Molybdenum Mines In Mongolia
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Molybdenum is a chemical element with the
symbol A symbol is a mark, sign, or word that indicates, signifies, or is understood as representing an idea, object, or relationship. Symbols allow people to go beyond what is known or seen by creating linkages between otherwise very different conc ...
Mo and atomic number 42 which is located in period 5 and group 6. The name is from
Neo-Latin New Latin (also called Neo-Latin or Modern Latin) is the revival of Literary Latin used in original, scholarly, and scientific works since about 1500. Modern scholarly and technical nomenclature, such as in zoological and botanical taxonomy ...
''molybdaenum'', which is based on Ancient Greek ', meaning lead, since its ores were confused with lead ores. Molybdenum minerals have been known throughout history, but the element was discovered (in the sense of differentiating it as a new entity from the mineral salts of other metals) in 1778 by Carl Wilhelm Scheele. The metal was first isolated in 1781 by
Peter Jacob Hjelm Peter (Petter) Jacob Hjelm (2 October 1746 – 7 October 1813) was a Swedish chemist and the first person to isolate the element molybdenum in 1781, four years after its discovery by Swedish chemist Carl Wilhelm Scheele. Working with Molybdic a ...
. Molybdenum does not occur naturally as a free metal on Earth; it is found only in various oxidation states in minerals. The free element, a silvery metal with a grey cast, has the sixth-highest melting point of any element. It readily forms hard, stable carbides in alloys, and for this reason most of the world production of the element (about 80%) is used in
steel Steel is an alloy made up of iron with added carbon to improve its strength and fracture resistance compared to other forms of iron. Many other elements may be present or added. Stainless steels that are corrosion- and oxidation-resistant ty ...
alloys, including high-strength alloys and
superalloy A superalloy, or high-performance alloy, is an alloy with the ability to operate at a high fraction of its melting point. Several key characteristics of a superalloy are excellent mechanical strength, resistance to thermal creep deformation, g ...
s. Most molybdenum compounds have low solubility in water, but when molybdenum-bearing minerals contact oxygen and water, the resulting
molybdate In chemistry a molybdate is a compound containing an oxoanion with molybdenum in its highest oxidation state of 6. Molybdenum can form a very large range of such oxoanions which can be discrete structures or polymeric extended structures, althoug ...
ion is quite soluble. Industrially, molybdenum compounds (about 14% of world production of the element) are used in
high-pressure In science and engineering the study of high pressure examines its effects on materials and the design and construction of devices, such as a diamond anvil cell, which can create high pressure. By ''high pressure'' is usually meant pressures of th ...
and high-temperature applications as pigments and catalysts. are by far the most common bacterial catalysts for breaking the chemical bond in atmospheric molecular nitrogen in the process of biological nitrogen fixation. At least 50 molybdenum enzymes are now known in bacteria, plants, and animals, although only bacterial and cyanobacterial enzymes are involved in nitrogen fixation. These nitrogenases contain an iron-molybdenum cofactor FeMoco, which is believed to contain either Mo(III) or Mo(IV). This is distinct from the fully oxidized Mo(VI) found complexed with molybdopterin in all other molybdenum-bearing enzymes, which perform a variety of crucial functions. The variety of crucial reactions catalyzed by these latter enzymes means that molybdenum is an
essential element In the context of nutrition, a mineral is a chemical element required as an essential nutrient by organisms to perform functions necessary for life. However, the four major structural elements in the human body by weight (oxygen, hydrogen, carbon ...
for all higher
eukaryote Eukaryotes () are organisms whose cells have a nucleus. All animals, plants, fungi, and many unicellular organisms, are Eukaryotes. They belong to the group of organisms Eukaryota or Eukarya, which is one of the three domains of life. Bacte ...
organisms, including humans.


Characteristics


Physical properties

In its pure form, molybdenum is a silvery-grey metal with a Mohs hardness of 5.5 and a standard atomic weight of 95.95 g/mol. It has a melting point of ; of the naturally occurring elements, only tantalum,
osmium Osmium (from Greek grc, ὀσμή, osme, smell, label=none) is a chemical element with the symbol Os and atomic number 76. It is a hard, brittle, bluish-white transition metal in the platinum group that is found as a trace element in alloys, mos ...
, rhenium, tungsten, and carbon have higher melting points. It has one of the lowest coefficients of thermal expansion among commercially used metals.


Chemical properties

Molybdenum is a transition metal with an electronegativity of 2.16 on the Pauling scale. It does not visibly react with oxygen or water at room temperature. Weak oxidation of molybdenum starts at ; bulk oxidation occurs at temperatures above 600 °C, resulting in molybdenum trioxide. Like many heavier transition metals, molybdenum shows little inclination to form a cation in aqueous solution, although the Mo3+ cation is known under carefully controlled conditions. Gaseous molybdenum consists of the diatomic species Mo2. That molecule is a singlet, with two unpaired electrons in bonding orbitals, in addition to 5 conventional bonds. The result is a sextuple bond.


