Vanadium: Difference between revisions

Vanadium, ₂₃V
Vanadium
Pronunciation	/vəˈneɪdiəm/ (və-NAY-dee-əm)
Appearance	blue-silver-grey metal
Standard atomic weight Ar°(V)
	50.9415±0.0001; 50.942±0.001 (abridged);
Vanadium in the periodic table
	titanium ← vanadium → chromium
Atomic number (Z)	23
Group	group 5
Period	period 4
Block	d-block
Electron configuration	[Ar] 3d3 4s2
Electrons per shell	2, 8, 11, 2
Physical properties
Phase at STP	solid
Melting point	2183 K (1910 °C, 3470 °F)
Boiling point	3680 K (3407 °C, 6165 °F)
Density (at 20° C)	6.099 g/cm3
when liquid (at m.p.)	5.5 g/cm3
Heat of fusion	21.5 kJ/mol
Heat of vaporization	444 kJ/mol
Molar heat capacity	24.89 J/(mol·K)
Atomic properties
Oxidation states	−3, −1, 0, +1, +2, +3, +4, +5 (an amphoteric oxide)
Electronegativity	Pauling scale: 1.63
Ionization energies	1st: 650.9 kJ/mol ; 2nd: 1414 kJ/mol ; 3rd: 2830 kJ/mol ; (more) ;
Atomic radius	empirical: 134 pm
Covalent radius	153±8 pm
	Spectral lines of vanadium
Other properties
Natural occurrence	primordial
Crystal structure	body-centered cubic (bcc) (cI2)
Lattice constant	a = 302.72 pm (at 20 °C)
Thermal expansion	8.77×10−6/K (at 20 °C)
Thermal conductivity	30.7 W/(m⋅K)
Electrical resistivity	197 nΩ⋅m (at 20 °C)
Magnetic ordering	paramagnetic
Molar magnetic susceptibility	+255.0×10−6 cm3/mol (298 K)
Young's modulus	128 GPa
Shear modulus	47 GPa
Bulk modulus	160 GPa
Speed of sound thin rod	4560 m/s (at 20 °C)
Poisson ratio	0.37
Mohs hardness	6.7
Vickers hardness	628–640 MPa
Brinell hardness	600–742 MPa
CAS Number	7440-62-2
History
Discovery	Andrés Manuel del Río (1801)
First isolation	Henry Enfield Roscoe (1867)
Named by	Nils Gabriel Sefström (1830)
Isotopes of vanadium v; e;
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Vanadium is a chemical element with the symbol V and atomic number 23. It is a hard, silvery-grey, malleable transition metal. The elemental metal is rarely found in nature, but once isolated artificially, the formation of an oxide layer (passivation) somewhat stabilizes the free metal against further oxidation.

Spanish-Mexican scientist Andrés Manuel del Río discovered compounds of vanadium in 1801 by analyzing a new lead-bearing mineral he called "brown lead". Though he initially presumed its qualities were due to the presence of a new element, he was later erroneously convinced by French chemist Hippolyte Victor Collet-Descotils that the element was just chromium. Then in 1830, Nils Gabriel Sefström generated chlorides of vanadium, thus proving there was a new element, and named it "vanadium" after the Scandinavian goddess of beauty and fertility, Vanadís (Freyja). The name was based on the wide range of colors found in vanadium compounds. Del Rio's lead mineral was ultimately named vanadinite for its vanadium content. In 1867 Henry Enfield Roscoe obtained the pure element.

Vanadium occurs naturally in about 65 minerals and fossil fuel deposits. It is produced in China and Russia from steel smelter slag. Other countries produce it either from magnetite directly, flue dust of heavy oil, or as a byproduct of uranium mining. It is mainly used to produce specialty steel alloys such as high-speed tool steels, and some aluminium alloys. The most important industrial vanadium compound, vanadium pentoxide, is used as a catalyst for the production of sulfuric acid. The vanadium redox battery for energy storage may be an important application in the future.

Large amounts of vanadium ions are found in a few organisms, possibly as a toxin. The oxide and some other salts of vanadium have moderate toxicity. Particularly in the ocean, vanadium is used by some life forms as an active center of enzymes, such as the vanadium bromoperoxidase of some ocean algae.

History

Vanadium was discovered in Mexico in 1801 by the Spanish mineralogist Andrés Manuel del Río. Del Río extracted the element from a sample of Mexican "brown lead" ore, later named vanadinite. He found that its salts exhibit a wide variety of colors, and as a result, he named the element panchromium (Greek: παγχρώμιο "all colors"). Later, Del Río renamed the element erythronium (Greek: ερυθρός "red") because most of the salts turned red upon heating. In 1805, French chemist Hippolyte Victor Collet-Descotils, backed by del Río's friend Baron Alexander von Humboldt, incorrectly declared that del Río's new element was an impure sample of chromium. Del Río accepted Collet-Descotils' statement and retracted his claim.^[6]

In 1831 Swedish chemist Nils Gabriel Sefström rediscovered the element in a new oxide he found while working with iron ores. Later that year, Friedrich Wöhler confirmed that this element was identical to that found by del Río and hence confirmed del Río's earlier work.^[7] Sefström chose a name beginning with V, which had not yet been assigned to any element. He called the element vanadium after Old Norse Vanadís (another name for the Norse Vanir goddess Freyja, whose attributes include beauty and fertility), because of the many beautifully colored chemical compounds it produces.^[7] On learning of Wöhler's findings, del Río began to passionately argue that his old claim be recognized, but the element kept the name vanadium.^[8] In 1831, the geologist George William Featherstonhaugh suggested that vanadium should be renamed "rionium" after del Río, but this suggestion was not followed.^[9]

The Model T used vanadium steel in its chassis.

As vanadium is usually found combined with other elements, the isolation of vanadium metal was difficult.^[10] In 1831, Berzelius reported the production of the metal, but Henry Enfield Roscoe showed that Berzelius had produced the nitride, vanadium nitride (VN). Roscoe eventually produced the metal in 1867 by reduction of vanadium(II) chloride, VCl₂, with hydrogen.^[11] In 1927, pure vanadium was produced by reducing vanadium pentoxide with calcium.^[12]

The first large-scale industrial use of vanadium was in the steel alloy chassis of the Ford Model T, inspired by French race cars. Vanadium steel allowed reduced weight while increasing tensile strength (ca. 1905).^[13] For the first decade of the 20th century, most vanadium ore were mined by the American Vanadium Company from the Minas Ragra in Peru. Later, the demand for uranium rose, leading to increased mining of that metal's ores. One major uranium ore was carnotite, which also contains vanadium. Thus, vanadium became available as a by-product of uranium production. Eventually, uranium mining began to supply a large share of the demand for vanadium.^[14]^[15]

In 1911, German chemist Martin Henze discovered vanadium in the hemovanadin proteins found in blood cells (or coelomic cells) of Ascidiacea (sea squirts).^[16]^[17]

Characteristics

Polycrystalline high-purity (99.95%) vanadium cuboids, ebeam remelted and macro-etched

Vanadium is an average-hard, ductile, steel-blue metal. It is electrically conductive and thermally insulating. Vanadium is usually described as "soft", because it is ductile, malleable, and not brittle.^[18]^[19] Vanadium is harder than most metals and steels (see Hardnesses of the elements (data page) and iron). It has good resistance to corrosion and it is stable against alkalis and sulfuric and hydrochloric acids.^[20] It is oxidized in air at about 933 K (660 °C, 1220 °F), although an oxide passivation layer forms even at room temperature.^[21]

Isotopes

Naturally occurring vanadium is composed of one stable isotope, ⁵¹V, and one radioactive isotope, ⁵⁰V. The latter has a half-life of 1.5×10¹⁷ years and a natural abundance of 0.25%. ⁵¹V has a nuclear spin of 7⁄2, which is useful for NMR spectroscopy.^[22] Twenty-four artificial radioisotopes have been characterized, ranging in mass number from 40 to 65. The most stable of these isotopes are ⁴⁹V with a half-life of 330 days, and ⁴⁸V with a half-life of 16.0 days. The remaining radioactive isotopes have half-lives shorter than an hour, most below 10 seconds. At least four isotopes have metastable excited states.^[23] Electron capture is the main decay mode for isotopes lighter than ⁵¹V. For the heavier ones, the most common mode is beta decay.^[24] The electron capture reactions lead to the formation of element 22 (titanium) isotopes, while beta decay leads to element 24 (chromium) isotopes.

Compounds

From left: [V(H₂O)₆]²⁺ (lilac), [V(H₂O)₆]³⁺ (green), [VO(H₂O)₅]²⁺ (blue) and [VO(H₂O)₅]³⁺ (yellow).

The chemistry of vanadium is noteworthy for the accessibility of the four adjacent oxidation states 2–5. In an aqueous solution, vanadium forms metal aquo complexes of which the colors are lilac [V(H₂O)₆]²⁺, green [V(H₂O)₆]³⁺, blue [VO(H₂O)₅]²⁺, yellow-orange oxides [VO(H₂O)₅]³⁺, the formula for which depends on pH. Vanadium(II) compounds are reducing agents, and vanadium(V) compounds are oxidizing agents. Vanadium(IV) compounds often exist as vanadyl derivatives, which contain the VO²⁺ center.^[20]

Ammonium vanadate(V) (NH₄VO₃) can be successively reduced with elemental zinc to obtain the different colors of vanadium in these four oxidation states. Lower oxidation states occur in compounds such as V(CO)₆, [V(CO)
₆]⁻
and substituted derivatives.^[20]

Vanadium pentoxide is a commercially important catalyst for the production of sulfuric acid, a reaction that exploits the ability of vanadium oxides to undergo redox reactions.^[20]

The vanadium redox battery utilizes all four oxidation states: one electrode uses the +5/+4 couple and the other uses the +3/+2 couple. Conversion of these oxidation states is illustrated by the reduction of a strongly acidic solution of a vanadium(V) compound with zinc dust or amalgam. The initial yellow color characteristic of the pervanadyl ion [VO₂(H₂O)₄]⁺ is replaced by the blue color of [VO(H₂O)₅]²⁺, followed by the green color of [V(H₂O)₆]³⁺ and then the violet color of [V(H₂O)₆]²⁺.^[20]

Oxyanions

In an aqueous solution, vanadium(V) forms an extensive family of oxyanions as established by ⁵¹V NMR spectroscopy.^[22] The interrelationships in this family are described by the predominance diagram, which shows at least 11 species, depending on pH and concentration.^[25] The tetrahedral orthovanadate ion, VO³⁻
₄, is the principal species present at pH 12–14. Similar in size and charge to phosphorus(V), vanadium(V) also parallels its chemistry and crystallography. Orthovanadate VO³⁻
₄ is used in protein crystallography^[26] to study the biochemistry of phosphate.^[27] Besides that, this anion also has been shown to interact with the activity of some specific enzymes.^[28]^[29] The tetrathiovanadate [VS₄]³⁻ is analogous to the orthovanadate ion.^[30]

At lower pH values, the monomer [HVO₄]²⁻ and dimer [V₂O₇]⁴⁻ are formed, with the monomer predominant at a vanadium concentration of less than c. 10⁻²M (pV > 2, where pV is equal to the minus value of the logarithm of the total vanadium concentration/M). The formation of the divanadate ion is analogous to the formation of the dichromate ion.^[31]^[32] As the pH is reduced, further protonation and condensation to polyvanadates occur: at pH 4–6 [H₂VO₄]⁻ is predominant at pV greater than ca. 4, while at higher concentrations trimers and tetramers are formed.^[33] Between pH 2–4 decavanadate predominates, its formation from orthovanadate is represented by this condensation reaction:

10 [VO₄]³⁻ + 24 H⁺ → [V₁₀O₂₈]⁶⁻ + 12 H₂O

In decavanadate, each V(V) center is surrounded by six oxide ligands.^[20] Vanadic acid, H₃VO₄, exists only at very low concentrations because protonation of the tetrahedral species [H₂VO₄]⁻ results in the preferential formation of the octahedral [VO₂(H₂O)₄]⁺ species.^[34] In strongly acidic solutions, pH < 2, [VO₂(H₂O)₄]⁺ is the predominant species, while the oxide V₂O₅ precipitates from solution at high concentrations. The oxide is formally the acid anhydride of vanadic acid. The structures of many vanadate compounds have been determined by X-ray crystallography.

The Pourbaix diagram for vanadium in water, which shows the redox potentials between various vanadium species in different oxidation states.^[35]

Vanadium(V) forms various peroxo complexes, most notably in the active site of the vanadium-containing bromoperoxidase enzymes. The species VO(O₂)(H₂O)₄⁺ is stable in acidic solutions. In alkaline solutions, species with 2, 3 and 4 peroxide groups are known; the last forms violet salts with the formula M₃V(O₂)₄ nH₂O (M= Li, Na, etc.), in which the vanadium has an 8-coordinate dodecahedral structure.^[36]^[37]

Halide derivatives

Twelve binary halides, compounds with the formula VX_n (n=2..5), are known.^[38] VI₄, VCl₅, VBr₅, and VI₅ do not exist or are extremely unstable. In combination with other reagents, VCl₄ is used as a catalyst for the polymerization of dienes. Like all binary halides, those of vanadium are Lewis acidic, especially those of V(IV) and V(V).^[38] Many of the halides form octahedral complexes with the formula VX_nL_6−n (X= halide; L= other ligand).

