropes (structural forms) of solid manganese are known, labeled α, β, γ and δ, and occurring at successively higher temperatures. All are metallic, stable at standard pressure, and have a cubic crystal lattice, but they vary widely in their atomic structures. Alpha manganese (α-Mn) is the equilibrium phase at room temperature. It has a body-centered cubic lattice and

1674-567: The alloys particularly useful in harsh automotive and industrial environments. Manganese oxide and sulfate are components of fertilizers. In the year 2000, an estimated 20,000 tons of these compounds were used in fertilizers in the US alone. A comparable amount of Mn compounds was also used in animal feeds. Methylcyclopentadienyl manganese tricarbonyl is an additive in some unleaded gasoline to boost octane rating and reduce engine knocking . Manganese(IV) oxide (manganese dioxide, MnO 2 )

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1728-481: The element, in the form of Spiegeleisen . Manganese comprises about 1000  ppm (0.1%) of the Earth's crust and is the 12th most abundant element. Soil contains 7–9000 ppm of manganese with an average of 440 ppm. The atmosphere contains 0.01 μg/m . Manganese occurs principally as pyrolusite ( MnO 2 ), braunite (Mn Mn 6 )SiO 12 ), psilomelane (Ba,H 2 O) 2 Mn 5 O 10 , and to

1782-518: The evidence from Al and Pd for the early history of the Solar System . Variations in Cr/ Cr and Mn/Cr ratios from several meteorites suggest an initial Mn/ Mn ratio, which indicate that Mn–Cr isotopic composition must result from in situ decay of Mn in differentiated planetary bodies. Hence, Mn provides additional evidence for nucleosynthetic processes immediately before coalescence of

1836-491: The form of ferrocene ( Fe(C 5 H 5 ) 2 ). When conducted under an atmosphere of carbon monoxide , reduction of Mn(II) salts gives dimanganese decacarbonyl Mn 2 (CO) 10 , an orange and volatile solid. The air-stability of this Mn(0) compound (and its many derivatives) reflects the powerful electron-acceptor properties of carbon monoxide. Many alkene complexes and alkyne complexes are derived from Mn 2 (CO) 10 . In Mn(CH 3 ) 2 (dmpe) 2 , Mn(II)

1890-465: The free element when it was isolated much later. Manganese dioxide, which is abundant in nature, has long been used as a pigment. The cave paintings in Gargas that are 30,000 to 24,000 years old are made from the mineral form of MnO 2 pigments. Manganese compounds were used by Egyptian and Roman glassmakers, either to add to, or remove, color from glass. Use as "glassmakers soap" continued through

1944-410: The human brain, the manganese is bound to manganese metalloproteins , most notably glutamine synthetase in astrocytes . It is familiar in the laboratory in the form of the deep violet salt potassium permanganate . It occurs at the active sites in some enzymes . Of particular interest is the use of a Mn-O cluster , the oxygen-evolving complex , in the production of oxygen by plants. Manganese

1998-412: The manganese content reaches 4%, the embrittlement of the steel becomes a dominant feature. The embrittlement decreases at higher manganese concentrations and reaches an acceptable level at 8%. Steel containing 8 to 15% of manganese has a high tensile strength of up to 863 MPa. Steel with 12% manganese was discovered in 1882 by Robert Hadfield and is still known as Hadfield steel (mangalloy) . It

2052-503: The manganese ore to manganese oxide (MnO), which is a leachable form. The ore then travels through a grinding circuit to reduce the particle size of the ore to between 150 and 250 μm, increasing the surface area to aid leaching. The ore is then added to a leach tank of sulfuric acid and ferrous iron (Fe ) in a 1.6:1 ratio. The iron reacts with the manganese dioxide (MnO 2 ) to form iron hydroxide (FeO(OH)) and elemental manganese (Mn). This process yields approximately 92% recovery of

2106-460: The manganese. For further purification, the manganese can then be sent to an electrowinning facility. In 1972, the CIA 's Project Azorian , through billionaire Howard Hughes , commissioned the ship Hughes Glomar Explorer with the cover story of harvesting manganese nodules from the sea floor. That triggered a rush of activity to collect manganese nodules, which was not actually practical until

2160-633: The metal, but that is uncertain. By the mid-18th century, the Swedish chemist Carl Wilhelm Scheele used manganese dioxide to produce chlorine . First, hydrochloric acid , or a mixture of dilute sulfuric acid and sodium chloride was made to react with manganese dioxide, and later hydrochloric acid from the Leblanc process was used and the manganese dioxide was recycled by the Weldon process . The production of chlorine and hypochlorite bleaching agents

2214-573: The metals and organic compounds can then cause them to be oxidized while the Mn(III,IV) oxides are reduced to Mn (e.g., Cr to Cr(VI) and colorless hydroquinone to tea-colored quinone polymers). Manganese is essential to iron and steel production by virtue of its sulfur -fixing, deoxidizing , and alloying properties. Manganese has no satisfactory substitute in these applications in metallurgy. Steelmaking , including its ironmaking component, has accounted for most manganese demand, presently in

