Molybdenum(0) Compounds
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Molybdenum is a
chemical element A chemical element is a species of atoms that have a given number of protons in their nuclei, including the pure substance consisting only of that species. Unlike chemical compounds, chemical elements cannot be broken down into simpler sub ...
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 The atomic number or nuclear charge number (symbol ''Z'') of a chemical element is the charge number of an atomic nucleus. For ordinary nuclei, this is equal to the proton number (''n''p) or the number of protons found in the nucleus of every ...
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 Ancient Greek includes the forms of the Greek language used in ancient Greece and the ancient world from around 1500 BC to 300 BC. It is often roughly divided into the following periods: Mycenaean Greek (), Dark Ages (), the Archaic peri ...
', meaning
lead Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
, 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 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, hydrog ...
. 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 state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
s in minerals. The free element, a silvery
metal A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...
with a grey cast, has the sixth-highest
melting point The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depends ...
of any element. It readily forms hard, stable
carbide In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece. Interstitial / Metallic carbides The carbides of the ...
s in
alloy An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductility, ...
s, 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 chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution. The extent of the solubil ...
in water, but when molybdenum-bearing minerals contact
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
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, althou ...
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
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 ...
s and
catalysts Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
. are by far the most common bacterial catalysts for breaking the
chemical bond A chemical bond is a lasting attraction between atoms or ions that enables the formation of molecules and crystals. The bond may result from the electrostatic force between oppositely charged ions as in ionic bonds, or through the sharing of ...
in atmospheric molecular
nitrogen Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
in the process of biological
nitrogen fixation Nitrogen fixation is a chemical process by which molecular nitrogen (), with a strong triple covalent bond, in the air is converted into ammonia () or related nitrogenous compounds, typically in soil or aquatic systems but also in industry. Atmo ...
. 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
nitrogenase Nitrogenases are enzymes () that are produced by certain bacteria, such as cyanobacteria (blue-green bacteria) and rhizobacteria. These enzymes are responsible for the Organic redox reaction, reduction of nitrogen (N2) to ammonia (NH3). Nitrog ...
s contain an iron-molybdenum cofactor
FeMoco FeMoco ( cofactor) is the primary cofactor of nitrogenase. Nitrogenase is the enzyme that catalyzes the conversion of atmospheric nitrogen molecules N2 into ammonia (NH3) through the process known as nitrogen fixation. Containing iron and molyb ...
, which is believed to contain either Mo(III) or Mo(IV). This is distinct from the fully oxidized Mo(VI) found complexed with
molybdopterin Molybdopterins are a class of cofactors found in most molybdenum-containing and all tungsten-containing enzymes. Synonyms for molybdopterin are: MPT and pyranopterin-dithiolate. The nomenclature for this biomolecule can be confusing: Molybdopter ...
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 The Mohs scale of mineral hardness () is a qualitative ordinal scale, from 1 to 10, characterizing scratch resistance of various minerals through the ability of harder material to scratch softer material. The scale was introduced in 1812 by th ...
of 5.5 and a standard atomic weight of 95.95 g/mol. It has a
melting point The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state from solid to liquid. At the melting point the solid and liquid phase exist in equilibrium. The melting point of a substance depends ...
of ; of the naturally occurring elements, only
tantalum Tantalum is a chemical element with the symbol Ta and atomic number 73. Previously known as ''tantalium'', it is named after Tantalus, a villain in Greek mythology. Tantalum is a very hard, ductile, lustrous, blue-gray transition metal that is ...
,
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 Rhenium is a chemical element with the symbol Re and atomic number 75. It is a silvery-gray, heavy, third-row transition metal in group 7 of the periodic table. With an estimated average concentration of 1 part per billion (ppb), rhenium is one ...
,
tungsten Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isolat ...
, and
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
have higher melting points. It has one of the lowest coefficients of
thermal expansion Thermal expansion is the tendency of matter to change its shape, area, volume, and density in response to a change in temperature, usually not including phase transitions. Temperature is a monotonic function of the average molecular kinetic ...
among commercially used metals.


Chemical properties

Molybdenum is a
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can ...
with an
electronegativity Electronegativity, symbolized as , is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the d ...
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 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, an ...