Many vanadium oxyhalides (formula VO_mX_n) are known.^[39] The oxytrichloride and oxytrifluoride (VOCl₃ and VOF₃) are the most widely studied. Akin to POCl₃, they are volatile,^[40] adopt tetrahedral structures in the gas phase, and are Lewis acidic.^[41]

Coordination compounds

Complexes of vanadium(II) and (III) are relatively exchange inert and reducing. Those of V(IV) and V(V) are oxidants. The vanadium ion is rather large and some complexes achieve coordination numbers greater than 6, as is the case in [V(CN)₇]⁴⁻. Oxovanadium(V) also forms 7 coordinate coordination complexes with tetradentate ligands and peroxides and these complexes are used for oxidative brominations and thioether oxidations. The coordination chemistry of V⁴⁺ is dominated by the vanadyl center, VO²⁺, which binds four other ligands strongly and one weakly (the one trans to the vanadyl center). An example is vanadyl acetylacetonate (V(O)(O₂C₅H₇)₂). In this complex, the vanadium is 5-coordinate, distorted square pyramidal, meaning that a sixth ligand, such as pyridine, may be attached, though the association constant of this process is small. Many 5-coordinate vanadyl complexes have a trigonal bipyramidal geometry, such as VOCl₂(NMe₃)₂.^[42] The coordination chemistry of V⁵⁺ is dominated by the relatively stable dioxovanadium coordination complexes^[43] which are often formed by aerial oxidation of the vanadium(IV) precursors indicating the stability of the +5 oxidation state and ease of interconversion between the +4 and +5 states.^[44]

Organometallic compounds

The organometallic chemistry of vanadium is well–developed. Vanadocene dichloride is a versatile starting reagent and has applications in organic chemistry.^[45] Vanadium carbonyl, V(CO)₆, is a rare example of a paramagnetic metal carbonyl. Reduction yields V(CO)⁻
₆ (isoelectronic with Cr(CO)₆), which may be further reduced with sodium in liquid ammonia to yield V(CO)³⁻
₅ (isoelectronic with Fe(CO)₅).^[46]^[47]

Occurrence

Vanadium is the 20th most abundant element in the earth's crust;^[48] metallic vanadium is rare in nature (known as native vanadium),^[49]^[50] but vanadium compounds occur naturally in about 65 different minerals.

At the beginning of the 20th century, a large deposit of vanadium ore was discovered, in the Minas Ragra vanadium mine near Junín, Cerro de Pasco, Peru.^[51]^[52]^[53] For several years this patrónite (VS₄)^[54] deposit was an economically significant source for vanadium ore. In 1920 roughly two-thirds of the worldwide production was supplied by the mine in Peru.^[55] With the production of uranium in the 1910s and 1920s from carnotite (K₂(UO₂)₂(VO₄)₂·3H₂O) vanadium became available as a side product of uranium production. Vanadinite (Pb₅(VO₄)₃Cl) and other vanadium bearing minerals are only mined in exceptional cases. With the rising demand, much of the world's vanadium production is now sourced from vanadium-bearing magnetite found in ultramafic gabbro bodies. If this titanomagnetite is used to produce iron, most of the vanadium goes to the slag and is extracted from it.^[56]^[53]

Vanadium is mined mostly in China, South Africa and eastern Russia. In 2022 these three countries mined more than 96% of the 100,000 tons of produced vanadium, with China providing 70%.^[57]

Vanadium is also present in bauxite and deposits of crude oil, coal, oil shale, and tar sands. In crude oil, concentrations up to 1200 ppm have been reported. When such oil products are burned, traces of vanadium may cause corrosion in engines and boilers.^[58] An estimated 110,000 tons of vanadium per year are released into the atmosphere by burning fossil fuels.^[59] Black shales are also a potential source of vanadium. During WW II some vanadium was extracted from alum shales in the south of Sweden.^[60]

In the universe, the cosmic abundance of vanadium is 0.0001%, making the element nearly as common as copper or zinc.^[61] Vanadium is detected spectroscopically in light from the Sun and sometimes in the light from other stars.^[62] The vanadyl ion is also abundant in seawater, having an average concentration of 30 nM (1.5 mg/m³).^[61] Some mineral water springs also contain the ion in high concentrations. For example, springs near Mount Fuji contain as much as 54 μg per liter.^[61]

Production

Vanadium metal is obtained by a multistep process that begins with roasting crushed ore with NaCl or Na₂CO₃ at about 850 °C to give sodium metavanadate (NaVO₃). An aqueous extract of this solid is acidified to produce "red cake", a polyvanadate salt, which is reduced with calcium metal. As an alternative for small-scale production, vanadium pentoxide is reduced with hydrogen or magnesium. Many other methods are also used, in all of which vanadium is produced as a byproduct of other processes.^[63] Purification of vanadium is possible by the crystal bar process developed by Anton Eduard van Arkel and Jan Hendrik de Boer in 1925. It involves the formation of the metal iodide, in this example vanadium(III) iodide, and the subsequent decomposition to yield pure metal:^[64]

2 V + 3 I₂ ⇌ 2 VI₃

Most vanadium is used as a steel alloy called ferrovanadium. Ferrovanadium is produced directly by reducing a mixture of vanadium oxide, iron oxides and iron in an electric furnace. The vanadium ends up in pig iron produced from vanadium-bearing magnetite. Depending on the ore used, the slag contains up to 25% of vanadium.^[63]

Applications

Alloys

Approximately 85% of the vanadium produced is used as ferrovanadium or as a steel additive.^[63] The considerable increase of strength in steel containing small amounts of vanadium was discovered in the early 20th century. Vanadium forms stable nitrides and carbides, resulting in a significant increase in the strength of steel.^[65] From that time on, vanadium steel was used for applications in axles, bicycle frames, crankshafts, gears, and other critical components. There are two groups of vanadium steel alloys. Vanadium high-carbon steel alloys contain 0.15% to 0.25% vanadium, and high-speed tool steels (HSS) have a vanadium content of 1% to 5%. For high-speed tool steels, a hardness above HRC 60 can be achieved. HSS steel is used in surgical instruments and tools.^[66] Powder-metallurgic alloys contain up to 18% percent vanadium. The high content of vanadium carbides in those alloys increases wear resistance significantly. One application for those alloys is tools and knives.^[67]

Vanadium stabilizes the beta form of titanium and increases the strength and temperature stability of titanium. Mixed with aluminium in titanium alloys, it is used in jet engines, high-speed airframes and dental implants. The most common alloy for seamless tubing is Titanium 3/2.5 containing 2.5% vanadium, the titanium alloy of choice in the aerospace, defense, and bicycle industries.^[68] Another common alloy, primarily produced in sheets, is Titanium 6AL-4V, a titanium alloy with 6% aluminium and 4% vanadium.^[69]

Several vanadium alloys show superconducting behavior. The first A15 phase superconductor was a vanadium compound, V₃Si, which was discovered in 1952.^[70] Vanadium-gallium tape is used in superconducting magnets (17.5 teslas or 175,000 gauss). The structure of the superconducting A15 phase of V₃Ga is similar to that of the more common Nb₃Sn and Nb₃Ti.^[71]

It has been found that a small amount, 40 to 270 ppm, of vanadium in Wootz steel significantly improved the strength of the product, and gave it the distinctive patterning. The source of the vanadium in the original Wootz steel ingots remains unknown.^[72]

Vanadium can be used as a substitute for molybdenum in armor steel, though the alloy produced is far more brittle and prone to spalling on non-penetrating impacts.^[73] The Third Reich was one of the most prominent users of such alloys, in armored vehicles like Tiger II or Jagdtiger.^[74]

Catalysts

Vanadium compounds are used extensively as catalysts;^[75] Vanadium pentoxide V₂O₅, is used as a catalyst in manufacturing sulfuric acid by the contact process^[76] In this process sulfur dioxide (SO
₂) is oxidized to the trioxide (SO
₃):^[20] In this redox reaction, sulfur is oxidized from +4 to +6, and vanadium is reduced from +5 to +4:

V₂O₅ + SO₂ → 2 VO₂ + SO₃

The catalyst is regenerated by oxidation with air:

4 VO₂ + O₂ → 2 V₂O₅

Similar oxidations are used in the production of maleic anhydride:

C₄H₁₀ + 3.5 O₂ → C₄H₂O₃ + 4 H₂O

Phthalic anhydride and several other bulk organic compounds are produced similarly. These green chemistry processes convert inexpensive feedstocks to highly functionalized, versatile intermediates.^[77]^[78]

Vanadium is an important component of mixed metal oxide catalysts used in the oxidation of propane and propylene to acrolein, acrylic acid or the ammoxidation of propylene to acrylonitrile.^[79]

Other uses

The vanadium redox battery, a type of flow battery, is an electrochemical cell consisting of aqueous vanadium ions in different oxidation states.^[80]^[81] Batteries of this type were first proposed in the 1930s and developed commercially from the 1980s onwards. Cells use +5 and +2 formal oxidization state ions. Vanadium redox batteries are used commercially for grid energy storage.^[82]

Vanadate can be used for protecting steel against rust and corrosion by conversion coating.^[83] Vanadium foil is used in cladding titanium to steel because it is compatible with both iron and titanium.^[84] The moderate thermal neutron-capture cross-section and the short half-life of the isotopes produced by neutron capture makes vanadium a suitable material for the inner structure of a fusion reactor.^[85]^[86]

Proposed

Lithium vanadium oxide has been proposed for use as a high energy density anode for lithium-ion batteries, at 745 Wh/L when paired with a lithium cobalt oxide cathode.^[87] Vanadium phosphates have been proposed as the cathode in the lithium vanadium phosphate battery, another type of lithium-ion battery.^[88]

Biological role

Vanadium has a more significant role in marine environments than terrestrial ones.^[89]

Vanadoenzymes

Several species of marine algae produce vanadium bromoperoxidase as well as the closely related chloroperoxidase (which may use a heme or vanadium cofactor) and iodoperoxidases. The bromoperoxidase produces an estimated 1–2 million tons of bromoform and 56,000 tons of bromomethane annually.^[90] Most naturally occurring organobromine compounds are produced by this enzyme,^[91] catalyzing the following reaction (R-H is hydrocarbon substrate):

R-H + Br⁻ + H₂O₂ → R-Br + H₂O + OH⁻

A vanadium nitrogenase is used by some nitrogen-fixing micro-organisms, such as Azotobacter. In this role, vanadium serves in place of the more common molybdenum or iron, and gives the nitrogenase slightly different properties.^[92]

Vanadium accumulation in tunicates

Vanadium is essential to tunicates, where it is stored in the highly acidified vacuoles of certain blood cell types, designated vanadocytes. Vanabins (vanadium-binding proteins) have been identified in the cytoplasm of such cells. The concentration of vanadium in the blood of ascidian tunicates is as much as ten million times higher^[specify]^[93]^[94] than the surrounding seawater, which normally contains 1 to 2 µg/L.^[95]^[96] The function of this vanadium concentration system and these vanadium-bearing proteins is still unknown, but the vanadocytes are later deposited just under the outer surface of the tunic, where they may deter predation.^[97]

Fungi

Amanita muscaria and related species of macrofungi accumulate vanadium (up to 500 mg/kg in dry weight). Vanadium is present in the coordination complex amavadin^[98] in fungal fruit-bodies. The biological importance of the accumulation is unknown.^[99]^[100] Toxic or peroxidase enzyme functions have been suggested.^[101]

Mammals

Deficiencies in vanadium result in reduced growth in rats.^[102] The U.S. Institute of Medicine has not confirmed that vanadium is an essential nutrient for humans, so neither a Recommended Dietary Intake nor an Adequate Intake have been established. Dietary intake is estimated at 6 to 18 µg/day, with less than 5% absorbed. The Tolerable Upper Intake Level (UL) of dietary vanadium, beyond which adverse effects may occur, is set at 1.8 mg/day.^[103]

Research

Vanadyl sulfate as a dietary supplement has been researched as a means of increasing insulin sensitivity or otherwise improving glycemic control in people who are diabetic. Some of the trials had significant treatment effects but were deemed as being of poor study quality. The amounts of vanadium used in these trials (30 to 150 mg) far exceeded the safe upper limit.^[104]^[105] The conclusion of the systemic review was "There is no rigorous evidence that oral vanadium supplementation improves glycaemic control in type 2 diabetes. The routine use of vanadium for this purpose cannot be recommended."^[104]

In astrobiology, it has been suggested that discrete vanadium accumulations on Mars could be a potential microbial biosignature when used in conjunction with Raman spectroscopy and morphology.^[106]^[107]

Safety

All vanadium compounds should be considered toxic.^[108] Tetravalent VOSO₄ has been reported to be at least 5 times more toxic than trivalent V₂O₃.^[109] The US Occupational Safety and Health Administration (OSHA) has set an exposure limit of 0.05 mg/m³ for vanadium pentoxide dust and 0.1 mg/m³ for vanadium pentoxide fumes in workplace air for an 8-hour workday, 40-hour work week.^[110] The US National Institute for Occupational Safety and Health (NIOSH) has recommended that 35 mg/m³ of vanadium be considered immediately dangerous to life and health, that is, likely to cause permanent health problems or death.^[110]

Vanadium compounds are poorly absorbed through the gastrointestinal system. Inhalation of vanadium and vanadium compounds results primarily in adverse effects on the respiratory system.^[111]^[112]^[113] Quantitative data are, however, insufficient to derive a subchronic or chronic inhalation reference dose. Other effects have been reported after oral or inhalation exposures on blood parameters,^[114]^[115] liver,^[116] neurological development,^[117] and other organs^[118] in rats.