Isotopes

There are 35 known isotopes of molybdenum, ranging in atomic mass from 83 to 117, as well as four metastable nuclear isomers. Seven isotopes occur naturally, with atomic masses of 92, 94, 95, 96, 97, 98, and 100. Of these naturally occurring isotopes, only molybdenum-100 is unstable. Molybdenum-98 is the most abundant isotope, comprising 24.14% of all molybdenum. Molybdenum-100 has a half-life of about 1019  y and undergoes double beta decay into ruthenium-100. All unstable isotopes of molybdenum decay into isotopes of
niobium Niobium is a chemical element with chemical symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and ductile transition metal. Pure niobium has a Mohs hardness rating similar to pure titanium, and it has sim ...
, technetium, and ruthenium. Of the
synthetic radioisotope A synthetic radioisotope is a radionuclide that is not found in nature: no natural process or mechanism exists which produces it, or it is so unstable that it decays away in a very short period of time. Examples include technetium-95 and prometh ...
s, the most stable is 93Mo, with a half-life of 4,000 years. The most common isotopic molybdenum application involves molybdenum-99, which is a
fission product Nuclear fission products are the atomic fragments left after a large atomic nucleus undergoes nuclear fission. Typically, a large nucleus like that of uranium fissions by splitting into two smaller nuclei, along with a few neutrons, the release ...
. It is a
parent radioisotope In nuclear physics, a decay product (also known as a daughter product, daughter isotope, radio-daughter, or daughter nuclide) is the remaining nuclide left over from radioactive decay. Radioactive decay often proceeds via a sequence of steps (de ...
to the short-lived gamma-emitting daughter radioisotope technetium-99m, a nuclear isomer used in various imaging applications in medicine. In 2008, the Delft University of Technology applied for a patent on the molybdenum-98-based production of molybdenum-99.


Compounds

Molybdenum forms chemical compounds in oxidation states −IV and from −II to +VI. Higher oxidation states are more relevant to its terrestrial occurrence and its biological roles, mid-level oxidation states are often associated with metal clusters, and very low oxidation states are typically associated with
organomolybdenum compound Organomolybdenum chemistry is the chemistry of chemical compounds with Mo-C bonds. The heavier group 6 elements molybdenum and tungsten form organometallic compounds similar to those in organochromium chemistry but higher oxidation states tend t ...
s. Mo and W chemistry shows strong similarities. The relative rarity of molybdenum(III), for example, contrasts with the pervasiveness of the chromium(III) compounds. The highest oxidation state is seen in
molybdenum(VI) oxide Molybdenum trioxide describes a family of inorganic compounds with the formula MoO3(H2O)n where n = 0, 1, 2. These compounds are produced on the largest scale of any molybdenum compound. The anhydrous oxide is a precursor to molybdenum metal, ...
(MoO3), whereas the normal sulfur compound is
molybdenum disulfide Molybdenum disulfide (or moly) is an inorganic compound composed of molybdenum and sulfur. Its chemical formula is . The compound is classified as a transition metal dichalcogenide. It is a silvery black solid that occurs as the mineral molybdenit ...
MoS2. From the perspective of commerce, the most important compounds are molybdenum disulfide () and molybdenum trioxide (). The black disulfide is the main mineral. It is roasted in air to give the trioxide: :2 + 7 → 2 + 4 The trioxide, which is volatile at high temperatures, is the precursor to virtually all other Mo compounds as well as alloys. Molybdenum has several oxidation states, the most stable being +4 and +6 (bolded in the table at left). Molybdenum(VI) oxide is soluble in strong
alkaline In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a base (chemistry), basic, ionic compound, ionic salt (chemistry), salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as ...
water, forming molybdates (MoO42−). Molybdates are weaker oxidants than chromates. They tend to form structurally complex oxyanions by condensation at lower pH values, such as o7O24sup>6− and o8O26sup>4−. Polymolybdates can incorporate other ions, forming polyoxometalates. The dark-blue phosphorus-containing heteropolymolybdate P o12O40sup>3− is used for the spectroscopic detection of phosphorus. The broad range of oxidation states of molybdenum is reflected in various molybdenum chlorides: * Molybdenum(II) chloride MoCl2, which exists as the hexamer Mo6Cl12 and the related dianion o6Cl14sup>2-. *
Molybdenum(III) chloride Molybdenum(III) chloride is the inorganic compound with the formula MoCl3. It forms purple crystals. Synthesis and structure Molybdenum(III) chloride is synthesized by the reduction of molybdenum(V) chloride with hydrogen. A higher yield is pro ...
MoCl3, a dark red solid, which converts to the anion trianionic complex oCl6sup>3-. * Molybdenum(IV) chloride MoCl4, a black solid, which adopts a polymeric structure. * Molybdenum(V) chloride MoCl5 dark green solid, which adopts a dimeric structure. *
Molybdenum(VI) chloride Molybdenum(VI) chloride is the inorganic compound with the formula MoCl6. It is a black diamagnetic solid. The molecules adopt an octahedral structure as seen in β- tungsten(VI) chloride. Preparation and reactions Molybdenum(VI) chloride is pr ...
MoCl6 is a black solid, which is monomeric and slowly decomposes to MoCl5 and Cl2 at room temperature. Like
chromium Chromium is a chemical element with the symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal. Chromium metal is valued for its high corrosion resistance and hardne ...
and some other transition metals, molybdenum forms quadruple bonds, such as in Mo2(CH3COO)4 and o2Cl8sup>4−. The
Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any sp ...
properties of the butyrate and perfluorobutyrate dimers, Mo2(O2CR)4 and Rh2(O2CR) 4, have been reported. The oxidation state 0 and lower are possible with carbon monoxide as ligand, such as in molybdenum hexacarbonyl, Mo(CO)6.