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2268-555: The number of raions of Dnipropetrovsk Oblast to seven. The area of Marhanets Municipality was merged into Nikopol Raion. Manganese Manganese is a chemical element ; it has symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron . Manganese was first isolated in the 1770s. It is a transition metal with a multifaceted array of industrial alloy uses, particularly in stainless steels . It improves strength, workability, and resistance to wear. Manganese oxide

2322-524: The ocean from river inputs. Surface dMn concentrations can also be elevated biologically through photosynthesis and physically from coastal upwelling and wind-driven surface currents. Internal cycling such as photo-reduction from UV radiation can also elevate levels by speeding up the dissolution of Mn-oxides and oxidative scavenging, preventing Mn from sinking to deeper waters. Elevated levels at mid-depths can occur near mid-ocean ridges and hydrothermal vents. The hydrothermal vents release dMn enriched fluid into

2376-441: The oxides to the divalent cation. The Mn(III,IV) oxides exist as brownish-black stains and small nodules on sand, silt, and clay particles. These surface coatings on other soil particles have high surface area and carry negative charge. The charged sites can adsorb and retain various cations, especially heavy metals (e.g., Cr , Cu , Zn , and Pb ). In addition, the oxides can adsorb organic acids and other compounds. The adsorption of

2430-576: The process has seen widespread use ever since. The invention of the Leclanché cell in 1866 and the subsequent improvement of batteries containing manganese dioxide as cathodic depolarizer increased the demand for manganese dioxide. Until the development of batteries with nickel–cadmium and lithium, most batteries contained manganese. The zinc–carbon battery and the alkaline battery normally use industrially produced manganese dioxide because naturally occurring manganese dioxide contains impurities. In

2484-400: The range of 85% to 90% of the total demand. Manganese is a key component of low-cost stainless steel . Often ferromanganese (usually about 80% manganese) is the intermediate in modern processes. Small amounts of manganese improve the workability of steel at high temperatures by forming a high-melting sulfide and preventing the formation of a liquid iron sulfide at the grain boundaries. If

2538-481: The regions of the Magnetes (either Magnesia , located within modern Greece, or Magnesia ad Sipylum , located within modern Turkey). They were both called magnes from their place of origin, but were considered to differ in sex. The male magnes attracted iron, and was the iron ore now known as lodestone or magnetite , and which probably gave us the term magnet . The female magnes ore did not attract iron, but

2592-415: The same basic reaction, but a different electrolyte mixture. In 2002, more than 230,000 tons of manganese dioxide was used for this purpose. Copper alloys of manganese, such as Manganin , are commonly found in metal element shunt resistors used for measuring relatively large amounts of current. These alloys have very low temperature coefficient of resistance and are resistant to sulfur. This makes

2646-589: The water. The dMn can then travel up to 4,000 km due to the microbial capsules present, preventing exchange with particles, lowing the sinking rates. Dissolved Mn concentrations are even higher when oxygen levels are low. Overall, dMn concentrations are normally higher in coastal regions and decrease when moving offshore. Manganese occurs in soils in three oxidation states: the divalent cation, Mn and as brownish-black oxides and hydroxides containing Mn (III,IV), such as MnOOH and MnO 2 . Soil pH and oxidation-reduction conditions affect which of these three forms of Mn

2700-482: Was a large consumer of manganese ores. Scheele and others were aware that pyrolusite (mineral form of manganese dioxide) contained a new element. Johan Gottlieb Gahn isolated an impure sample of manganese metal in 1774, which he did by reducing the dioxide with carbon . The manganese content of some iron ores used in Greece led to speculations that steel produced from that ore contains additional manganese, making

2754-540: Was administered as a part of Reichskommissariat Ukraine . The Germans operated a forced labour camp in the town. On October 12, 2010, at least 43 people died in the Marhanets train accident . Until 18 July 2020, Marhanets was incorporated as a city of oblast significance and the center of Marhanets Municipality . The municipality was abolished in July 2020 as part of the administrative reform of Ukraine, which reduced

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2808-572: Was used for British military steel helmets and later by the U.S. military. Manganese is used in production of alloys with aluminium. Aluminium with roughly 1.5% manganese has increased resistance to corrosion through grains that absorb impurities which would lead to galvanic corrosion . The corrosion-resistant aluminium alloys 3004 and 3104 (0.8 to 1.5% manganese) are used for most beverage cans . Before 2000, more than 1.6 million tonnes of those alloys were used; at 1% manganese, this consumed 16,000 tonnes of manganese. Manganese(IV) oxide

2862-414: Was used in the original type of dry cell battery as an electron acceptor from zinc, and is the blackish material in carbon–zinc type flashlight cells. The manganese dioxide is reduced to the manganese oxide-hydroxide MnO(OH) during discharging, preventing the formation of hydrogen at the anode of the battery. The same material also functions in newer alkaline batteries (usually battery cells), which use

2916-438: Was used to decolorize glass. This female magnes was later called magnesia , known now in modern times as pyrolusite or manganese dioxide . Neither this mineral nor elemental manganese is magnetic. In the 16th century, manganese dioxide was called manganesum (note the two Ns instead of one) by glassmakers, possibly as a corruption and concatenation of two words, since alchemists and glassmakers eventually had to differentiate

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