There is little evidence that vanadium or vanadium compounds are reproductive toxins or teratogens. Vanadium pentoxide was reported to be carcinogenic in male rats and in male and female mice by inhalation in an NTP study,^[112] although the interpretation of the results has been disputed a few years after the report.^[119] The carcinogenicity of vanadium has not been determined by the United States Environmental Protection Agency.^[120]

Vanadium traces in diesel fuels are the main fuel component in high temperature corrosion. During combustion, vanadium oxidizes and reacts with sodium and sulfur, yielding vanadate compounds with melting points as low as 530 °C, which attack the passivation layer on steel and render it susceptible to corrosion. The solid vanadium compounds also abrade engine components.^[121]^[122]

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^ Marshall, James L.; Marshall, Virginia R. (2004). "Rediscovery of the Elements: The "Undiscovery" of Vanadium" (PDF). unt.edu. The Hexagon. p. 45.
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External links

Videos

Vanadium at The Periodic Table of Videos (University of Nottingham)

Research papers

[1] "Standard Atomic Weights: Vanadium". CIAAW. 1977.

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 ==History==
-Vanadium was [[discovery of the chemical elements|discovered]] in Mexico in 1801 by the Spanish mineralogist [[Andrés Manuel del Río]]. Del Río extracted the element from a sample of Mexican "brown lead" ore, later named [[vanadinite]]. He found that its salts exhibit a wide variety of colors, and as a result, he named the element ''panchromium'' (Greek: παγχρώμιο "all colors"). Later, Del Río renamed the element ''erythronium'' (Greek: ερυθρός "red") because most of the salts turned red upon heating. In 1805, French chemist [[Hippolyte Victor Collet-Descotils]], backed by del Río's friend Baron [[Alexander von Humboldt]], incorrectly declared that del Río's new element was an impure sample of [[chromium]]. Del Río accepted Collet-Descotils' statement and retracted his claim.<ref name="Cintas">{{cite journal|title= The Road to Chemical Names and Eponyms: Discovery, Priority, and Credit|author= Cintas, Pedro|journal= Angewandte Chemie International Edition|volume= 43|issue= 44|date= 2004|pmid= 15376297|doi= 10.1002/anie.200330074|pages= 5888–94}}</ref>
+Vanadium was [[discovery of the chemical elements|discovered]] in Mexico in 1801 by the Spanish mineralogist [[Andrés Manuel del Río]]. Del Río extracted the element from a sample of Mexican "brown lead" ore, later named [[vanadinite]]. He found that its salts exhibit a wide variety of colors, and as a result, he named the element ''panchromium'' (Greek: παγχρώμιο "all colors"). Later, Del Río renamed the element ''erythronium'' (Greek: ερυθρός "red") because most of the salts turned red upon heating. In 1805, French chemist [[Hippolyte Victor Collet-Descotils]], backed by del Río's friend Baron [[Alexander von Humboldt]], incorrectly declared that del Río's new element was an impure sample of [[chromium]]. Del Río accepted Collet-Descotils' statement and retracted his claim.<ref name="Cintas">{{cite journal |last1=Cintas |first1=Pedro |title=The Road to Chemical Names and Eponyms: Discovery, Priority, and Credit |journal=Angewandte Chemie International Edition |date=12 November 2004 |volume=43 |issue=44 |pages=5888–5894 |doi=10.1002/anie.200330074 |pmid=15376297 }}</ref>
 In 1831 Swedish chemist [[Nils Gabriel Sefström]] rediscovered the element in a new oxide he found while working with [[iron ore]]s. Later that year, [[Friedrich Wöhler]] confirmed that this element was identical to that found by del Río and hence confirmed del Río's earlier work.<ref name="sefs">{{cite journal|title= Ueber das Vanadin, ein neues Metall, gefunden im Stangeneisen von Eckersholm, einer Eisenhütte, die ihr Erz von Taberg in Småland bezieht|first= N. G.|last= Sefström|journal= [[Annalen der Physik und Chemie]]|volume= 97|issue= 1|pages= 43–49|date= 1831|doi= 10.1002/andp.18310970103|bibcode= 1831AnP....97...43S|url= https://zenodo.org/record/1423544}}</ref> Sefström chose a name beginning with V, which had not yet been assigned to any element. He called the element ''vanadium'' after [[Old Norse]] ''[[list of names of Freyja|Vanadís]]'' (another name for the [[Norse mythology|Norse]] [[Vanir]] goddess [[Freyja]], whose attributes include beauty and fertility), because of the many beautifully colored [[chemical compound]]s it produces.<ref name="sefs" /> On learning of Wöhler's findings, del Río began to passionately argue that his old claim be recognized, but the element kept the name ''vanadium''.<ref name=vanadium3>{{cite web |url=https://digital.library.unt.edu/ark:/67531/metadc111200/m2/1/high_res_d/metadc111200.pdf |title=Rediscovery of the Elements: The "Undiscovery" of Vanadium |last1=Marshall |first1=James L. |last2=Marshall |first2=Virginia R. |date=2004 |website=unt.edu |publisher=The Hexagon |page=45 |access-date= |quote=}}</ref> In 1831, the geologist [[George William Featherstonhaugh]] suggested that vanadium should be renamed "''rionium''" after del Río, but this suggestion was not followed.<ref>{{cite journal |journal= The Monthly American Journal of Geology and Natural Science |first= George William|last= Featherstonhaugh |title=New Metal, provisionally called Vanadium |year= 1831|page=69 |url= https://archive.org/stream/monthlyamericanj11831phil#page/68/mode/2up/search/rionium}}</ref><!--Featherstonhaugh, the editor of the journal cited, comments on a letter from Berzelius to [[Pierre Louis Dulong]]-->
 [[File:1910Ford-T.jpg|thumb|left|The [[Model T]] used vanadium steel in its [[chassis]].]]
-As vanadium is usually found combined with other elements, the isolation of vanadium metal was difficult.<ref>{{Cite journal |last=HABASHI |first=FATHI |date=2001-01-01 |title=Historical Introduction to Refractory Metals |url=https://doi.org/10.1080/08827509808962488 |journal=Mineral Processing and Extractive Metallurgy Review |volume=22 |issue=1 |pages=25–53 |doi=10.1080/08827509808962488 |bibcode=2001MPEMR..22...25H |s2cid=100370649 |issn=0882-7508}}</ref> In 1831, [[Jöns Jakob Berzelius|Berzelius]] reported the production of the metal, but [[Henry Enfield Roscoe]] showed that Berzelius had produced the nitride, [[vanadium nitride]] (VN). Roscoe eventually produced the metal in 1867 by reduction of [[vanadium(II) chloride]], VCl<sub>2</sub>, with [[hydrogen]].<ref name="Roscoe">{{cite journal|title= Researches on Vanadium. Part II|author= Roscoe, Henry E. |journal= [[Proceedings of the Royal Society of London]]|volume= 18|pages=37–42|date= 1869–1870|doi= 10.1098/rspl.1869.0012|issue= 114–122|url= https://zenodo.org/record/1432055|doi-access= free}}</ref> In 1927, pure vanadium was produced by reducing [[vanadium pentoxide]] with [[calcium]].<ref name="Marden">{{cite journal|title= Vanadium|first= J. W.|last= Marden|author2=Rich, M. N. |journal= Industrial and Engineering Chemistry|date= 1927|volume= 19|pages=786–788|doi= 10.1021/ie50211a012|issue= 7}}</ref>
+As vanadium is usually found combined with other elements, the isolation of vanadium metal was difficult.<ref>{{cite journal |last1=Habashi |first1=Fathi |title=Historical Introduction to Refractory Metals |journal=Mineral Processing and Extractive Metallurgy Review |date=January 2001 |volume=22 |issue=1 |pages=25–53 |doi=10.1080/08827509808962488 |bibcode=2001MPEMR..22...25H |s2cid=100370649 }}</ref> In 1831, [[Jöns Jakob Berzelius|Berzelius]] reported the production of the metal, but [[Henry Enfield Roscoe]] showed that Berzelius had produced the nitride, [[vanadium nitride]] (VN). Roscoe eventually produced the metal in 1867 by reduction of [[vanadium(II) chloride]], VCl<sub>2</sub>, with [[hydrogen]].<ref name="Roscoe">{{cite journal |title=XIX. Researches on vanadium |journal=Proceedings of the Royal Society of London |date=31 December 1870 |volume=18 |issue=114-122 |pages=37–42 |doi=10.1098/rspl.1869.0012 }}</ref> In 1927, pure vanadium was produced by reducing [[vanadium pentoxide]] with [[calcium]].<ref name="Marden">{{cite journal |last1=Marden |first1=J. W. |last2=Rich |first2=M. N. |title=Vanadium 1 |journal=Industrial & Engineering Chemistry |date=July 1927 |volume=19 |issue=7 |pages=786–788 |doi=10.1021/ie50211a012 }}</ref>
-The first large-scale industrial use of vanadium was in the [[steel]] alloy chassis of the [[Ford Model T]], inspired by French race cars. Vanadium steel allowed reduced weight while increasing [[tensile strength]] (ca. 1905).<ref>{{cite book|title=Managing Technological Innovation: Competitive Advantage from Change|first= Frederick|last= Betz|publisher=Wiley-IEEE|date= 2003|isbn= 978-0-471-22563-8|pages=158–159 |url= https://books.google.com/books?id=KnpGtu-R77UC&pg=PA158}}</ref> For the first decade of the 20th century, most vanadium ore were mined by the [[American Vanadium Company]] from the [[Minas Ragra]] in Peru. Later, the demand for uranium rose, leading to increased mining of that metal's ores. One major uranium ore was [[carnotite]], which also contains vanadium. Thus, vanadium became available as a by-product of uranium production. Eventually, uranium mining began to supply a large share of the demand for vanadium.<ref name="Busch1961">{{cite book|author=Phillip Maxwell Busch|title=Vanadium: A Materials Survey|url=https://books.google.com/books?id=5gZS8X-NDHQC|year=1961|publisher=U.S. Department of the Interior, Bureau of Mines |page=65}}</ref><ref>{{cite web |first= James M. |last= Wise |date= May 2018 |url= https://www.southamericatotheworld.com/remarkable-folded-dacitic-dikes-at-mina-ragra-peru/ |title= Remarkable folded dacitic dikes at Mina Ragra, Peru}}</ref>
+The first large-scale industrial use of vanadium was in the [[steel]] alloy chassis of the [[Ford Model T]], inspired by French race cars. Vanadium steel allowed reduced weight while increasing [[tensile strength]] (ca. 1905).<ref>{{cite book|title=Managing Technological Innovation: Competitive Advantage from Change|first= Frederick|last= Betz|publisher=Wiley-IEEE|date= 2003|isbn= 978-0-471-22563-8|pages=158–159 |url= https://books.google.com/books?id=KnpGtu-R77UC&pg=PA158}}</ref> For the first decade of the 20th century, most vanadium ore were mined by the [[American Vanadium Company]] from the [[Minas Ragra]] in Peru. Later, the demand for uranium rose, leading to increased mining of that metal's ores. One major uranium ore was [[carnotite]], which also contains vanadium. Thus, vanadium became available as a by-product of uranium production. Eventually, uranium mining began to supply a large share of the demand for vanadium.<ref name="Busch1961">{{cite book |last1=Busch |first1=Phillip Maxwell |title=Vanadium: A Materials Survey |date=1961 |publisher=U.S. Department of the Interior, Bureau of Mines |page=65 |url=http://digital.library.unt.edu/ark:/67531/metadc170746/ |oclc=934517147 }}</ref><ref>{{cite web |first= James M. |last= Wise |date= May 2018 |url= https://www.southamericatotheworld.com/remarkable-folded-dacitic-dikes-at-mina-ragra-peru/ |title= Remarkable folded dacitic dikes at Mina Ragra, Peru}}</ref>