. 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 A sextuple bond is a type of covalent bond involving 12 bonding electrons and in which the bond order is 6. The only known molecules with true sextuple bonds are the diatomic dimolybdenum ( Mo2) and ditungsten ( W2), which exist in the gaseous pha ...
.


Isotopes

There are 35 known
isotopes Isotopes are two or more types of atoms that have the same atomic number (number of protons in their nuclei) and position in the periodic table (and hence belong to the same chemical element), and that differ in nucleon numbers (mass numbers) ...
of molybdenum, ranging in
atomic mass The atomic mass (''m''a or ''m'') is the mass of an atom. Although the SI unit of mass is the kilogram (symbol: kg), atomic mass is often expressed in the non-SI unit dalton (symbol: Da) – equivalently, unified atomic mass unit (u). 1&nbs ...
from 83 to 117, as well as four metastable
nuclear isomer A nuclear isomer is a metastable state of an atomic nucleus, in which one or more nucleons (protons or neutrons) occupy excited state, higher energy levels than in the ground state of the same nucleus. "Metastable" describes nuclei whose excited ...
s. 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 Half-life (symbol ) is the time required for a quantity (of substance) to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how long stable ato ...
of about 1019  y and undergoes
double beta decay In nuclear physics, double beta decay is a type of radioactive decay in which two neutrons are simultaneously transformed into two protons, or vice versa, inside an atomic nucleus. As in single beta decay, this process allows the atom to move clos ...
into
ruthenium Ruthenium is a chemical element with the Symbol (chemistry), symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to ...
-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 Technetium is a chemical element with the symbol Tc and atomic number 43. It is the lightest element whose isotopes are all radioactive. All available technetium is produced as a synthetic element. Naturally occurring technetium is a spontaneous ...
, and
ruthenium Ruthenium is a chemical element with the Symbol (chemistry), symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to ...
. Of the synthetic radioisotopes, the most stable is 93Mo, with a half-life of 4,000 years. The most common isotopic molybdenum application involves
molybdenum-99 Molybdenum (42Mo) has 33 known isotopes, ranging in atomic mass from 83 to 115, as well as four metastable nuclear isomers. Seven isotopes occur naturally, with atomic masses of 92, 94, 95, 96, 97, 98, and 100. All unstable isotopes of molybdenum ...
, 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 Technetium-99m (99mTc) is a metastable nuclear isomer of technetium-99 (itself an isotope of technetium), symbolized as 99mTc, that is used in tens of millions of medical diagnostic procedures annually, making it the most commonly used medical ra ...
, a
nuclear isomer A nuclear isomer is a metastable state of an atomic nucleus, in which one or more nucleons (protons or neutrons) occupy excited state, higher energy levels than in the ground state of the same nucleus. "Metastable" describes nuclei whose excited ...
used in various imaging applications in medicine. In 2008, the
Delft University of Technology Delft University of Technology ( nl, Technische Universiteit Delft), also known as TU Delft, is the oldest and largest Dutch public technical university, located in Delft, Netherlands. As of 2022 it is ranked by QS World University Rankings among ...
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 cluster In chemistry, an atom cluster (or simply cluster) is an ensemble of bound atoms or molecules that is intermediate in size between a simple molecule and a nanoparticle; that is, up to a few nanometers (nm) in diameter. The term ''microcluster ...
s, 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 state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
s, 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 Chromate salts contain the chromate anion, . Dichromate salts contain the dichromate anion, . They are oxyanions of chromium in the +6 oxidation state and are moderately strong oxidizing agents. In an aqueous solution, chromate and dichromate ...
. They tend to form structurally complex
oxyanion An oxyanion, or oxoanion, is an ion with the generic formula (where A represents a chemical element and O represents an oxygen atom). Oxyanions are formed by a large majority of the chemical elements. The formulae of simple oxyanions are determine ...
s by condensation at lower pH values, such as o7O24sup>6− and o8O26sup>4−. Polymolybdates can incorporate other ions, forming
polyoxometalate In chemistry, a polyoxometalate (abbreviated POM) is a polyatomic ion, usually an anion, that consists of three or more transition metal oxyanions linked together by shared oxygen atoms to form closed 3-dimensional frameworks. The metal atoms are ...
s. The dark-blue
phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ear ...