History

Molybdenite—the principal ore from which molybdenum is now extracted—was previously known as molybdena. Molybdena was confused with and often utilized as though it were graphite. Like graphite, molybdenite can be used to blacken a surface or as a solid lubricant. Even when molybdena was distinguishable from graphite, it was still confused with the common lead ore PbS (now called
galena Galena, also called lead glance, is the natural mineral form of lead(II) sulfide (PbS). It is the most important ore of lead and an important source of silver. Galena is one of the most abundant and widely distributed sulfide minerals. It cryst ...
); the name comes from Ancient Greek ', meaning ''lead''. (The Greek word itself has been proposed as a loanword from
Anatolian Anatolian or anatolica may refer to: * Anything of, from, or related to the region Anatolia * Anatolians, ancient Indo-European peoples who spoke the Anatolian languages * Anatolian High School, a type of Turkish educational institution * Anatol ...
Luvian and Lydian languages). Although (reportedly) molybdenum was deliberately alloyed with steel in one 14th-century Japanese sword (mfd. ca. 1330), that art was never employed widely and was later lost. In the West in 1754, Bengt Andersson Qvist examined a sample of molybdenite and determined that it did not contain lead and thus was not galena. By 1778
Swedish Swedish or ' may refer to: Anything from or related to Sweden, a country in Northern Europe. Or, specifically: * Swedish language, a North Germanic language spoken primarily in Sweden and Finland ** Swedish alphabet, the official alphabet used by ...
chemist Carl Wilhelm Scheele stated firmly that molybdena was (indeed) neither galena nor graphite. Instead, Scheele correctly proposed that molybdena was an ore of a distinct new element, named ''molybdenum'' for the mineral in which it resided, and from which it might be isolated.
Peter Jacob Hjelm Peter (Petter) Jacob Hjelm (2 October 1746 – 7 October 1813) was a Swedish chemist and the first person to isolate the element molybdenum in 1781, four years after its discovery by Swedish chemist Carl Wilhelm Scheele. Working with Molybdic a ...
successfully isolated molybdenum using carbon and
linseed oil Linseed oil, also known as flaxseed oil or flax oil (in its edible form), is a colourless to yellowish oil obtained from the dried, ripened seeds of the flax plant (''Linum usitatissimum''). The oil is obtained by pressing, sometimes followed by ...
in 1781. For the next century, molybdenum had no industrial use. It was relatively scarce, the pure metal was difficult to extract, and the necessary techniques of metallurgy were immature. Early molybdenum steel alloys showed great promise of increased hardness, but efforts to manufacture the alloys on a large scale were hampered with inconsistent results, a tendency toward brittleness, and recrystallization. In 1906,
William D. Coolidge William David Coolidge (; October 23, 1873 – February 3, 1975) was an American physicist and engineer, who made major contributions to X-ray machines. He was the director of the General Electric Research Laboratory and a vice-president of t ...
filed a patent for rendering molybdenum ductile, leading to applications as a heating element for high-temperature furnaces and as a support for tungsten-filament light bulbs; oxide formation and degradation require that molybdenum be physically sealed or held in an inert gas. In 1913,
Frank E. Elmore Frank or Franks may refer to: People * Frank (given name) * Frank (surname) * Franks (surname) * Franks, a medieval Germanic people * Frank, a term in the Muslim world for all western Europeans, particularly during the Crusades - see Farang Curre ...
developed a
froth flotation process Froth flotation is a process for selectively separating hydrophobic materials from hydrophilic. This is used in mineral processing, paper recycling and waste-water treatment industries. Historically this was first used in the mining industry, wher ...
to recover molybdenite from ores; flotation remains the primary isolation process. During World War I, demand for molybdenum spiked; it was used both in armor plating and as a substitute for tungsten in high-speed steels. Some British tanks were protected by 75 mm (3 in)
manganese steel Mangalloy, also called manganese steel or Hadfield steel, is an alloy steel containing an average of around 13% manganese. Mangalloy is known for its high impact strength and resistance to abrasion once in its work-hardened state. Material proper ...
plating, but this proved to be ineffective. The manganese steel plates were replaced with much lighter molybdenum steel plates allowing for higher speed, greater maneuverability, and better protection. The Germans also used molybdenum-doped
steel Steel is an alloy made up of iron with added carbon to improve its strength and fracture resistance compared to other forms of iron. Many other elements may be present or added. Stainless steels that are corrosion- and oxidation-resistant ty ...
for heavy artillery, like in the super-heavy howitzer Big Bertha, because traditional steel melts at the temperatures produced by the propellant of the one ton shell. After the war, demand plummeted until metallurgical advances allowed extensive development of peacetime applications. In World War II, molybdenum again saw strategic importance as a substitute for tungsten in steel alloys.