 In 1911, German chemist [[Friedrich Wolfgang Martin Henze|Martin Henze]] discovered vanadium in the [[hemovanadin]] proteins found in [[blood cell]]s (or [[coelom]]ic cells) of [[Ascidiacea]] (sea squirts).<ref>{{cite journal |last= Henze |first=M. |date= 1911 |title= Untersuchungen über das Blut der Ascidien. I. Mitteilung |url= https://books.google.com/books?id=x5g8AAAAIAAJ |journal= Z. Physiol. Chem. |volume= 72 |issue= 5–6 |pages= 494–50 |doi= 10.1515/bchm2.1911.72.5-6.494 |author-link=Friedrich Wolfgang Martin Henze}}</ref><ref name="michibata2002">{{cite journal|doi= 10.1002/jemt.10042|last1= Michibata|first1= H.|last2= Uyama|first2= T.|last3= Ueki|first3= T.|last4= Kanamori|first4= K.|date= 2002|title= Vanadocytes, cells hold the key to resolving the highly selective accumulation and reduction of vanadium in ascidians|journal= Microscopy Research and Technique|volume= 56|issue= 6 |pages= 421–434|pmid= 11921344|s2cid= 15127292|url= http://ir.lib.hiroshima-u.ac.jp/files/public/0/22/20141016115442843522/MicroscopResTech_56_421-434_2002.pdf}}</ref>
@@ Line 44: / Line 44: @@
 ===Oxyanions===
 [[File:decavanadate polyhedra.png|thumb|The [[decavanadate]] structure]]
-<!-- [[File:Ammonium-metavanadate-chains-3D.png|thumb|upright|Metavanadate chains]] -->In an aqueous solution, vanadium(V) forms an extensive family of [[oxyanion]]s as established by [[Vanadium-51 nuclear magnetic resonance|<sup>51</sup>V NMR spectroscopy]].<ref name="Rehder">{{cite book |doi=10.1016/S0066-4103(07)62002-X|title=Vanadium-51 NMR|series=Annual Reports on NMR Spectroscopy|year=2007|last1=Rehder|first1=D.|last2=Polenova|first2=T.|last3=Bühl|first3=M.|volume=62|pages=49–114|isbn=9780123739193}}</ref> The interrelationships in this family are described by the [[predominance diagram]], which shows at least 11 species, depending on pH and concentration.<ref>{{Greenwood&Earnshaw|page=984}}</ref> The tetrahedral orthovanadate ion, {{chem|VO|4|3−}}, is the principal species present at pH 12–14. Similar in size and charge to phosphorus(V), vanadium(V) also parallels its chemistry and crystallography. [[Sodium orthovanadate|Orthovanadate]] V{{chem|O|4|3−}} is used in [[protein crystallography]]<ref>{{cite journal|volume= 577|issue= 3|doi= 10.1016/j.febslet.2004.10.022|pmid= 15556602|date= 2004|title= The power of vanadate in crystallographic investigations of phosphoryl transfer enzymes|first1= Irmgard|last1= Sinning|journal= FEBS Letters|last2= Hol|first2= Wim G. J.|pages= 315–21|s2cid= 8328704|doi-access= free}}</ref> to study the [[biochemistry]] of phosphate.<ref>{{cite journal|volume= 181|pmc= 1161148|date= 1979|title= Inhibition of human alkaline phosphatases by vanadate|first= Lorne E.|last= Seargeant|author2=Stinson, Robert A. |journal= Biochemical Journal|pmid=486156|issue=1|pages= 247–50|doi= 10.1042/bj1810247}}</ref> Besides that, this anion also has been shown to interact with the activity of some specific enzymes.<ref>{{Cite journal |last1=Crans |first1=Debbie C. |last2=Simone |first2=Carmen M. |date=1991-07-09 |title=Nonreductive interaction of vanadate with an enzyme containing a thiol group in the active site: glycerol-3-phosphate dehydrogenase |url=https://pubs.acs.org/doi/abs/10.1021/bi00241a015 |journal=Biochemistry |volume=30 |issue=27 |pages=6734–6741 |doi=10.1021/bi00241a015 |pmid=2065057 |issn=0006-2960}}</ref><ref>{{Cite journal |last1=Karlish |first1=S. J. D. |last2=Beaugé |first2=L. A. |last3=Glynn |first3=I. M. |date=Nov 1979 |title=Vanadate inhibits (Na+ + K+)ATPase by blocking a conformational change of the unphosphorylated form |url=https://www.nature.com/articles/282333a0 |journal=Nature |volume=282 |issue=5736 |pages=333–335 |doi=10.1038/282333a0 |pmid=228199 |bibcode=1979Natur.282..333K |s2cid=4341480 |issn=1476-4687}}</ref> The tetrathiovanadate [VS<sub>4</sub>]<sup>3−</sup> is analogous to the orthovanadate ion.<ref>{{Greenwood&Earnshaw|page=988}}</ref>
+<!-- [[File:Ammonium-metavanadate-chains-3D.png|thumb|upright|Metavanadate chains]] -->In an aqueous solution, vanadium(V) forms an extensive family of [[oxyanion]]s as established by [[Vanadium-51 nuclear magnetic resonance|<sup>51</sup>V NMR spectroscopy]].<ref name="Rehder">{{cite book |doi=10.1016/S0066-4103(07)62002-X|title=Vanadium-51 NMR|series=Annual Reports on NMR Spectroscopy|year=2007|last1=Rehder|first1=D.|last2=Polenova|first2=T.|last3=Bühl|first3=M.|volume=62|pages=49–114|isbn=9780123739193}}</ref> The interrelationships in this family are described by the [[predominance diagram]], which shows at least 11 species, depending on pH and concentration.<ref>{{Greenwood&Earnshaw|page=984}}</ref> The tetrahedral orthovanadate ion, {{chem|VO|4|3−}}, is the principal species present at pH 12–14. Similar in size and charge to phosphorus(V), vanadium(V) also parallels its chemistry and crystallography. [[Sodium orthovanadate|Orthovanadate]] V{{chem|O|4|3−}} is used in [[protein crystallography]]<ref>{{cite journal|volume= 577|issue= 3|doi= 10.1016/j.febslet.2004.10.022|pmid= 15556602|date= 2004|title= The power of vanadate in crystallographic investigations of phosphoryl transfer enzymes|first1= Irmgard|last1= Sinning|journal= FEBS Letters|last2= Hol|first2= Wim G. J.|pages= 315–21|s2cid= 8328704|doi-access= free}}</ref> to study the [[biochemistry]] of phosphate.<ref>{{cite journal |last1=Seargeant |first1=L E |last2=Stinson |first2=R A |title=Inhibition of human alkaline phosphatases by vanadate |journal=Biochemical Journal |date=1 July 1979 |volume=181 |issue=1 |pages=247–250 |doi=10.1042/bj1810247 }}</ref> Besides that, this anion also has been shown to interact with the activity of some specific enzymes.<ref>{{cite journal |last1=Crans |first1=Debbie C. |last2=Simone |first2=Carmen M. |title=Nonreductive interaction of vanadate with an enzyme containing a thiol group in the active site: glycerol-3-phosphate dehydrogenase |journal=Biochemistry |date=9 July 1991 |volume=30 |issue=27 |pages=6734–6741 |doi=10.1021/bi00241a015 |pmid=2065057 }}</ref><ref>{{cite journal |last1=Karlish |first1=S. J. D. |last2=Beaugé |first2=L. A. |last3=Glynn |first3=I. M. |title=Vanadate inhibits (Na+ + K+)ATPase by blocking a conformational change of the unphosphorylated form |journal=Nature |date=November 1979 |volume=282 |issue=5736 |pages=333–335 |doi=10.1038/282333a0 |pmid=228199 |bibcode=1979Natur.282..333K |s2cid=4341480 }}</ref> The tetrathiovanadate [VS<sub>4</sub>]<sup>3−</sup> is analogous to the orthovanadate ion.<ref>{{Greenwood&Earnshaw|page=988}}</ref>
-At lower pH values, the monomer [HVO<sub>4</sub>]<sup>2−</sup> and dimer [V<sub>2</sub>O<sub>7</sub>]<sup>4−</sup> are formed, with the monomer predominant at a vanadium concentration of less than c. 10<sup>−2</sup>M (pV > 2, where pV is equal to the minus value of the logarithm of the total vanadium concentration/M). The formation of the divanadate ion is analogous to the formation of the [[dichromate]] ion.<ref>{{Cite web |last=Crans |first=Debbie C. |date=6 November 2015 |title=Antidiabetic, Chemical, and Physical Properties of Organic Vanadates as Presumed Transition-State Inhibitors for Phosphatases |url=https://pubs.acs.org/doi/10.1021/acs.joc.5b02229 |url-status=live |access-date=2023-04-16 |language=en |doi=10.1021/acs.joc.5b02229}}</ref><ref>{{Cite web |title=Speciation of Molybdenum- and Vanadium-Based Polyoxometalate Species in Aqueous Medium and Gas-Phase and Its Consequences for M1 Structured MoV Oxide Synthesis - ProQuest |url=https://www.proquest.com/openview/f7a2550da721522a6886360b6ff334e6/1?pq-origsite=gscholar&cbl=2026366 |access-date=2023-04-16 |website=www.proquest.com |language=en}}</ref> As the pH is reduced, further protonation and condensation to [[vanadate|polyvanadates]] occur: at pH 4–6 [H<sub>2</sub>VO<sub>4</sub>]<sup>−</sup> is predominant at pV greater than ca. 4, while at higher concentrations trimers and tetramers are formed.<ref>{{Citation |last=Cruywagen |first=J. J. |title=Protonation, Oligomerization, and Condensation Reactions of Vanadate(V), Molybdate(vi), and Tungstate(vi) |date=1999-01-01 |url=https://www.sciencedirect.com/science/article/pii/S0898883808602706 |work=Advances in Inorganic Chemistry |volume=49 |pages=127–182 |editor-last=Sykes |editor-first=A. G. |access-date=2023-04-16 |publisher=Academic Press |language=en}}</ref> Between pH 2–4 [[decavanadate]] predominates, its formation from orthovanadate is represented by this condensation reaction:
+At lower pH values, the monomer [HVO<sub>4</sub>]<sup>2−</sup> and dimer [V<sub>2</sub>O<sub>7</sub>]<sup>4−</sup> are formed, with the monomer predominant at a vanadium concentration of less than c. 10<sup>−2</sup>M (pV > 2, where pV is equal to the minus value of the logarithm of the total vanadium concentration/M). The formation of the divanadate ion is analogous to the formation of the [[dichromate]] ion.<ref>{{cite journal |last1=Crans |first1=Debbie C. |title=Antidiabetic, Chemical, and Physical Properties of Organic Vanadates as Presumed Transition-State Inhibitors for Phosphatases |journal=The Journal of Organic Chemistry |date=18 December 2015 |volume=80 |issue=24 |pages=11899–11915 |doi=10.1021/acs.joc.5b02229 }}</ref><ref>{{cite thesis |last1=Jung |first1=Sabrina |title=Speciation of molybdenum- and vanadium-based polyoxometalate species in aqueous medium and gas-phase and its consequences for M1 structured MoV oxide synthesis |date=2018 |doi=10.14279/depositonce-7254 }}</ref> As the pH is reduced, further protonation and condensation to [[vanadate|polyvanadates]] occur: at pH 4–6 [H<sub>2</sub>VO<sub>4</sub>]<sup>−</sup> is predominant at pV greater than ca. 4, while at higher concentrations trimers and tetramers are formed.<ref>{{Citation |last=Cruywagen |first=J. J. |title=Protonation, Oligomerization, and Condensation Reactions of Vanadate(V), Molybdate(vi), and Tungstate(vi) |date=1999-01-01 |url=https://www.sciencedirect.com/science/article/pii/S0898883808602706 |work=Advances in Inorganic Chemistry |volume=49 |pages=127–182 |editor-last=Sykes |editor-first=A. G. |access-date=2023-04-16 |publisher=Academic Press |language=en}}</ref> Between pH 2–4 [[decavanadate]] predominates, its formation from orthovanadate is represented by this condensation reaction:
 :10 [VO<sub>4</sub>]<sup>3−</sup> + 24 H<sup>+</sup> → [V<sub>10</sub>O<sub>28</sub>]<sup>6−</sup> + 12 H<sub>2</sub>O
 In decavanadate, each V(V) center is surrounded by six oxide [[ligand]]s.<ref name="HollemanAF" /> Vanadic acid, H<sub>3</sub>VO<sub>4</sub>, exists only at very low concentrations because protonation of the tetrahedral species [H<sub>2</sub>VO<sub>4</sub>]<sup>−</sup> results in the preferential formation of the octahedral [VO<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]<sup>+</sup> species.<ref>{{Cite book |last=Tracey |first=Alan S. |url=https://books.google.com/books?hl=en&lr=&id=vkMGP3PiuyYC&oi=fnd&pg=PP1&dq=+protonation+of+the+tetrahedral+species+%5BH2VO4%5D%E2%88%92+results+in+the+preferential+formation+of+the+octahedral+%5BVO2(H2O)4%5D++species&ots=dw08jAg4kL&sig=Rhob-fPsGLqTrni7WZnNG3zg-f0 |title=Vanadium: Chemistry, Biochemistry, Pharmacology and Practical Applications |last2=Willsky |first2=Gail R. |last3=Takeuchi |first3=Esther S. |date=2007-03-19 |publisher=CRC Press |isbn=978-1-4200-4614-4 |language=en}}</ref> In strongly acidic solutions, pH&nbsp;<&nbsp;2, [VO<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>]<sup>+</sup> is the predominant species, while the oxide V<sub>2</sub>O<sub>5</sub> precipitates from solution at high concentrations. The oxide is formally the [[acidic oxide|acid anhydride]] of vanadic acid. The structures of many [[vanadate]] compounds have been determined by X-ray crystallography.