-containing heteropolymolybdate P o12O40sup>3− is used for the
spectroscopic Spectroscopy is the field of study that measures and interprets the electromagnetic spectra that result from the interaction between electromagnetic radiation and matter as a function of the wavelength or frequency of the radiation. Matter wa ...
detection of phosphorus. The broad range of
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
s of molybdenum is reflected in various molybdenum chlorides: *
Molybdenum(II) chloride Molybdenum dichloride describes chemical compounds with the empirical formula MoCl2. At least two forms are known, and both have attracted much attention from academic researchers because of the unexpected structures seen for these compounds and t ...
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 Molybdenum tetrachloride is the inorganic compound with the empirical formula MoCl4. The material exists as two polymorphs, both being dark-colored paramagnetic solids. These compounds are mainly of interest as precursors to other molybdenum comp ...
MoCl4, a black solid, which adopts a polymeric structure. *
Molybdenum(V) chloride Molybdenum(V) chloride is the inorganic compound with the empirical formula . This dark volatile solid is used in research to prepare other molybdenum compounds. It is moisture-sensitive and soluble in chlorinated solvents. Structure Usually cal ...
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 bond A quadruple bond is a type of chemical bond between two atoms involving eight electrons. This bond is an extension of the more familiar types double bonds and triple bonds. Stable quadruple bonds are most common among the transition metals in the m ...
s, 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 Molybdenum hexacarbonyl (also called molybdenum carbonyl) is the chemical compound with the formula Mo(CO)6. This colorless solid, like its chromium and tungsten analogues, is noteworthy as a volatile, air-stable derivative of a metal in its zero ...
, Mo(CO)6.


History

Molybdenite Molybdenite is a mineral of molybdenum disulfide, Mo S2. Similar in appearance and feel to graphite, molybdenite has a lubricating effect that is a consequence of its layered structure. The atomic structure consists of a sheet of molybdenum ato ...
—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 Graphite () is a crystalline form of the element carbon. It consists of stacked layers of graphene. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on large ...
. 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 Lead is a chemical element with the symbol Pb (from the Latin ) and atomic number 82. It is a heavy metal that is denser than most common materials. Lead is soft and malleable, and also has a relatively low melting point. When freshly cu ...
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 Ancient Greek includes the forms of the Greek language used in ancient Greece and the ancient world from around 1500 BC to 300 BC. It is often roughly divided into the following periods: Mycenaean Greek (), Dark Ages (), the Archaic peri ...
', meaning ''lead''. (The Greek word itself has been proposed as a
loanword A loanword (also loan word or loan-word) is a word at least partly assimilated from one language (the donor language) into another language. This is in contrast to cognates, which are words in two or more languages that are similar because th ...
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 Luwian (), sometimes known as Luvian or Luish, is an ancient language, or group of languages, within the Anatolian branch of the Indo-European language family. The ethnonym Luwian comes from ''Luwiya'' (also spelled ''Luwia'' or ''Luvia'') – ...
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 Bengt Andersson Qvist (sometimes Benct Qvist or Bengt Quist (21 October 1726 – 14 October 1799) was a Swedish chemist and mineralogist. He was assistant of Sven Rinman and after a visit to steel plants in Britain he built a demonstration pl ...
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 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, hydrog ...
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 Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
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 Ductility is a mechanical property commonly described as a material's amenability to drawing (e.g. into wire). In materials science, ductility is defined by the degree to which a material can sustain plastic deformation under tensile stres ...
, 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 to recover
molybdenite Molybdenite is a mineral of molybdenum disulfide, Mo S2. Similar in appearance and feel to graphite, molybdenite has a lubricating effect that is a consequence of its layered structure. The atomic structure consists of a sheet of molybdenum ato ...
from ores; flotation remains the primary isolation process. During
World War I World War I (28 July 1914 11 November 1918), often abbreviated as WWI, was one of the deadliest global conflicts in history. Belligerents included much of Europe, the Russian Empire, the United States, and the Ottoman Empire, with fightin ...