Occurrence and production

Molybdenum is the 54th most abundant element in the Earth's crust with an average of 1.5 parts per million and the 25th most abundant element in its oceans, with an average of 10 parts per billion; it is the 42nd most abundant element in the Universe. The Russian Luna 24 mission discovered a molybdenum-bearing grain (1 × 0.6 µm) in a
pyroxene The pyroxenes (commonly abbreviated to ''Px'') are a group of important rock-forming inosilicate minerals found in many igneous and metamorphic rocks. Pyroxenes have the general formula , where X represents calcium (Ca), sodium (Na), iron (Fe II) ...
fragment taken from Mare Crisium on the Moon. The comparative rarity of molybdenum in the Earth's crust is offset by its concentration in a number of water-insoluble ores, often combined with sulfur in the same way as copper, with which it is often found. Though molybdenum is found in such minerals as wulfenite (PbMoO4) and
powellite Powellite is a calcium molybdate mineral with formula CaMoO4. Powellite crystallizes with tetragonal - dipyramidal crystal structure as transparent adamantine blue, greenish brown, yellow to grey typically anhedral forms. It exhibits distinct cle ...
(CaMoO4), the main commercial source is molybdenite (Mo S2). Molybdenum is mined as a principal ore and is also recovered as a byproduct of copper and tungsten mining. The world's production of molybdenum was 250,000 tonnes in 2011, the largest producers being China (94,000 t), the United States (64,000 t), Chile (38,000 t), Peru (18,000 t) and Mexico (12,000 t). The total reserves are estimated at 10 million tonnes, and are mostly concentrated in China (4.3 Mt), the US (2.7 Mt) and Chile (1.2 Mt). By continent, 93% of world molybdenum production is about evenly shared between North America, South America (mainly in Chile), and China. Europe and the rest of Asia (mostly Armenia, Russia, Iran and Mongolia) produce the remainder. In molybdenite processing, the ore is first roasted in air at a temperature of . The process gives gaseous sulfur dioxide and the
molybdenum(VI) oxide Molybdenum trioxide describes a family of inorganic compounds with the formula MoO3(H2O)n where n = 0, 1, 2. These compounds are produced on the largest scale of any molybdenum compound. The anhydrous oxide is a precursor to molybdenum metal, ...
: :2MoS2 + 7O2 -> 2MoO3 + 4SO2 The oxidized ore is then usually extracted with aqueous ammonia to give ammonium molybdate: :MoO3 + 2NH3 + H2O -> (NH4)2(MoO4) Copper, an impurity in molybdenite, is less soluble in ammonia. To completely remove it from the solution, it is precipitated with
hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic foul odor of rotten eggs. The unde ...
. Ammonium molybdate converts to ammonium dimolybdate, which is isolated as a solid. Heating this solid gives molybdenum trioxide:Sebenik, Roger F. et al. (2005) "Molybdenum and Molybdenum Compounds" in ''Ullmann's Encyclopedia of Chemical Technology''. Wiley-VCH, Weinheim. : (NH4)2Mo2O7 -> 2MoO3 + 2NH3 + H2O Crude trioxide can be further purified by sublimation at . Metallic molybdenum is produced by reduction of the oxide with hydrogen: :MoO3 + 3H2 -> Mo + 3H2O The molybdenum for steel production is reduced by the aluminothermic reaction with addition of iron to produce ferromolybdenum. A common form of ferromolybdenum contains 60% molybdenum. Molybdenum had a value of approximately $30,000 per tonne as of August 2009. It maintained a price at or near $10,000 per tonne from 1997 through 2003, and reached a peak of $103,000 per tonne in June 2005. In 2008, the London Metal Exchange announced that molybdenum would be traded as a commodity.


Mining

Historically, the Knaben mine in southern Norway, opened in 1885, was the first dedicated molybdenum mine. It was closed in 1973 but was reopened in 2007. and now produces of molybdenum disulfide per year. Large mines in Colorado (such as the
Henderson mine The Henderson molybdenum mine is a large underground molybdenum mine west of the town of Empire in Clear Creek County, Colorado, USA. The Henderson mine, which has produced molybdenum since 1976, is owned by Freeport-McMoRan. The Henderson min ...
and the
Climax mine The Climax mine, located in Climax, Colorado, United States, is a major molybdenum mine in Lake County, Colorado, Lake and Summit County, Colorado, Summit counties, Colorado. Shipments from the mine began in 1915. At its highest output, the Clima ...
) and in British Columbia yield molybdenite as their primary product, while many porphyry copper deposits such as the Bingham Canyon Mine in Utah and the Chuquicamata mine in northern Chile produce molybdenum as a byproduct of copper mining.