-[[File:VinwaterPourbaixdiagram2.svg|thumb|right|The [[Pourbaix diagram]] for vanadium in water, which shows the [[redox]] potentials between various vanadium species in different oxidation states.<ref>{{cite journal|journal= Electrochimica Acta|volume= 42|date= 1997|pages= 579–586|doi= 10.1016/S0013-4686(96)00202-2|title= Electrochemical behavior of vanadium in aqueous solutions of different pH|first= F. M.|last= Al-Kharafi|author2=Badawy, W. A. |issue= 4}}</ref>]]
+[[File:VinwaterPourbaixdiagram2.svg|thumb|right|The [[Pourbaix diagram]] for vanadium in water, which shows the [[redox]] potentials between various vanadium species in different oxidation states.<ref>{{cite journal |last1=Al-Kharafi |first1=F.M. |last2=Badawy |first2=W.A. |title=Electrochemical behaviour of vanadium in aqueous solutions of different pH |journal=Electrochimica Acta |date=January 1997 |volume=42 |issue=4 |pages=579–586 |doi=10.1016/S0013-4686(96)00202-2 }}</ref>]]
 Vanadium(V) forms various peroxo complexes, most notably in the active site of the vanadium-containing [[bromoperoxidase]] enzymes. The species VO(O<sub>2</sub>)(H<sub>2</sub>O)<sub>4</sub><sup>+</sup> is stable in acidic solutions. In alkaline solutions, species with 2, 3 and 4 peroxide groups are known; the last forms violet salts with the formula M<sub>3</sub>V(O<sub>2</sub>)<sub>4</sub> nH<sub>2</sub>O (M= Li, Na, etc.), in which the vanadium has an 8-coordinate dodecahedral structure.<ref>{{Greenwood&Earnshaw}}, p994.</ref><ref>{{cite book|date=1992|url=https://books.google.com/books?id=Lmt3x9CyfLgC&pg=PA128|page=128|title=Catalytic oxidations with hydrogen peroxide as oxidant|author=Strukul, Giorgio|publisher=Springer|isbn=978-0-7923-1771-5}}</ref>
@@ Line 58: / Line 58: @@
 Twelve binary [[halides]], compounds with the formula VX<sub>n</sub> (n=2..5), are known.<ref name="G&E989">{{Greenwood&Earnshaw2nd|page=989}}</ref> VI<sub>4</sub>, VCl<sub>5</sub>, VBr<sub>5</sub>, and VI<sub>5</sub> do not exist or are extremely unstable. In combination with other reagents, [[vanadium(IV) chloride|VCl<sub>4</sub>]] is used as a catalyst for the polymerization of [[diene]]s. Like all binary halides, those of vanadium are [[Lewis acid]]ic, especially those of V(IV) and V(V).<ref name="G&E989" /> Many of the halides form octahedral complexes with the formula VX<sub>''n''</sub>L<sub>6−''n''</sub> (X= halide; L= other ligand).
-Many vanadium [[oxyhalide]]s (formula VO<sub>m</sub>X<sub>n</sub>) are known.<ref>{{Greenwood&Earnshaw|page=993}}</ref> The oxytrichloride and oxytrifluoride ([[vanadium oxytrichloride|VOCl<sub>3</sub>]] and [[Vanadium(V) oxytrifluoride|VOF<sub>3</sub>]]) are the most widely studied. Akin to POCl<sub>3</sub>, they are volatile,<ref>{{Cite web |last=Flesch |first=Gerald D. |last2=Svec |first2=Harry J. |date=1975-08-01 |title=Thermochemistry of vanadium oxytrichloride and vanadium oxytrifluoride by mass spectrometry |url=https://pubs.acs.org/doi/pdf/10.1021/ic50150a015 |access-date=2023-04-16 |doi=10.1021/ic50150a015}}</ref> adopt tetrahedral structures in the gas phase, and are Lewis acidic.<ref>{{Cite web |last=Iqbal |first=Javed |last2=Bhatia |first2=Beena |last3=Nayyar |first3=Naresh K. |date=1994-03-01 |title=Transition Metal-Promoted Free-Radical Reactions in Organic Synthesis: The Formation of Carbon-Carbon Bonds |url=https://pubs.acs.org/doi/pdf/10.1021/cr00026a008 |url-status=live |access-date=2023-04-16 |language=en |doi=10.1021/cr00026a008}}</ref>
+Many vanadium [[oxyhalide]]s (formula VO<sub>m</sub>X<sub>n</sub>) are known.<ref>{{Greenwood&Earnshaw|page=993}}</ref> The oxytrichloride and oxytrifluoride ([[vanadium oxytrichloride|VOCl<sub>3</sub>]] and [[Vanadium(V) oxytrifluoride|VOF<sub>3</sub>]]) are the most widely studied. Akin to POCl<sub>3</sub>, they are volatile,<ref>{{cite journal |last1=Flesch |first1=Gerald D. |last2=Svec |first2=Harry J. |title=Thermochemistry of vanadium oxytrichloride and vanadium oxytrifluoride by mass spectrometry |journal=Inorganic Chemistry |date=1 August 1975 |volume=14 |issue=8 |pages=1817–1822 |doi=10.1021/ic50150a015 }}</ref> adopt tetrahedral structures in the gas phase, and are Lewis acidic.<ref>{{cite journal |last1=Iqbal |first1=Javed |last2=Bhatia |first2=Beena |last3=Nayyar |first3=Naresh K. |title=Transition Metal-Promoted Free-Radical Reactions in Organic Synthesis: The Formation of Carbon-Carbon Bonds |journal=Chemical Reviews |date=March 1994 |volume=94 |issue=2 |pages=519–564 |doi=10.1021/cr00026a008 }}</ref>
 ===Coordination compounds===
 [[File:Vanadyl-acetylacetonate-from-xtal-3D-balls.png|thumb|right|A [[ball-and-stick model]] of [[vanadyl acetylacetonate|VO(O<sub>2</sub>C<sub>5</sub>H<sub>7</sub>)<sub>2</sub>]].]]
-Complexes of vanadium(II) and (III) are relatively exchange inert and reducing. Those of V(IV) and V(V) are oxidants. The vanadium ion is rather large and some complexes achieve coordination numbers greater than 6, as is the case in [V(CN)<sub>7</sub>]<sup>4−</sup>. Oxovanadium(V) also forms 7 coordinate coordination complexes with tetradentate ligands and peroxides and these complexes are used for oxidative brominations and thioether oxidations. The coordination chemistry of V<sup>4+</sup> is dominated by the [[vanadyl]] center, VO<sup>2+</sup>, which binds four other ligands strongly and one weakly (the one trans to the vanadyl center). An example is [[vanadyl acetylacetonate]] (V(O)(O<sub>2</sub>C<sub>5</sub>H<sub>7</sub>)<sub>2</sub>). In this complex, the vanadium is 5-coordinate, distorted square pyramidal, meaning that a sixth ligand, such as pyridine, may be attached, though the [[association constant]] of this process is small. Many 5-coordinate vanadyl complexes have a trigonal bipyramidal geometry, such as VOCl<sub>2</sub>(NMe<sub>3</sub>)<sub>2</sub>.<ref>{{Greenwood&Earnshaw2nd|page=995}}</ref> The coordination chemistry of V<sup>5+</sup> is dominated by the relatively stable dioxovanadium coordination complexes<ref>{{Cite journal |last=Geiser |first=Jan Nicholas |date=2019 |title=Development of an improved state-of-charge sensor for the all-vanadium redox flow battery |url=https://publikationen.sulb.uni-saarland.de/handle/20.500.11880/27971 |language=en |doi=10.22028/D291-29229}}</ref> which are often formed by aerial oxidation of the vanadium(IV) precursors indicating the stability of the +5 oxidation state and ease of interconversion between the +4 and +5 states.<ref>{{Cite journal |last=Nica |first=Simona |last2=Rudolph |first2=Manfred |last3=Görls |first3=Helmar |last4=Plass |first4=Winfried |date=2007-04-01 |title=Structural characterization and electrochemical behavior of oxovanadium(V) complexes with N-salicylidene hydrazides |url=https://www.sciencedirect.com/science/article/pii/S002016930600630X |journal=Inorganica Chimica Acta |language=en |volume=360 |issue=5 |pages=1743–1752 |doi=10.1016/j.ica.2006.09.018 |issn=0020-1693}}</ref>
+Complexes of vanadium(II) and (III) are relatively exchange inert and reducing. Those of V(IV) and V(V) are oxidants. The vanadium ion is rather large and some complexes achieve coordination numbers greater than 6, as is the case in [V(CN)<sub>7</sub>]<sup>4−</sup>. Oxovanadium(V) also forms 7 coordinate coordination complexes with tetradentate ligands and peroxides and these complexes are used for oxidative brominations and thioether oxidations. The coordination chemistry of V<sup>4+</sup> is dominated by the [[vanadyl]] center, VO<sup>2+</sup>, which binds four other ligands strongly and one weakly (the one trans to the vanadyl center). An example is [[vanadyl acetylacetonate]] (V(O)(O<sub>2</sub>C<sub>5</sub>H<sub>7</sub>)<sub>2</sub>). In this complex, the vanadium is 5-coordinate, distorted square pyramidal, meaning that a sixth ligand, such as pyridine, may be attached, though the [[association constant]] of this process is small. Many 5-coordinate vanadyl complexes have a trigonal bipyramidal geometry, such as VOCl<sub>2</sub>(NMe<sub>3</sub>)<sub>2</sub>.<ref>{{Greenwood&Earnshaw2nd|page=995}}</ref> The coordination chemistry of V<sup>5+</sup> is dominated by the relatively stable dioxovanadium coordination complexes<ref>{{cite thesis |last1=Geiser |first1=Jan Nicholas |title=Development of an improved state-of-charge sensor for the all-vanadium redox flow battery |date=2019 |doi=10.22028/D291-29229 }}</ref> which are often formed by aerial oxidation of the vanadium(IV) precursors indicating the stability of the +5 oxidation state and ease of interconversion between the +4 and +5 states.<ref>{{cite journal |last1=Nica |first1=Simona |last2=Rudolph |first2=Manfred |last3=Görls |first3=Helmar |last4=Plass |first4=Winfried |title=Structural characterization and electrochemical behavior of oxovanadium(V) complexes with N-salicylidene hydrazides |journal=Inorganica Chimica Acta |date=April 2007 |volume=360 |issue=5 |pages=1743–1752 |doi=10.1016/j.ica.2006.09.018 }}</ref>
 ===Organometallic compounds===
 {{Main|Organovanadium chemistry}}
-The organometallic chemistry of vanadium is well{{en dash}}developed. [[Vanadocene dichloride]] is a versatile starting reagent and has applications in organic chemistry.<ref name="wilkinson">{{cite journal|author=Wilkinson, G.|author2=Birmingham, J.G.|name-list-style=amp|title=Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta|journal=[[Journal of the American Chemical Society]]|volume=76|date=1954|pages=4281–4284|doi= 10.1021/ja01646a008|issue=17}}</ref> [[Vanadium carbonyl]], V(CO)<sub>6</sub>, is a rare example of a paramagnetic [[metal carbonyl]]. Reduction yields V{{chem|(CO)|6|−}} ([[isoelectronic]] with [[hexacarbonylchromium|Cr(CO)<sub>6</sub>]]), which may be further reduced with sodium in liquid ammonia to yield V{{chem|(CO)|5|3−}} (isoelectronic with Fe(CO)<sub>5</sub>).<ref>{{cite journal|last= Bellard|first= S.|author2= Rubinson, K. A.|author3= Sheldrick, G. M.|title= Crystal and molecular structure of vanadium hexacarbonyl|journal= Acta Crystallographica|date= 1979|volume= B35|pages= 271–274|doi= 10.1107/S0567740879003332|issue= 2|url= http://journals.iucr.org/b/issues/1979/02/00/a17244/a17244.pdf|access-date= 27 August 2019|archive-date= 10 March 2020|archive-url= https://web.archive.org/web/20200310010122/http://journals.iucr.org/b/issues/1979/02/00/a17244/a17244.pdf|url-status= dead}}</ref><ref>{{cite book|first= C.|last= Elschenbroich|author2=Salzer A. |title= Organometallics: A Concise Introduction|date= 1992|publisher= Wiley-VCH|isbn= 978-3-527-28165-7}}</ref>