, demand for molybdenum spiked; it was used both in
armor plating Military vehicles are commonly armoured (or armored; see spelling differences) to withstand the impact of shrapnel, bullets, shells, rockets, and missiles, protecting the personnel inside from enemy fire. Such vehicles include armoured fighti ...
and as a substitute for tungsten in
high-speed steel High-speed steel (HSS or HS) is a subset of tool steels, commonly used as cutting tool material. It is often used in power-saw blades and drill bits. It is superior to the older high-carbon steel tools used extensively through the 1940s in tha ...
s. 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 World War II or the Second World War, often abbreviated as WWII or WW2, was a world war that lasted from 1939 to 1945. It involved the vast majority of the world's countries—including all of the great powers—forming two opposin ...
, 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 ''Luna 24'' was a robotic probe of the Soviet Union's Luna programme. The last of the Luna series of spacecraft, the mission of the ''Luna 24'' probe was the third Soviet mission to return lunar soil samples from the Moon (the first two sampl ...
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 Mare Crisium (Latin ''crisium'', the "Sea of Crises") is a lunar mare located in the Moon's Crisium basin, just northeast of Mare Tranquillitatis. The basin is of the Pre-Imbrian period, 4.55 to 3.85 billion years ago. Characteristics Mare Cri ...
on the
Moon The Moon is Earth's only natural satellite. It is the fifth largest satellite in the Solar System and the largest and most massive relative to its parent planet, with a diameter about one-quarter that of Earth (comparable to the width of ...
. 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
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. ( ...
s as
wulfenite 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 ...
(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 Molybdenite is a mineral of molybdenum disulfide, Mo S2. Similar in appearance and feel to graphite, molybdenite has a lubricating effect that is a consequence of its layered structure. The atomic structure consists of a sheet of molybdenum ato ...
(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 Ammonium dimolybdate (ADM) is the inorganic compound with the formula (NH4)2Mo2O7. It is a white, water-soluble solid. ADM is an intermediate in the production of molybdenum compounds from its ores. Roasting typical ore produces crude molybdenum( ...
, 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 Aluminothermic reactions are exothermic chemical reactions using aluminum as the reducing agent at high temperature. The process is industrially useful for production of alloys of iron. The most prominent example is the thermite reaction between ...
with addition of iron to produce
ferromolybdenum Ferro molybdenum is an important iron-molybdenum metal alloy, with a molybdenum content of 60-75% It is the main source for molybdenum alloying of HSLA steel. Production The alloy is produced by heating a mixture of molybdenum(VI) oxide MoO3, alumi ...
. 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 The London Metal Exchange (LME) is a futures and forwards exchange with the world's largest market in standarised forward contracts, futures contracts and options on base metals. The exchange also offers contracts on ferrous metals and precious ...
announced that molybdenum would be traded as a commodity.


Mining

Historically, the
Knaben Knaben is an old mining village in the northern part of Kvinesdal municipality in Agder county, Norway. Currently, the mine is no longer in use, but the area has become a popular ski resort. The village lies at an elevation of above sea level, ab ...
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 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 Porphyry copper deposits are copper ore bodies that are formed from hydrothermal fluids that originate from a voluminous magma chamber several kilometers below the deposit itself. Predating or associated with those fluids are vertical dikes of ...
deposits such as the
Bingham Canyon Mine The Bingham Canyon Mine, more commonly known as Kennecott Copper Mine among locals, is an open-pit mining operation extracting a large porphyry copper deposit southwest of Salt Lake City, Utah, in the Oquirrh Mountains. The mine is the largest ...
in Utah and the
Chuquicamata Chuquicamata ( ; referred to as Chuqui for short) is the largest open pit copper mine in terms of excavated volume in the world. It is located in the north of Chile, just outside Calama, at above sea level. It is northeast of Antofagasta and n ...
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 Cast iron is a class of iron–carbon alloys with a carbon content more than 2%. Its usefulness derives from its relatively low melting temperature. The alloy constituents affect its color when fractured: white cast iron has carbide impuriti ...
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 An electric light, lamp, or light bulb is an electrical component that produces light. It is the most common form of artificial lighting. Lamps usually have a base made of ceramic, metal, glass, or plastic, which secures the lamp in the soc ...