Applications


Alloys

About 86% of molybdenum produced is used in
metallurgy Metallurgy is a domain of materials science and engineering that studies the physical and chemical behavior of metallic elements, their inter-metallic compounds, and their mixtures, which are known as alloys. Metallurgy encompasses both the sc ...
, with the rest used in chemical applications. The estimated global use is structural steel 35%,
stainless steel Stainless steel is an alloy of iron that is resistant to rusting and corrosion. It contains at least 11% chromium and may contain elements such as carbon, other nonmetals and metals to obtain other desired properties. Stainless steel's corros ...
25%, chemicals 14%, tool & high-speed steels 9%, cast iron 6%, molybdenum elemental metal 6%, and
superalloy A superalloy, or high-performance alloy, is an alloy with the ability to operate at a high fraction of its melting point. Several key characteristics of a superalloy are excellent mechanical strength, resistance to thermal creep deformation, g ...
s 5%. Molybdenum can withstand extreme temperatures without significantly expanding or softening, making it useful in environments of intense heat, including military armor, aircraft parts, electrical contacts, industrial motors, and supports for filaments in light bulbs. Most high-strength steel alloys (for example,
41xx steel 41xx steel is a family of SAE steel grades, as specified by the Society of Automotive Engineers (SAE). Alloying elements include chromium and molybdenum, and as a result these materials are often informally referred to as chromoly steel (common va ...
s) contain 0.25% to 8% molybdenum. Even in these small portions, more than 43,000 tonnes of molybdenum are used each year in
stainless steel Stainless steel is an alloy of iron that is resistant to rusting and corrosion. It contains at least 11% chromium and may contain elements such as carbon, other nonmetals and metals to obtain other desired properties. Stainless steel's corros ...
s, tool steels, cast irons, and high-temperature
superalloy A superalloy, or high-performance alloy, is an alloy with the ability to operate at a high fraction of its melting point. Several key characteristics of a superalloy are excellent mechanical strength, resistance to thermal creep deformation, g ...
s. Molybdenum is also valued in steel alloys for its high corrosion resistance and weldability. Molybdenum contributes corrosion resistance to type-300 stainless steels (specifically type-316) and especially so in the so-called super austenitic stainless steels (such as alloy
AL-6XN AL-6XN (unified numbering system, UNS designation N08367) is a type of welding, weldable stainless steel that consist of an alloy of nickel (24%), chromium (22%) and molybdenum (6.3%) with other trace elements such as nitrogen. The high nickel and ...
, 254SMO and 1925hMo). Molybdenum increases lattice strain, thus increasing the energy required to dissolve iron atoms from the surface. Molybdenum is also used to enhance the corrosion resistance of ferritic (for example grade 444) and martensitic (for example 1.4122 and 1.4418) stainless steels. Because of its lower density and more stable price, molybdenum is sometimes used in place of tungsten. An example is the 'M' series of high-speed steels such as M2, M4 and M42 as substitution for the 'T' steel series, which contain tungsten. Molybdenum can also be used as a flame-resistant coating for other metals. Although its melting point is , molybdenum rapidly oxidizes at temperatures above making it better-suited for use in vacuum environments. TZM (Mo (~99%), Ti (~0.5%), Zr (~0.08%) and some C) is a corrosion-resisting molybdenum superalloy that resists molten fluoride salts at temperatures above . It has about twice the strength of pure Mo, and is more ductile and more weldable, yet in tests it resisted corrosion of a standard eutectic salt ( FLiBe) and salt vapors used in molten salt reactors for 1100 hours with so little corrosion that it was difficult to measure. Other molybdenum-based alloys that do not contain iron have only limited applications. For example, because of its resistance to molten zinc, both pure molybdenum and molybdenum- tungsten alloys (70%/30%) are used for piping, stirrers and pump impellers that come into contact with molten zinc.


Other applications as a pure element

* Molybdenum powder is used as a fertilizer for some plants, such as cauliflower * Elemental molybdenum is used in NO, NO2, NOx analyzers in power plants for pollution controls. At , the element acts as a catalyst for NO2/NOx to form NO molecules for detection by infrared light. * Molybdenum anodes replace tungsten in certain low voltage X-ray sources for specialized uses such as
mammography Mammography (also called mastography) is the process of using low-energy X-rays (usually around 30 kVp) to examine the human breast for diagnosis and screening. The goal of mammography is the early detection of breast cancer, typically through d ...
. * The radioactive isotope molybdenum-99 is used to generate technetium-99m, used for medical imaging The isotope is handled and stored as the molybdate.