+The organometallic chemistry of vanadium is well{{en dash}}developed. [[Vanadocene dichloride]] is a versatile starting reagent and has applications in organic chemistry.<ref name="wilkinson">{{cite journal |last1=Wilkinson |first1=G. |last2=Birmingham |first2=J. M. |title=Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta |journal=Journal of the American Chemical Society |date=September 1954 |volume=76 |issue=17 |pages=4281–4284 |doi=10.1021/ja01646a008 }}</ref> [[Vanadium carbonyl]], V(CO)<sub>6</sub>, is a rare example of a paramagnetic [[metal carbonyl]]. Reduction yields V{{chem|(CO)|6|−}} ([[isoelectronic]] with [[hexacarbonylchromium|Cr(CO)<sub>6</sub>]]), which may be further reduced with sodium in liquid ammonia to yield V{{chem|(CO)|5|3−}} (isoelectronic with Fe(CO)<sub>5</sub>).<ref>{{cite journal |last1=Bellard |first1=S. |last2=Rubinson |first2=K. A. |last3=Sheldrick |first3=G. M. |title=Crystal and molecular structure of vanadium hexacarbonyl |journal=Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry |date=15 February 1979 |volume=35 |issue=2 |pages=271–274 |doi=10.1107/S0567740879003332 }}</ref><ref>{{cite book|first= C.|last= Elschenbroich|author2=Salzer A. |title= Organometallics: A Concise Introduction|date= 1992|publisher= Wiley-VCH|isbn= 978-3-527-28165-7}}</ref>
 ==Occurrence==
@@ Line 77: / Line 77: @@
 Vanadium is mined mostly in [[China]], [[South Africa]] and eastern [[Russia]]. In 2022 these three countries mined more than 96% of the 100,000 [[tonne|ton]]s of produced vanadium, with China providing 70%.<ref name=usgs>{{cite web|publisher= [[United States Geological Survey]]|first= Désirée E. |last= Polyak|url=https://pubs.usgs.gov/periodicals/mcs2023/mcs2023-vanadium.pdf|title= Mineral Commodity Summaries 2023: Vanadium}}</ref>
-Vanadium is also present in [[bauxite]] and deposits of [[crude oil]], [[coal]], [[oil shale]], and [[tar sand]]s. In crude oil, concentrations up to 1200&nbsp;ppm have been reported. When such oil products are burned, traces of vanadium may cause [[corrosion]] in engines and boilers.<ref>{{cite journal|title= Vanadium and nickel complexes in petroleum resid acid, base, and neutral fractions|first= C. D.|last= Pearson|author2=Green J. B. |journal= Energy Fuels|date= 1993|volume= 7|pages= 338–346|doi= 10.1021/ef00039a001|issue= 3|url= https://digital.library.unt.edu/ark:/67531/metadc1198139/}}</ref> An estimated 110,000 tons of vanadium per year are released into the atmosphere by burning fossil fuels.<ref>{{cite journal|journal= Anal. Real Acad. Nac. Farm.|date= 2004|volume= 70|page= 961|title= Vanadium – An element both essential and toxic to plants, animals and humans?|first= Manfred|last= Anke}}</ref> [[Black shale]]s are also a potential source of vanadium. During WW II some vanadium was extracted from [[alum shale]]s in the south of Sweden.<ref>{{cite book | doi = 10.3133/sir29955294 | page = 22| chapter = Geology and resources of some world oil-shale deposits| title = Scientific Investigations Report| year = 2006| last1 = Dyni| first1 = John R.| s2cid = 19814608}}</ref>
+Vanadium is also present in [[bauxite]] and deposits of [[crude oil]], [[coal]], [[oil shale]], and [[tar sand]]s. In crude oil, concentrations up to 1200&nbsp;ppm have been reported. When such oil products are burned, traces of vanadium may cause [[corrosion]] in engines and boilers.<ref>{{cite journal |last1=Pearson |first1=C. D. |last2=Green |first2=J. B. |title=Vanadium and nickel complexes in petroleum resid acid, base, and neutral fractions |journal=Energy & Fuels |date=1 May 1993 |volume=7 |issue=3 |pages=338–346 |doi=10.1021/ef00039a001 }}</ref> An estimated 110,000 tons of vanadium per year are released into the atmosphere by burning fossil fuels.<ref>{{cite journal|journal= Anal. Real Acad. Nac. Farm.|date= 2004|volume= 70|page= 961|title= Vanadium – An element both essential and toxic to plants, animals and humans?|first= Manfred|last= Anke}}</ref> [[Black shale]]s are also a potential source of vanadium. During WW II some vanadium was extracted from [[alum shale]]s in the south of Sweden.<ref>{{cite book | doi = 10.3133/sir29955294 | page = 22| chapter = Geology and resources of some world oil-shale deposits| title = Scientific Investigations Report| year = 2006| last1 = Dyni| first1 = John R.| s2cid = 19814608}}</ref>
-In the universe, the [[Abundance of the chemical elements#Abundance of elements in the Universe|cosmic abundance]] of vanadium is 0.0001%, making the element nearly as common as [[copper]] or [[zinc]].<ref name="Dieter">{{cite book|last1=Rehder|first1=Dieter|title=Bioinorganic Vanadium Chemistry|date=2008|publisher=John Wiley & Sons, Ltd|location=Hamburg, Germany|isbn=9780470065099|pages=5 & 9–10|edition=1st|doi=10.1002/9780470994429|series=Inorganic Chemistry}}</ref> Vanadium is detected [[Optical spectrometer|spectroscopically]] in light from the [[Sun]] and sometimes in the light from other [[star]]s.<ref>{{cite journal|title= Vanadium abundances in early A stars|last= Cowley|first= C. R.|author2= Elste, G. H.|author3= Urbanski, J. L.|journal= Publications of the Astronomical Society of the Pacific|volume= 90|date= 1978|page=536|bibcode= 1978PASP...90..536C|doi= 10.1086/130379|doi-access= free}}</ref> The [[vanadyl ion]] is also abundant in [[seawater]], having an average concentration of 30 [[Molar concentration#Units|nM]] (1.5&nbsp;mg/m<sup>3</sup>).<ref name="Dieter" /> Some [[mineral water]] [[spring (hydrology)|springs]] also contain the ion in high concentrations. For example, springs near [[Mount Fuji]] contain as much as 54 [[microgram|μg]] per [[liter]].<ref name="Dieter" />
+In the universe, the [[Abundance of the chemical elements#Abundance of elements in the Universe|cosmic abundance]] of vanadium is 0.0001%, making the element nearly as common as [[copper]] or [[zinc]].<ref name="Dieter">{{cite book|last1=Rehder|first1=Dieter|title=Bioinorganic Vanadium Chemistry|date=2008|publisher=John Wiley & Sons, Ltd|location=Hamburg, Germany|isbn=9780470065099|pages=5 & 9–10|edition=1st|doi=10.1002/9780470994429|series=Inorganic Chemistry}}</ref> Vanadium is detected [[Optical spectrometer|spectroscopically]] in light from the [[Sun]] and sometimes in the light from other [[star]]s.<ref>{{cite journal |last1=Cowley |first1=C. R. |last2=Elste |first2=G. H. |last3=Urbanski |first3=J. L. |title=Vanadium abundances in early A stars |journal=Publications of the Astronomical Society of the Pacific |date=October 1978 |volume=90 |pages=536 |doi=10.1086/130379 }}</ref> The [[vanadyl ion]] is also abundant in [[seawater]], having an average concentration of 30 [[Molar concentration#Units|nM]] (1.5&nbsp;mg/m<sup>3</sup>).<ref name="Dieter" /> Some [[mineral water]] [[spring (hydrology)|springs]] also contain the ion in high concentrations. For example, springs near [[Mount Fuji]] contain as much as 54 [[microgram|μg]] per [[liter]].<ref name="Dieter" />
 ==Production==
@@ Line 85: / Line 85: @@
 [[File:Vanadium crystal vakuum sublimed.jpg|thumb|left|Vacuum sublimed vanadium [[dendrite (crystal)|dendritic]] crystals (99.9%)]]
-Vanadium metal is obtained by a multistep process that begins with roasting crushed ore with [[sodium chloride|NaCl]] or [[sodium carbonate|Na<sub>2</sub>CO<sub>3</sub>]] at about 850&nbsp;°C to give [[sodium metavanadate]] (NaVO<sub>3</sub>). An aqueous extract of this solid is acidified to produce "red cake", a polyvanadate salt, which is reduced with [[calcium]] metal. As an alternative for small-scale production, vanadium pentoxide is reduced with [[hydrogen]] or [[magnesium]]. Many other methods are also used, in all of which vanadium is produced as a [[byproduct]] of other processes.<ref name="Moskalyk" /> Purification of vanadium is possible by the [[crystal bar process]] developed by [[Anton Eduard van Arkel]] and [[Jan Hendrik de Boer]] in 1925. It involves the formation of the metal iodide, in this example [[vanadium(III) iodide]], and the subsequent decomposition to yield pure metal:<ref>{{cite journal|title= Preparation of High-Purity Vanadium Metals by the Iodide Refining Process|journal= Journal of the Electrochemical Society|volume= 108|page=88|date= 1961|first= O. N.|last= Carlson|author2=Owen, C. V. |doi= 10.1149/1.2428019}}</ref>
+Vanadium metal is obtained by a multistep process that begins with roasting crushed ore with [[sodium chloride|NaCl]] or [[sodium carbonate|Na<sub>2</sub>CO<sub>3</sub>]] at about 850&nbsp;°C to give [[sodium metavanadate]] (NaVO<sub>3</sub>). An aqueous extract of this solid is acidified to produce "red cake", a polyvanadate salt, which is reduced with [[calcium]] metal. As an alternative for small-scale production, vanadium pentoxide is reduced with [[hydrogen]] or [[magnesium]]. Many other methods are also used, in all of which vanadium is produced as a [[byproduct]] of other processes.<ref name="Moskalyk" /> Purification of vanadium is possible by the [[crystal bar process]] developed by [[Anton Eduard van Arkel]] and [[Jan Hendrik de Boer]] in 1925. It involves the formation of the metal iodide, in this example [[vanadium(III) iodide]], and the subsequent decomposition to yield pure metal:<ref>{{cite journal |last1=Carlson |first1=O. N. |last2=Owen |first2=C. V. |title=Preparation of High-Purity Vanadium Metalb by the Iodide Refining Process |journal=Journal of The Electrochemical Society |date=1961 |volume=108 |issue=1 |pages=88 |doi=10.1149/1.2428019 }}</ref>
 :2 V + 3 I<sub>2</sub> {{eqm}} 2 VI<sub>3</sub>
@@ Line 96: / Line 96: @@
 ===Alloys===
-Approximately 85% of the vanadium produced is used as [[ferrovanadium]] or as a [[steel]] additive.<ref name="Moskalyk">{{cite journal|journal= Minerals Engineering|volume= 16|pages= 793–805|doi= 10.1016/S0892-6875(03)00213-9|first= R. R.|last= Moskalyk|author2=Alfantazi, A. M. |title= Processing of vanadium: a review|date= 2003|issue= 9|bibcode= 2003MiEng..16..793M}}</ref> The considerable increase of strength in steel containing small amounts of vanadium was discovered in the early 20th century. Vanadium forms stable nitrides and carbides, resulting in a significant increase in the strength of steel.<ref name="Chandler">{{cite book|title= Metallurgy for the Non-metallurgist|first= Harry|last= Chandler|publisher= ASM International|isbn= 978-0-87170-652-2|pages= 6–7|url= https://books.google.com/books?id=arupok8PTBEC|date= 1998}}</ref> From that time on, vanadium steel was used for applications in [[axle]]s, bicycle frames, [[crankshaft]]s, gears, and other critical components. There are two groups of vanadium steel alloys. Vanadium high-carbon steel alloys contain 0.15% to 0.25% vanadium, and [[High-speed steel|high-speed tool steels]] (HSS) have a vanadium content of 1% to 5%. For high-speed tool steels, a hardness above [[Rockwell hardness|HRC]] 60 can be achieved. HSS steel is used in [[surgical instrument]]s and [[tool]]s.<ref>{{cite book|url= https://books.google.com/books?id=Kws7x68r_aUC&pg=PA11|title= Tool Materials: Tool Materials|first= Joseph R.|last= Davis|publisher= ASM International|date= 1995|isbn= 978-0-87170-545-7}}</ref> [[Powder metallurgy|Powder-metallurgic]] alloys contain up to 18% percent vanadium. The high content of vanadium carbides in those alloys increases wear resistance significantly. One application for those alloys is tools and knives.<ref>{{cite book |url= https://books.google.com/books?id=6aP3te2hGuQC&pg=PA490 |page=490 |title= Handbook of Non-Ferrous Metal Powders: Technologies and Applications |isbn= 9780080559407 |author1=Oleg D. Neikov |last2=Naboychenko |first2=Stanislav |last3=Mourachova |first3=Irina |author4=Victor G. Gopienko |author5=Irina V. Frishberg |author6=Dina V. Lotsko |date= 2009-02-24 |access-date=17 October 2013}}</ref><!--http://www.wujii.com.tw/PDF/CPM%2015V.pdf-->