. Most high-strength steel
alloy An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductility, ...
s (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 steel Tool steel is any of various carbon steels and alloy steels that are particularly well-suited to be made into tools and tooling, including cutting tools, dies, hand tools, knives, and others. Their suitability comes from their distinctive har ...
s, 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 Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engine ...
resistance and
weldability The weldability, also known as joinability,. of a material refers to its ability to be welded. Many metals and thermoplastics can be welded, but some are easier to weld than others (see Rheological weldability). A material's weldability is used to ...
. Molybdenum contributes corrosion resistance to type-300 stainless steels (specifically type-316) and especially so in the so-called super
austenitic Austenite, also known as gamma-phase iron (γ-Fe), is a metallic, non-magnetic allotrope of iron or a solid solution of iron with an alloying element. In plain-carbon steel, austenite exists above the critical eutectoid temperature of 1000 ...
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 FLiBe is a molten salt made from a mixture of lithium fluoride (LiF) and beryllium fluoride (BeF2). It is both a nuclear reactor coolant and solvent for fertile or fissile material. It served both purposes in the Molten-Salt Reactor Experim ...
) and salt vapors used in
molten salt reactor A molten salt reactor (MSR) is a class of nuclear fission reactor in which the primary nuclear reactor coolant and/or the fuel is a molten salt mixture. Only two MSRs have ever operated, both research reactors in the United States. The 1950's Ai ...
s 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 Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isolat ...
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 Molybdenum (42Mo) has 33 known isotopes, ranging in atomic mass from 83 to 115, as well as four metastable nuclear isomers. Seven isotopes occur naturally, with atomic masses of 92, 94, 95, 96, 97, 98, and 100. All unstable isotopes of molybdenum ...
is used to generate
technetium-99m Technetium-99m (99mTc) is a metastable nuclear isomer of technetium-99 (itself an isotope of technetium), symbolized as 99mTc, that is used in tens of millions of medical diagnostic procedures annually, making it the most commonly used medical ra ...
, 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 Graphene () is an allotrope of carbon consisting of a single layer of atoms arranged in a hexagonal lattice nanostructure.
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 Molybdenum disilicide (MoSi2, or molybdenum silicide), an intermetallic compound, a silicide of molybdenum, is a refractory ceramic with primary use in heating elements. It has moderate density, melting point 2030 °C, and is electrically co ...
(MoSi2) is an electrically conducting
ceramic A ceramic is any of the various hard, brittle, heat-resistant and corrosion-resistant materials made by shaping and then firing an inorganic, nonmetallic material, such as clay, at a high temperature. Common examples are earthenware, porcelain ...
with primary use in
heating element A heating element converts electrical energy into heat through the process of Joule heating. Electric current through the element encounters resistance, resulting in heating of the element. Unlike the Peltier effect, this process is independe ...
s operating at temperatures above 1500 °C in air. *
Molybdenum trioxide 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, an ...
(MoO3) is used as an adhesive between enamels and metals. * Lead molybdate (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 Ammonium heptamolybdate is the inorganic compound whose chemical formula is (NH4)6Mo7O24, normally encountered as the tetrahydrate. A dihydrate is also known. It is a colorless solid, often referred to as ammonium paramolybdate or simply as ammoni ...
is used in biological staining. * Molybdenum coated soda lime glass is used in CIGS (
copper indium gallium selenide Copper indium gallium (di)selenide (CIGS) is a I-III- VI2 semiconductor material composed of copper, indium, gallium, and selenium. The material is a solid solution of copper indium selenide (often abbreviated "CIS") and copper gallium selenide. ...
)
solar cell A solar cell, or photovoltaic cell, is an electronic device that converts the energy of light directly into electricity by the photovoltaic effect, which is a physical and chemical phenomenon.
s, 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 Thin-layer chromatography (TLC) is a chromatography technique used to separate non-volatile mixtures. Thin-layer chromatography is performed on a sheet of an inert substrate such as glass, plastic, or aluminium foil, which is coated with a t ...
.


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 Aldehyde oxidase (AO) is a metabolizing enzyme, located in the cytosolic compartment of tissues in many organisms. AO catalyzes the oxidation of aldehydes into carboxylic acid, and in addition, catalyzes the hydroxylation of some heterocycles. ...