Compounds (14% of global use)

*
Molybdenum disulfide Molybdenum disulfide (or moly) is an inorganic compound composed of molybdenum and sulfur. Its chemical formula is . The compound is classified as a transition metal dichalcogenide. It is a silvery black solid that occurs as the mineral molybdenit ...
(MoS2) is used as a solid
lubricant A lubricant (sometimes shortened to lube) is a substance that helps to reduce friction between surfaces in mutual contact, which ultimately reduces the heat generated when the surfaces move. It may also have the function of transmitting forces, t ...
and a high-pressure high-temperature (HPHT) anti-wear agent. It forms strong films on metallic surfaces and is a common additive to HPHT greases — in the event of a catastrophic grease failure, a thin layer of molybdenum prevents contact of the lubricated parts. It also has semiconducting properties with distinct advantages over traditional silicon or graphene in electronics applications. MoS2 is also used as a catalyst in
hydrocracking In petrochemistry, petroleum geology and organic chemistry, cracking is the process whereby complex organic molecules such as kerogens or long-chain hydrocarbons are broken down into simpler molecules such as light hydrocarbons, by the breaking of ...
of petroleum fractions containing nitrogen, sulfur and oxygen. * Molybdenum disilicide (MoSi2) is an electrically conducting ceramic with primary use in heating elements operating at temperatures above 1500 °C in air. * Molybdenum trioxide (MoO3) is used as an adhesive between enamels and metals. *
Lead molybdate Wulfenite is a lead molybdate mineral with the formula Pb Mo O4. It can be most often found as thin tabular crystals with a bright orange-red to yellow-orange color, sometimes brown, although the color can be highly variable. In its yellow form ...
(wulfenite) co-precipitated with lead chromate and lead sulfate is a bright-orange pigment used with ceramics and plastics. * The molybdenum-based mixed oxides are versatile catalysts in the chemical industry. Some examples are the catalysts for the oxidation of carbon monoxide, selective oxidation of propylene to acrolein and acrylic acid, the ammoxidation of glycerol and propylene to acrylonitrile. Suitable catalysts and process for the direct selective oxidation of propane to acrylic acid are being researched. * Molybdenum carbides, nitride and phosphides can be used for hydrotreatment of rapeseed oil. * Ammonium heptamolybdate is used in biological staining. * Molybdenum coated soda lime glass is used in CIGS ( copper indium gallium selenide) solar cells, called CIGS solar cells. *
Phosphomolybdic acid Phosphomolybdic acid is the heteropolymetalate with the formula . It is a yellow solid, although even slightly impure samples have a greenish coloration. It is also known as dodeca molybdophosphoric acid or PMA, is a yellow-green chemical compound ...
is a stain used in thin-layer chromatography.


Biological role


Mo-containing enzymes

Molybdenum is an essential element in most organisms; a 2008 research paper speculated that a scarcity of molybdenum in the Earth's early oceans may have strongly influenced the evolution of eukaryotic life (which includes all plants and animals). At least 50 molybdenum-containing enzymes have been identified, mostly in bacteria. Those enzymes include aldehyde oxidase, sulfite oxidase and xanthine oxidase. With one exception, Mo in proteins is bound by molybdopterin to give the molybdenum cofactor. The only known exception is nitrogenase, which uses the FeMoco cofactor, which has the formula Fe7MoS9C. In terms of function, molybdoenzymes catalyze the oxidation and sometimes reduction of certain small molecules in the process of regulating nitrogen,
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
, and carbon. In some animals, and in humans, the oxidation of xanthine to uric acid, a process of purine
catabolism Catabolism () is the set of metabolic pathways that breaks down molecules into smaller units that are either oxidized to release energy or used in other anabolic reactions. Catabolism breaks down large molecules (such as polysaccharides, lipids, ...
, is catalyzed by xanthine oxidase, a molybdenum-containing enzyme. The activity of xanthine oxidase is directly proportional to the amount of molybdenum in the body. An extremely high concentration of molybdenum reverses the trend and can inhibit purine catabolism and other processes. Molybdenum concentration also affects
protein synthesis Protein biosynthesis (or protein synthesis) is a core biological process, occurring inside Cell (biology), cells, homeostasis, balancing the loss of cellular proteins (via Proteolysis, degradation or Protein targeting, export) through the product ...
, metabolism, and growth. Mo is a component in most nitrogenases. Among molybdoenzymes, nitrogenases are unique in lacking the molybdopterin. Nitrogenases catalyze the production of ammonia from atmospheric nitrogen: : \mathrm The
biosynthesis Biosynthesis is a multi-step, enzyme-catalyzed process where substrates are converted into more complex products in living organisms. In biosynthesis, simple compounds are modified, converted into other compounds, or joined to form macromolecules. ...
of the FeMoco
active site In biology and biochemistry, the active site is the region of an enzyme where substrate molecules bind and undergo a chemical reaction. The active site consists of amino acid residues that form temporary bonds with the substrate (binding site) a ...
is highly complex. Molybdate is transported in the body as MoO42−.


Human metabolism and deficiency

Molybdenum is an essential trace dietary element. Four mammalian Mo-dependent enzymes are known, all of them harboring a pterin-based molybdenum cofactor (Moco) in their active site: sulfite oxidase, xanthine oxidoreductase, aldehyde oxidase, and mitochondrial amidoxime reductase. People severely deficient in molybdenum have poorly functioning sulfite oxidase and are prone to toxic reactions to sulfites in foods. The human body contains about 0.07 mg of molybdenum per kilogram of body weight, with higher concentrations in the liver and kidneys and lower in the vertebrae. Molybdenum is also present within human tooth enamel and may help prevent its decay. Acute toxicity has not been seen in humans, and the toxicity depends strongly on the chemical state. Studies on rats show a
median lethal dose In toxicology, the median lethal dose, LD50 (abbreviation for "lethal dose, 50%"), LC50 (lethal concentration, 50%) or LCt50 is a toxic unit that measures the lethal dose of a toxin, radiation, or pathogen. The value of LD50 for a substance is the ...
(LD50) as low as 180 mg/kg for some Mo compounds. Although human toxicity data is unavailable, animal studies have shown that chronic ingestion of more than 10 mg/day of molybdenum can cause diarrhea, growth retardation,
infertility Infertility is the inability of a person, animal or plant to reproduce by natural means. It is usually not the natural state of a healthy adult, except notably among certain eusocial species (mostly haplodiploid insects). It is the normal state ...
, low birth weight, and gout; it can also affect the lungs, kidneys, and liver. Sodium tungstate is a competitive inhibitor of molybdenum. Dietary tungsten reduces the concentration of molybdenum in tissues. Low soil concentration of molybdenum in a geographical band from northern China to Iran results in a general dietary
molybdenum deficiency Molybdenum deficiency refers to the clinical consequences of inadequate supplies of molybdenum in the diet. The amount of molybdenum required is relatively small, and molybdenum deficiency usually does not occur in natural settings. However, it c ...
, and is associated with increased rates of
esophageal cancer Esophageal cancer is cancer arising from the esophagus—the food pipe that runs between the throat and the stomach. Symptoms often include difficulty in swallowing and weight loss. Other symptoms may include pain when swallowing, a hoarse voice ...
. Compared to the United States, which has a greater supply of molybdenum in the soil, people living in those areas have about 16 times greater risk for esophageal
squamous cell carcinoma Squamous-cell carcinomas (SCCs), also known as epidermoid carcinomas, comprise a number of different types of cancer that begin in squamous cells. These cells form on the surface of the skin, on the lining of hollow organs in the body, and on the ...
. Molybdenum deficiency has also been reported as a consequence of non-molybdenum supplemented total parenteral nutrition (complete intravenous feeding) for long periods of time. It results in high blood levels of
sulfite Sulfites or sulphites are compounds that contain the sulfite ion (or the sulfate(IV) ion, from its correct systematic name), . The sulfite ion is the conjugate base of bisulfite. Although its acid ( sulfurous acid) is elusive, its salts are wide ...
and urate, in much the same way as molybdenum cofactor deficiency. Since pure molybdenum deficiency from this cause occurs primarily in adults, the neurological consequences are not as marked as in cases of congenital cofactor deficiency. A congenital molybdenum cofactor deficiency disease, seen in infants, is an inability to synthesize molybdenum cofactor, the heterocyclic molecule discussed above that binds molybdenum at the active site in all known human enzymes that use molybdenum. The resulting deficiency results in high levels of
sulfite Sulfites or sulphites are compounds that contain the sulfite ion (or the sulfate(IV) ion, from its correct systematic name), . The sulfite ion is the conjugate base of bisulfite. Although its acid ( sulfurous acid) is elusive, its salts are wide ...
and urate, and neurological damage.


Excretion

Most molybdenum is excreted from the human body as molybdate in the urine. Furthermore, urinary excretion of molybdenum increases as dietary molybdenum intake increases. Small amounts of molybdenum are excreted from the body in the feces by way of the bile; small amounts also can be lost in sweat and in hair.


Excess and copper antagonism

High levels of molybdenum can interfere with the body's uptake of copper, producing copper deficiency. Molybdenum prevents plasma proteins from binding to copper, and it also increases the amount of copper that is excreted in urine. Ruminants that consume high levels of molybdenum suffer from diarrhea, stunted growth, anemia, and achromotrichia (loss of fur pigment). These symptoms can be alleviated by copper supplements, either dietary and injection. The effective copper deficiency can be aggravated by excess
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
. Copper reduction or deficiency can also be deliberately induced for therapeutic purposes by the compound ammonium tetrathiomolybdate, in which the bright red anion tetrathiomolybdate is the copper-chelating agent. Tetrathiomolybdate was first used therapeutically in the treatment of copper toxicosis in animals. It was then introduced as a treatment in Wilson's disease, a hereditary copper metabolism disorder in humans; it acts both by competing with copper absorption in the bowel and by increasing excretion. It has also been found to have an inhibitory effect on
angiogenesis Angiogenesis is the physiological process through which new blood vessels form from pre-existing vessels, formed in the earlier stage of vasculogenesis. Angiogenesis continues the growth of the vasculature by processes of sprouting and splitting ...
, potentially by inhibiting the membrane translocation process that is dependent on copper ions. This is a promising avenue for investigation of treatments for cancer,
age-related macular degeneration Macular degeneration, also known as age-related macular degeneration (AMD or ARMD), is a medical condition which may result in blurred or no vision in the center of the visual field. Early on there are often no symptoms. Over time, however, som ...
, and other diseases that involve a pathologic proliferation of blood vessels. In some grazing livestock, most strongly in cattle, molybdenum excess in the soil of pasturage can produce scours ( diarrhea) if the pH of the soil is neutral to alkaline; see teartness.