,
sulfite oxidase Sulfite oxidase () is an enzyme in the mitochondria of all eukaryotes, with exception of the yeasts. It oxidizes sulfite to sulfate and, via cytochrome c, transfers the electrons produced to the electron transport chain, allowing generation o ...
and
xanthine oxidase Xanthine oxidase (XO, sometimes XAO) is a form of xanthine oxidoreductase, a type of enzyme that generates reactive oxygen species. These enzymes catalyze the oxidation of hypoxanthine to xanthine and can further catalyze the oxidation of xanthin ...
. With one exception, Mo in proteins is bound by
molybdopterin Molybdopterins are a class of cofactors found in most molybdenum-containing and all tungsten-containing enzymes. Synonyms for molybdopterin are: MPT and pyranopterin-dithiolate. The nomenclature for this biomolecule can be confusing: Molybdopter ...
to give the molybdenum cofactor. The only known exception is
nitrogenase Nitrogenases are enzymes () that are produced by certain bacteria, such as cyanobacteria (blue-green bacteria) and rhizobacteria. These enzymes are responsible for the Organic redox reaction, reduction of nitrogen (N2) to ammonia (NH3). Nitrog ...
, which uses the
FeMoco FeMoco ( cofactor) is the primary cofactor of nitrogenase. Nitrogenase is the enzyme that catalyzes the conversion of atmospheric nitrogen molecules N2 into ammonia (NH3) through the process known as nitrogen fixation. Containing iron and molyb ...
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 Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
,
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 Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
. In some animals, and in humans, the oxidation of
xanthine Xanthine ( or ; archaically xanthic acid; systematic name 3,7-dihydropurine-2,6-dione) is a purine base (genetics), base found in most human body tissues and fluids, as well as in other organisms. Several stimulants are derived from xanthine, incl ...
to
uric acid Uric acid is a heterocyclic compound of carbon, nitrogen, oxygen, and hydrogen with the formula C5H4N4O3. It forms ions and salts known as urates and acid urates, such as ammonium acid urate. Uric acid is a product of the metabolic breakdown of ...
, a process of
purine Purine is a heterocyclic compound, heterocyclic aromatic organic compound that consists of two rings (pyrimidine and imidazole) fused together. It is water-soluble. Purine also gives its name to the wider class of molecules, purines, which includ ...
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 Xanthine oxidase (XO, sometimes XAO) is a form of xanthine oxidoreductase, a type of enzyme that generates reactive oxygen species. These enzymes catalyze the oxidation of hypoxanthine to xanthine and can further catalyze the oxidation of xanthin ...
, 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 Metabolism (, from el, μεταβολή ''metabolē'', "change") is the set of life-sustaining chemical reactions in organisms. The three main functions of metabolism are: the conversion of the energy in food to energy available to run cell ...
, and growth. Mo is a component in most
nitrogenase Nitrogenases are enzymes () that are produced by certain bacteria, such as cyanobacteria (blue-green bacteria) and rhizobacteria. These enzymes are responsible for the Organic redox reaction, reduction of nitrogen (N2) to ammonia (NH3). Nitrog ...
s. 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 FeMoco ( cofactor) is the primary cofactor of nitrogenase. Nitrogenase is the enzyme that catalyzes the conversion of atmospheric nitrogen molecules N2 into ammonia (NH3) through the process known as nitrogen fixation. Containing iron and molyb ...
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 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, ...
. Four mammalian Mo-dependent enzymes are known, all of them harboring a
pterin Pterin is a heterocyclic compound composed of a pteridine ring system, with a "keto group" (a lactam) and an amino group on positions 4 and 2 respectively. It is structurally related to the parent bicyclic heterocycle called pteridine. Pterins, a ...
-based
molybdenum cofactor A molybdenum cofactor is a biochemical cofactor that contains molybdenum. Examples include: * Molybdopterin (or, strictly speaking, the molybdopterin-molybdenum-complex), the organophosphate-dithiolate ligand that binds molybdenum and tungsten ...
(Moco) in their active site:
sulfite oxidase Sulfite oxidase () is an enzyme in the mitochondria of all eukaryotes, with exception of the yeasts. It oxidizes sulfite to sulfate and, via cytochrome c, transfers the electrons produced to the electron transport chain, allowing generation o ...
,
xanthine oxidoreductase Xanthine oxidase (XO, sometimes XAO) is a form of xanthine oxidoreductase, a type of enzyme that generates reactive oxygen species. These enzymes catalyze the oxidation of hypoxanthine to xanthine and can further catalyze the oxidation of xanthin ...
,
aldehyde oxidase Aldehyde oxidase (AO) is a metabolizing enzyme, located in the cytosolic compartment of tissues in many organisms. AO catalyzes the oxidation of aldehydes into carboxylic acid, and in addition, catalyzes the hydroxylation of some heterocycles. ...
, 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 Tooth enamel is one of the four major Tissue (biology), tissues that make up the tooth in humans and many other animals, including some species of fish. It makes up the normally visible part of the tooth, covering the Crown (tooth), crown. The ...
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 Gout ( ) is a form of inflammatory arthritis characterized by recurrent attacks of a red, tender, hot and swollen joint, caused by deposition of monosodium urate monohydrate crystals. Pain typically comes on rapidly, reaching maximal intensit ...
; it can also affect the lungs, kidneys, and liver.
Sodium tungstate Sodium tungstate is the inorganic compound with the formula Na2WO4. This white, water-soluble solid is the sodium salt of tungstic acid. It is useful as a source of tungsten for chemical synthesis. It is an intermediate in the conversion of tungs ...
is a
competitive inhibitor Competitive inhibition is interruption of a chemical pathway owing to one chemical substance inhibiting the effect of another by competing with it for binding or bonding. Any metabolic or chemical messenger system can potentially be affected b ...
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 Parenteral nutrition (PN) is the feeding of nutritional products to a person intravenously, bypassing the usual process of eating and digestion. The products are made by pharmaceutical compounding companies. The person receives a nutritional mix ...
(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 Uric acid is a heterocyclic compound of carbon, nitrogen, oxygen, and hydrogen with the formula C5H4N4O3. It forms ions and salts known as urates and acid urates, such as ammonium acid urate. Uric acid is a product of the metabolic breakdown o ...
, in much the same way as
molybdenum cofactor deficiency Molybdenum cofactor deficiency is a rare human disease in which the absence of molybdopterin – and consequently its molybdenum complex, commonly called molybdenum cofactor – leads to accumulation of toxic levels of sulphite and neurological da ...
. 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 Molybdenum cofactor deficiency is a rare human disease in which the absence of molybdopterin – and consequently its molybdenum complex, commonly called molybdenum cofactor – leads to accumulation of toxic levels of sulphite and neurological da ...
disease, seen in infants, is an inability to synthesize
molybdenum cofactor A molybdenum cofactor is a biochemical cofactor that contains molybdenum. Examples include: * Molybdopterin (or, strictly speaking, the molybdopterin-molybdenum-complex), the organophosphate-dithiolate ligand that binds molybdenum and tungsten ...
, 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 Uric acid is a heterocyclic compound of carbon, nitrogen, oxygen, and hydrogen with the formula C5H4N4O3. It forms ions and salts known as urates and acid urates, such as ammonium acid urate. Uric acid is a product of the metabolic breakdown o ...
, 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 Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkis ...
, producing
copper deficiency Copper deficiency, or hypocupremia, is defined either as insufficient copper to meet the needs of the body, or as a serum copper level below the normal range. Symptoms may include fatigue, decreased red blood cells, early greying of the hair, a ...
. Molybdenum prevents plasma proteins from binding to copper, and it also increases the amount of copper that is excreted in
urine Urine is a liquid by-product of metabolism in humans and in many other animals. Urine flows from the kidneys through the ureters to the urinary bladder. Urination results in urine being excretion, excreted from the body through the urethra. Cel ...
.
Ruminant Ruminants (suborder Ruminantia) are ungulate, hoofed herbivorous grazing or browsing mammals that are able to acquire nutrients from plant-based food by Enteric fermentation, fermenting it in a specialized stomach prior to digestion, principally ...
s that consume high levels of molybdenum suffer from
diarrhea Diarrhea, also spelled diarrhoea, is the condition of having at least three loose, liquid, or watery bowel movements each day. It often lasts for a few days and can result in dehydration due to fluid loss. Signs of dehydration often begin wi ...