Dietary recommendations

In 2000, the then U.S. Institute of Medicine (now the National Academy of Medicine, NAM) updated its Estimated Average Requirements (EARs) and Recommended Dietary Allowances (RDAs) for molybdenum. If there is not sufficient information to establish EARs and RDAs, an estimate designated Adequate Intake (AI) is used instead. An AI of 2  micrograms (μg) of molybdenum per day was established for infants up to 6 months of age, and 3 μg/day from 7 to 12 months of age, both for males and females. For older children and adults, the following daily RDAs have been established for molybdenum: 17 μg from 1 to 3 years of age, 22 μg from 4 to 8 years, 34 μg from 9 to 13 years, 43 μg from 14 to 18 years, and 45 μg for persons 19 years old and older. All these RDAs are valid for both sexes.
Pregnant Pregnancy is the time during which one or more offspring develops (gestation, gestates) inside a woman, woman's uterus (womb). A multiple birth, multiple pregnancy involves more than one offspring, such as with twins. Pregnancy usually occur ...
or
lactating Lactation describes the secretion of milk from the mammary glands and the period of time that a mother lactates to feed her young. The process naturally occurs with all sexually mature female mammals, although it may predate mammals. The proces ...
females from 14 to 50 years of age have a higher daily RDA of 50 μg of molybdenum. As for safety, the NAM sets tolerable upper intake levels (ULs) for vitamins and minerals when evidence is sufficient. In the case of molybdenum, the UL is 2000 μg/day. Collectively the EARs, RDAs, AIs and ULs are referred to as Dietary Reference Intakes (DRIs). The European Food Safety Authority (EFSA) refers to the collective set of information as Dietary Reference Values, with Population Reference Intake (PRI) instead of RDA, and Average Requirement instead of EAR. AI and UL defined the same as in United States. For women and men ages 15 and older the AI is set at 65 μg/day. Pregnant and lactating women have the same AI. For children aged 1–14 years, the AIs increase with age from 15 to 45 μg/day. The adult AIs are higher than the U.S. RDAs, but on the other hand, the European Food Safety Authority reviewed the same safety question and set its UL at 600 μg/day, which is much lower than the U.S. value.


Labeling

For U.S. food and dietary supplement labeling purposes, the amount in a serving is expressed as a percent of Daily Value (%DV). For molybdenum labeling purposes 100% of the Daily Value was 75 μg, but as of May 27, 2016 it was revised to 45 μg. A table of the old and new adult daily values is provided at
Reference Daily Intake The Reference Daily Intake (RDI) used in nutrition labeling on food and dietary supplement products in the U.S. and Canada is the daily intake level of a nutrient that is considered to be sufficient to meet the requirements of 97–98% of health ...
.


Food sources

Average daily intake varies between 120 and 240 μg/day, which is higher than dietary recommendations. Pork, lamb, and beef liver each have approximately 1.5 parts per million of molybdenum. Other significant dietary sources include green beans, eggs, sunflower seeds, wheat flour, lentils, cucumbers, and cereal grain.


Precautions

Molybdenum dusts and fumes, generated by mining or metalworking, can be toxic, especially if ingested (including dust trapped in the sinuses and later swallowed). Low levels of prolonged exposure can cause irritation to the eyes and skin. Direct inhalation or ingestion of molybdenum and its oxides should be avoided. OSHA regulations specify the maximum permissible molybdenum exposure in an 8-hour day as 5 mg/m3. Chronic exposure to 60 to 600 mg/m3 can cause symptoms including fatigue, headaches and joint pains. At levels of 5000 mg/m3, molybdenum is
immediately dangerous to life and health The term immediately dangerous to life or health (IDLH) is defined by the US National Institute for Occupational Safety and Health (NIOSH) as exposure to airborne contaminants that is "likely to cause death or immediate or delayed permanent advers ...
.


See also

* List of molybdenum mines *
Molybdenum mining in the United States Molybdenum mining in the United States produced 65,500 metric tons of molybdenum in 2014, worth US$1.8 billion. The US was the world's second-largest molybdenum producer, after China, and provided 25% of the world's supply of molybdenum. The US ...


References


Bibliography

*


External links


Molybdenum
at '' The Periodic Table of Videos'' (University of Nottingham)
Mineral & Exploration
– Map of World Molybdenum Producers 2009
"Mining A Mountain" ''Popular Mechanics'', July 1935 pp. 63–64

Site for global molybdenum info


{{Authority control Chemical elements Transition metals Refractory metals Dietary minerals Chemical elements with body-centered cubic structure Native element minerals