, stunted growth,
anemia Anemia or anaemia (British English) is a blood disorder in which the blood has a reduced ability to carry oxygen due to a lower than normal number of red blood cells, or a reduction in the amount of hemoglobin. When anemia comes on slowly, th ...
, 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 Ammonium tetrathiomolybdate is the chemical compound with the formula (NH4)2MoS4. This bright red ammonium salt is an important reagent in the chemistry of molybdenum and has been used as a building block in bioinorganic chemistry. The thiometalla ...
, in which the bright red anion tetrathiomolybdate is the copper-chelating agent. Tetrathiomolybdate was first used therapeutically in the treatment of
copper toxicosis Wilson's disease is a genetic disorder in which excess copper builds up in the body. Symptoms are typically related to the brain and liver. Liver-related symptoms include vomiting, weakness, fluid build up in the abdomen, swelling of the legs, ...
in animals. It was then introduced as a treatment in
Wilson's disease Wilson's disease is a genetic disorder in which excess copper builds up in the body. Symptoms are typically related to the brain and liver. Liver-related symptoms include vomiting, weakness, fluid build up in the abdomen, swelling of the legs, ...
, 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 Cancer is a group of diseases involving abnormal cell growth with the potential to invade or spread to other parts of the body. These contrast with benign tumors, which do not spread. Possible signs and symptoms include a lump, abnormal b ...
,
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 Diarrhea, also spelled diarrhoea, is the condition of having at least three loose, liquid, or watery bowel movements each day. It often lasts for a few days and can result in dehydration due to fluid loss. Signs of dehydration often begin wi ...
) 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 The National Academy of Medicine (NAM), formerly called the Institute of Medicine (IoM) until 2015, is an American nonprofit, non-governmental organization. The National Academy of Medicine is a part of the National Academies of Sciences, En ...
, 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 The Dietary Reference Intake (DRI) is a system of nutrition recommendations from the National Academy of Medicine (NAM) of the National Academies (United States). It was introduced in 1997 in order to broaden the existing guidelines known as Reco ...
(AI) is used instead. An AI of 2 
microgram In the metric system, a microgram or microgramme is a unit of mass equal to one millionth () of a gram. The unit symbol is μg according to the International System of Units (SI); the recommended symbol in the United States and United Kingdom whe ...
s (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 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 level The Dietary Reference Intake (DRI) is a system of nutrition recommendations from the National Academy of Medicine (NAM) of the National Academies (United States). It was introduced in 1997 in order to broaden the existing guidelines known as Re ...
s (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 Intake The Dietary Reference Intake (DRI) is a system of nutrition recommendations from the National Academy of Medicine (NAM) of the National Academies (United States). It was introduced in 1997 in order to broaden the existing guidelines known as Reco ...
s (DRIs). The
European Food Safety Authority The European Food Safety Authority (EFSA) is the agency of the European Union (EU) that provides independent scientific advice and communicates on existing and emerging risks associated with the food chain. EFSA was established in February 2002, ...
(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 The liver is a major Organ (anatomy), organ only found in vertebrates which performs many essential biological functions such as detoxification of the organism, and the Protein biosynthesis, synthesis of proteins and biochemicals necessary for ...
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 Paranasal sinuses are a group of four paired air-filled spaces that surround the nasal cavity. The maxillary sinuses are located under the eyes; the frontal sinuses are above the eyes; the ethmoidal sinuses are between the eyes and the sphenoid ...
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 OSHA or Osha may refer to: Work * Occupational Safety and Health Administration, a federal agency of the United States that regulates workplace safety and health * Occupational Safety and Health Act (United States) of 1970, a federal law in the Un ...
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 This list of molybdenum mines is subsidiary to the list of mines This lists of mines is a meta-list (list of lists) containing links to mine-related lists. By production *List of coal mines **List of coal mines in Australia ***List of collieri ...
*
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 ''Periodic Videos'' (also known as ''The Periodic Table of Videos'') is a video project and YouTube channel on chemistry. It consists of a series of videos about chemical elements and the periodic table, with additional videos on other topics i ...
'' (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