+Approximately 85% of the vanadium produced is used as [[ferrovanadium]] or as a [[steel]] additive.<ref name="Moskalyk">{{cite journal |last1=Moskalyk |first1=R.R |last2=Alfantazi |first2=A.M |title=Processing of vanadium: a review |journal=Minerals Engineering |date=September 2003 |volume=16 |issue=9 |pages=793–805 |doi=10.1016/S0892-6875(03)00213-9 }}</ref> The considerable increase of strength in steel containing small amounts of vanadium was discovered in the early 20th century. Vanadium forms stable nitrides and carbides, resulting in a significant increase in the strength of steel.<ref name="Chandler">{{cite book|title= Metallurgy for the Non-metallurgist|first= Harry|last= Chandler|publisher= ASM International|isbn= 978-0-87170-652-2|pages= 6–7|url= https://books.google.com/books?id=arupok8PTBEC|date= 1998}}</ref> From that time on, vanadium steel was used for applications in [[axle]]s, bicycle frames, [[crankshaft]]s, gears, and other critical components. There are two groups of vanadium steel alloys. Vanadium high-carbon steel alloys contain 0.15% to 0.25% vanadium, and [[High-speed steel|high-speed tool steels]] (HSS) have a vanadium content of 1% to 5%. For high-speed tool steels, a hardness above [[Rockwell hardness|HRC]] 60 can be achieved. HSS steel is used in [[surgical instrument]]s and [[tool]]s.<ref>{{cite book|url= https://books.google.com/books?id=Kws7x68r_aUC&pg=PA11|title= Tool Materials: Tool Materials|first= Joseph R.|last= Davis|publisher= ASM International|date= 1995|isbn= 978-0-87170-545-7}}</ref> [[Powder metallurgy|Powder-metallurgic]] alloys contain up to 18% percent vanadium. The high content of vanadium carbides in those alloys increases wear resistance significantly. One application for those alloys is tools and knives.<ref>{{cite book |url= https://books.google.com/books?id=6aP3te2hGuQC&pg=PA490 |page=490 |title= Handbook of Non-Ferrous Metal Powders: Technologies and Applications |isbn= 9780080559407 |author1=Oleg D. Neikov |last2=Naboychenko |first2=Stanislav |last3=Mourachova |first3=Irina |author4=Victor G. Gopienko |author5=Irina V. Frishberg |author6=Dina V. Lotsko |date= 2009-02-24 |access-date=17 October 2013}}</ref><!--http://www.wujii.com.tw/PDF/CPM%2015V.pdf-->
-Vanadium stabilizes the beta form of titanium and increases the strength and temperature stability of titanium. Mixed with [[aluminium]] in [[titanium]] alloys, it is used in [[jet engine]]s, high-speed airframes and [[dental implant]]s. The most common alloy for seamless tubing is [[titanium alloy#Grades of titanium|Titanium 3/2.5]] containing 2.5% vanadium, the titanium alloy of choice in the aerospace, defense, and bicycle industries.<ref>{{cite web|title=Technical Supplement: Titanium|url=http://www.sevencycles.com/buildingbike/techsupplement/ti.php|website=Seven Cycles|access-date=1 November 2016|archive-date=3 November 2016|archive-url=https://web.archive.org/web/20161103173648/http://www.sevencycles.com/buildingbike/techsupplement/ti.php|url-status=dead}}</ref> Another common alloy, primarily produced in sheets, is [[Titanium 6AL-4V]], a titanium alloy with 6% aluminium and 4% vanadium.<ref>{{cite book|title= Titan und Titanlegierungen|chapter= Metastabile β-Legierungen|first= Manfred|last= Peters|author2= Leyens, C.|publisher= Wiley-VCH|date= 2002|chapter-url= https://books.google.com/books?id=sxdR882jQpYC&pg=PA23|isbn= 978-3-527-30539-1|pages= 23–24}}{{Dead link|date=January 2023 |bot=InternetArchiveBot |fix-attempted=yes }}</ref>
+Vanadium stabilizes the beta form of titanium and increases the strength and temperature stability of titanium. Mixed with [[aluminium]] in [[titanium]] alloys, it is used in [[jet engine]]s, high-speed airframes and [[dental implant]]s. The most common alloy for seamless tubing is [[titanium alloy#Grades of titanium|Titanium 3/2.5]] containing 2.5% vanadium, the titanium alloy of choice in the aerospace, defense, and bicycle industries.<ref>{{cite web|title=Technical Supplement: Titanium|url=http://www.sevencycles.com/buildingbike/techsupplement/ti.php|website=Seven Cycles|access-date=1 November 2016|archive-date=3 November 2016|archive-url=https://web.archive.org/web/20161103173648/http://www.sevencycles.com/buildingbike/techsupplement/ti.php|url-status=dead}}</ref> Another common alloy, primarily produced in sheets, is [[Titanium 6AL-4V]], a titanium alloy with 6% aluminium and 4% vanadium.<ref>{{cite journal |doi=10.1007/978-3-642-80587-5_2 }}</ref>
-Several vanadium alloys show superconducting behavior. The first [[A15 phase]] superconductor was a vanadium compound, V<sub>3</sub>Si, which was discovered in 1952.<ref>{{cite journal |journal= Physical Review|volume= 89|pages= 884|date= 1953|title= Superconducting Silicides and Germanides|first= George F.|last= Hardy|author2=Hulm, John K. |doi= 10.1103/PhysRev.89.884|bibcode=1953PhRv...89Q.884H |issue= 4}}</ref> [[Vanadium-gallium]] tape is used in [[superconductivity|superconducting]] magnets (17.5 [[tesla (unit)|teslas]] or 175,000 [[gauss (unit)|gauss]]). The structure of the superconducting A15 phase of V<sub>3</sub>Ga is similar to that of the more common [[niobium-tin|Nb<sub>3</sub>Sn]] and [[niobium-titanium|Nb<sub>3</sub>Ti]].<ref>{{cite journal |journal= IEEE Transactions on Magnetics |volume= 13 |issue= 1 |date= 1977 |pages= 35–37 |title= A 17.5 Tesla superconducting concentric Nb<sub>3</sub>Sn and V<sup>3</sup>Ga magnet system|last= Markiewicz |first= W.|author2=Mains, E. |author3=Vankeuren, R. |author4=Wilcox, R. |author5=Rosner, C. |author6=Inoue, H. |author7=Hayashi, C. |author8= Tachikawa, K. |doi= 10.1109/TMAG.1977.1059431|bibcode= 1977ITM....13...35M}}</ref>
+Several vanadium alloys show superconducting behavior. The first [[A15 phase]] superconductor was a vanadium compound, V<sub>3</sub>Si, which was discovered in 1952.<ref>{{cite journal |last1=Hardy |first1=George F. |last2=Hulm |first2=John K. |title=Superconducting Silicides and Germanides |journal=Physical Review |date=15 February 1953 |volume=89 |issue=4 |pages=884–884 |doi=10.1103/PhysRev.89.884 }}</ref> [[Vanadium-gallium]] tape is used in [[superconductivity|superconducting]] magnets (17.5 [[tesla (unit)|teslas]] or 175,000 [[gauss (unit)|gauss]]). The structure of the superconducting A15 phase of V<sub>3</sub>Ga is similar to that of the more common [[niobium-tin|Nb<sub>3</sub>Sn]] and [[niobium-titanium|Nb<sub>3</sub>Ti]].<ref>{{cite journal |last1=Markiewicz |first1=W. |last2=Mains |first2=E. |last3=Vankeuren |first3=R. |last4=Wilcox |first4=R. |last5=Rosner |first5=C. |last6=Inoue |first6=H. |last7=Hayashi |first7=C. |last8=Tachikawa |first8=K. |title=A 17.5 Tesla superconducting concentric Nb&lt;inf&gt;3&lt;/inf&gt;Sn and V&lt;inf&gt;3&lt;/inf&gt;Ga magnet system |journal=IEEE Transactions on Magnetics |date=January 1977 |volume=13 |issue=1 |pages=35–37 |doi=10.1109/TMAG.1977.1059431 }}</ref>
-It has been found that a small amount, 40 to 270&nbsp;ppm, of vanadium in [[Wootz steel]] significantly improved the strength of the product, and gave it the distinctive patterning. The source of the vanadium in the original Wootz steel ingots remains unknown.<ref>{{cite journal |title= The key role of impurities in ancient damascus steel blades|journal= Journal of the Minerals, Metals and Materials Society |volume= 50|issue= 9|pages= 58–64|doi= 10.1007/s11837-998-0419-y|first= J. D.|last= Verhoeven|author2= Pendray, A. H.|author3= Dauksch, W. E. |date= 1998|bibcode= 1998JOM....50i..58V|s2cid= 135854276 }}</ref>
+It has been found that a small amount, 40 to 270&nbsp;ppm, of vanadium in [[Wootz steel]] significantly improved the strength of the product, and gave it the distinctive patterning. The source of the vanadium in the original Wootz steel ingots remains unknown.<ref>{{cite journal |last1=Verhoeven |first1=J. D. |last2=Pendray |first2=A. H. |last3=Dauksch |first3=W. E. |title=The key role of impurities in ancient damascus steel blades |journal=JOM |date=September 1998 |volume=50 |issue=9 |pages=58–64 |doi=10.1007/s11837-998-0419-y }}</ref>
 Vanadium can be used as a substitute for molybdenum in armor steel, though the alloy produced is far more brittle and prone to [[spalling]] on non-penetrating impacts.<ref>{{cite journal |title=Vanadium in South Africa (Metal Review Series no. 2) |last=Rohrmann |first=B. |hdl=10520/AJA0038223X_1959 |journal=Journal of the Southern African Institute of Mining and Metallurgy|volume=85|issue=5|year=1985|pages=141–150}}</ref> The Third Reich was one of the most prominent users of such alloys, in armored vehicles like [[Tiger II]] or [[Jagdtiger]].<ref>{{cite journal | last=Overy | first=R. J. | title=Transportation and Rearmament in the Third Reich | journal=The Historical Journal| volume=16 | issue=2 | year=1973| doi=10.1017/s0018246x00005926 | pages=389–409| s2cid=153437214 }}</ref>
@@ Line 109: / Line 109: @@
 [[File:Vanadium pentoxide powder.jpg|thumb|upright|[[Vanadium(V) oxide]] is a catalyst in the [[contact process]] for producing sulfuric acid]]
-Vanadium compounds are used extensively as catalysts;<ref>{{cite journal |last1=Langeslay |first1=Ryan R. |last2=Kaphan |first2=David M. |last3=Marshall |first3=Christopher L. |last4=Stair |first4=Peter C. |last5=Sattelberger |first5=Alfred P. |last6=Delferro |first6=Massimiliano |title=Catalytic Applications of Vanadium: A Mechanistic Perspective |journal=Chemical Reviews |volume=119 |issue=4 |pages=2128–2191 |date=8 October 2018 |doi=10.1021/acs.chemrev.8b00245|pmid=30296048 |osti=1509906 |s2cid=52943647 }}</ref> [[vanadium(V) oxide|Vanadium pentoxide]] V<sub>2</sub>O<sub>5</sub>, is used as a [[catalyst]] in manufacturing sulfuric acid by the [[contact process]]<ref>{{cite journal|journal= Journal of Catalysis|volume= 155|issue= 1|date= 1995|pages= 32–42|doi= 10.1006/jcat.1995.1185|title= Deactivation and Compound Formation in Sulfuric-Acid Catalysts and Model Systems|last= Eriksen|first= K. M.|author2= Karydis, D. A.|author3= Boghosian, S.|author4= Fehrmann, R.}}</ref> In this process [[sulfur dioxide]] ({{chem|SO|2}}) is oxidized to the [[sulfur trioxide|trioxide]] ({{chem|SO|3}}):<ref name="HollemanAF" /> In this [[redox reaction]], sulfur is oxidized from +4 to +6, and vanadium is reduced from +5 to +4:
+Vanadium compounds are used extensively as catalysts;<ref>{{cite journal |last1=Langeslay |first1=Ryan R. |last2=Kaphan |first2=David M. |last3=Marshall |first3=Christopher L. |last4=Stair |first4=Peter C. |last5=Sattelberger |first5=Alfred P. |last6=Delferro |first6=Massimiliano |title=Catalytic Applications of Vanadium: A Mechanistic Perspective |journal=Chemical Reviews |volume=119 |issue=4 |pages=2128–2191 |date=8 October 2018 |doi=10.1021/acs.chemrev.8b00245|pmid=30296048 |osti=1509906 |s2cid=52943647 }}</ref> [[vanadium(V) oxide|Vanadium pentoxide]] V<sub>2</sub>O<sub>5</sub>, is used as a [[catalyst]] in manufacturing sulfuric acid by the [[contact process]]<ref>{{cite journal |last1=Eriksen |first1=K.M. |last2=Karydis |first2=D.A. |last3=Boghosian |first3=S. |last4=Fehrmann |first4=R. |title=Deactivation and Compound Formation in Sulfuric-Acid Catalysts and Model Systems |journal=Journal of Catalysis |date=August 1995 |volume=155 |issue=1 |pages=32–42 |doi=10.1006/jcat.1995.1185 }}</ref> In this process [[sulfur dioxide]] ({{chem|SO|2}}) is oxidized to the [[sulfur trioxide|trioxide]] ({{chem|SO|3}}):<ref name="HollemanAF" /> In this [[redox reaction]], sulfur is oxidized from +4 to +6, and vanadium is reduced from +5 to +4:
 :V<sub>2</sub>O<sub>5</sub> + SO<sub>2</sub> → 2 VO<sub>2</sub> + SO<sub>3</sub>
@@ Line 116: / Line 116: @@
 Similar oxidations are used in the production of [[maleic anhydride]]:
 :C<sub>4</sub>H<sub>10</sub>  + 3.5 O<sub>2</sub>  →   C<sub>4</sub>H<sub>2</sub>O<sub>3</sub>  +  4 H<sub>2</sub>O
-[[Phthalic anhydride]] and several other bulk organic compounds are produced similarly. These [[green chemistry]] processes convert inexpensive feedstocks to highly functionalized, versatile intermediates.<ref name="Ullmann">{{Ullmann|doi=10.1002/14356007.a27_367|title=Vanadium and Vanadium Compounds|year=2000|last1=Bauer|first1=Günter|last2=Güther|first2=Volker|last3=Hess|first3=Hans|last4=Otto|first4=Andreas|last5=Roidl|first5=Oskar|last6=Roller|first6=Heinz|last7=Sattelberger|first7=Siegfried|isbn=3527306730}}</ref><ref>{{cite journal|journal= Applied Catalysis A: General|volume= 157|issue= 1–2|date= 1997|pages= 173–193|title= Vanadium phosphorus oxides for n-butane oxidation to maleic anhydride |doi= 10.1016/S0926-860X(97)00016-1|first= Michel|last= Abon|author2=Volta, Jean-Claude}}</ref>
+[[Phthalic anhydride]] and several other bulk organic compounds are produced similarly. These [[green chemistry]] processes convert inexpensive feedstocks to highly functionalized, versatile intermediates.<ref name="Ullmann">{{Ullmann|doi=10.1002/14356007.a27_367|title=Vanadium and Vanadium Compounds|year=2000|last1=Bauer|first1=Günter|last2=Güther|first2=Volker|last3=Hess|first3=Hans|last4=Otto|first4=Andreas|last5=Roidl|first5=Oskar|last6=Roller|first6=Heinz|last7=Sattelberger|first7=Siegfried|isbn=3527306730}}</ref><ref>{{cite journal |last1=Abon |first1=Michel |last2=Volta |first2=Jean-Claude |title=Vanadium phosphorus oxides for n-butane oxidation to maleic anhydride |journal=Applied Catalysis A: General |date=September 1997 |volume=157 |issue=1-2 |pages=173–193 |doi=10.1016/S0926-860X(97)00016-1 }}</ref>
 Vanadium is an important component of mixed metal oxide catalysts used in the oxidation of propane and propylene to acrolein, acrylic acid or the ammoxidation of propylene to acrylonitrile.<ref>{{cite book|editor1-last=Fierro|editor1-first=J. G. L. |title=Metal Oxides, Chemistry and Applications|date=2006|publisher=CRC Press|pages=415–455|isbn=9780824723712}}</ref>
 ===Other uses===
-The [[vanadium redox battery]], a type of [[flow battery]], is an electrochemical cell consisting of aqueous vanadium ions in different oxidation states.<ref>{{cite journal|journal= Journal of Power Sources|volume= 127|issue= 1–2|date= 2004|pages= 98–104|title= Possible use of vanadium redox-flow batteries for energy storage in small grids and stand-alone photovoltaic systems|doi= 10.1016/j.jpowsour.2003.09.066|first= Ludwig|last= Joerissen|author2= Garche, Juergen|author3= Fabjan, Ch.|author4= Tomazic G.|bibcode= 2004JPS...127...98J}}</ref><ref name="RychcikSkyllas-Kazacos1988">{{cite journal|last1=Rychcik|first1=M.|last2=Skyllas-Kazacos|first2=M.|title=Characteristics of a new all-vanadium redox flow battery|journal=Journal of Power Sources|volume=22|issue=1|year=1988|pages=59–67|issn=0378-7753|doi=10.1016/0378-7753(88)80005-3|bibcode=1988JPS....22...59R}}</ref> Batteries of this type were first proposed in the 1930s and developed commercially from the 1980s onwards. Cells use +5 and +2 formal oxidization state ions.
+The [[vanadium redox battery]], a type of [[flow battery]], is an electrochemical cell consisting of aqueous vanadium ions in different oxidation states.<ref>{{cite journal |last1=Joerissen |first1=Ludwig |last2=Garche |first2=Juergen |last3=Fabjan |first3=Ch. |last4=Tomazic |first4=G. |title=Possible use of vanadium redox-flow batteries for energy storage in small grids and stand-alone photovoltaic systems |journal=Journal of Power Sources |date=March 2004 |volume=127 |issue=1-2 |pages=98–104 |doi=10.1016/j.jpowsour.2003.09.066 }}</ref><ref name="RychcikSkyllas-Kazacos1988">{{cite journal |last1=Rychcik |first1=M. |last2=Skyllas-Kazacos |first2=M. |title=Characteristics of a new all-vanadium redox flow battery |journal=Journal of Power Sources |date=January 1988 |volume=22 |issue=1 |pages=59–67 |doi=10.1016/0378-7753(88)80005-3 |bibcode=1988JPS....22...59R }}</ref> Batteries of this type were first proposed in the 1930s and developed commercially from the 1980s onwards. Cells use +5 and +2 formal oxidization state ions.
 Vanadium redox batteries are used commercially for [[grid energy storage]].<ref>{{Cite journal |last1=Li |first1=Liyu |last2=Kim |first2=Soowhan |last3=Wang |first3=Wei |last4=Vijayakumar |first4=M. |last5=Nie |first5=Zimin |last6=Chen |first6=Baowei |last7=Zhang |first7=Jianlu |last8=Xia |first8=Guanguang |last9=Hu |first9=Jianzhi |last10=Graff |first10=Gordon |last11=Liu |first11=Jun |last12=Yang |first12=Zhenguo |date=May 2011 |title=A Stable Vanadium Redox-Flow Battery with High Energy Density for Large-Scale Energy Storage |journal=Advanced Energy Materials |volume=1 |issue=3 |pages=394–400 |doi=10.1002/aenm.201100008|s2cid=33277301 }}</ref>
-[[Vanadate]] can be used for protecting steel against rust and corrosion by [[conversion coating]].<ref>{{cite journal|title= Corrosion Protection of Aluminum Alloy 2024-T3 by Vanadate Conversion Coatings|first= H.|last= Guan|author2=Buchheit R. G. |journal= Corrosion|date= 2004|volume= 60|issue= 3|pages= 284–296|doi= 10.5006/1.3287733}}</ref> Vanadium foil is used in [[cladding (metalworking)|cladding]] titanium to steel because it is compatible with both iron and titanium.<ref>{{cite journal|title= Welding of chemical equipment made from two-layer sheet with titanium protective layer (review of foreign literature)|journal= Chemical and Petroleum Engineering|volume= 2|issue= 12|date= 1966|doi= 10.1007/BF01146317|pages= 854–856|first= N. T.|last= Lositskii|author2= Grigor'ev A. A.|author3= Khitrova, G. V.|s2cid= 108903737}}</ref> The moderate [[neutron capture|thermal neutron-capture cross-section]] and the short half-life of the isotopes produced by neutron capture makes vanadium a suitable material for the inner structure of a [[fusion reactor]].<ref>{{cite journal|journal= Journal of Nuclear Materials|volume= 233–237|issue= 1|date= 1996|pages= 92–99|doi= 10.1016/S0022-3115(96)00331-5|title= Status of vanadium alloys for fusion reactors|first= H.|last= Matsui|author2=Fukumoto, K. |author3=Smith, D. L. |author4=Chung, Hee M. |author5=Witzenburg, W. van |author6= Votinov, S. N. |bibcode=1996JNuM..233...92M|url= https://zenodo.org/record/1259631}}</ref><ref>{{cite web|url= http://www.wahchang.com/pages/products/data/pdf/Vanadium.pdf|title= Vanadium Data Sheet |access-date=16 January 2009 |publisher= [[ATI Wah Chang]] |archive-url=https://web.archive.org/web/20090225153938/http://www.wahchang.com/pages/products/data/pdf/Vanadium.pdf |archive-date=25 February 2009}}</ref>
+[[Vanadate]] can be used for protecting steel against rust and corrosion by [[conversion coating]].<ref>{{cite journal |last1=Guan |first1=H. |last2=Buchheit |first2=R. G. |title=Corrosion Protection of Aluminum Alloy 2024-T3 by Vanadate Conversion Coatings |journal=Corrosion |date=1 March 2004 |volume=60 |issue=3 |pages=284–296 |doi=10.5006/1.3287733 }}</ref> Vanadium foil is used in [[cladding (metalworking)|cladding]] titanium to steel because it is compatible with both iron and titanium.<ref>{{cite journal |last1=Lositskii |first1=N. T. |last2=Grigor'ev |first2=A. A. |last3=Khitrova |first3=G. V. |title=Welding of chemical equipment made from two-layer sheet with titanium protective layer (review of foreign literature) |journal=Chemical and Petroleum Engineering |date=December 1966 |volume=2 |issue=12 |pages=854–856 |doi=10.1007/BF01146317 }}</ref> The moderate [[neutron capture|thermal neutron-capture cross-section]] and the short half-life of the isotopes produced by neutron capture makes vanadium a suitable material for the inner structure of a [[fusion reactor]].<ref>{{cite journal |last1=Matsui |first1=H. |last2=Fukumoto |first2=K. |last3=Smith |first3=D.L. |last4=Chung |first4=Hee M. |last5=van Witzenburg |first5=W. |last6=Votinov |first6=S.N. |title=Status of vanadium alloys for fusion reactors |journal=Journal of Nuclear Materials |date=October 1996 |volume=233-237 |pages=92–99 |doi=10.1016/S0022-3115(96)00331-5 }}</ref><ref>{{cite web|url= http://www.wahchang.com/pages/products/data/pdf/Vanadium.pdf|title= Vanadium Data Sheet |access-date=16 January 2009 |publisher= [[ATI Wah Chang]] |archive-url=https://web.archive.org/web/20090225153938/http://www.wahchang.com/pages/products/data/pdf/Vanadium.pdf |archive-date=25 February 2009}}</ref>
 ====Proposed====
@@ Line 135: / Line 135: @@
 ===Vanadoenzymes===
-Several species of marine [[algae]] produce [[vanadium bromoperoxidase]] as well as the closely related [[chloroperoxidase]] (which may use a [[heme]] or vanadium cofactor) and [[iodoperoxidase]]s. The bromoperoxidase produces an estimated 1–2 million tons of [[bromoform]] and 56,000 tons of [[bromomethane]] annually.<ref>{{cite journal |last1= Gribble |first1= Gordon W. |date= 1999 |title= The diversity of naturally occurring organobromine compounds |journal= Chemical Society Reviews |volume= 28 |issue= 5 |pages= 335–346 |doi= 10.1039/a900201d}}</ref> Most naturally occurring [[organobromine compound]]s are produced by this enzyme,<ref>{{cite journal|journal= Natural Product Reports|date= 2004|volume= 21|issue= 1|pmid= 15039842|doi= 10.1039/b302337k|title= The role of vanadium bromoperoxidase in the biosynthesis of halogenated marine natural products|first= Alison|last= Butler|author2=Carter-Franklin, Jayme N. |s2cid= 19115256|pages= 180–8}}</ref> catalyzing the following reaction (R-H is hydrocarbon substrate):
+Several species of marine [[algae]] produce [[vanadium bromoperoxidase]] as well as the closely related [[chloroperoxidase]] (which may use a [[heme]] or vanadium cofactor) and [[iodoperoxidase]]s. The bromoperoxidase produces an estimated 1–2 million tons of [[bromoform]] and 56,000 tons of [[bromomethane]] annually.<ref>{{cite journal |last1= Gribble |first1= Gordon W. |date= 1999 |title= The diversity of naturally occurring organobromine compounds |journal= Chemical Society Reviews |volume= 28 |issue= 5 |pages= 335–346 |doi= 10.1039/a900201d}}</ref> Most naturally occurring [[organobromine compound]]s are produced by this enzyme,<ref>{{cite journal |last1=Butler |first1=Alison |last2=Carter-Franklin |first2=Jayme N. |title=The role of vanadium bromoperoxidase in the biosynthesis of halogenated marine natural products |journal=Natural Product Reports |date=2004 |volume=21 |issue=1 |pages=180 |doi=10.1039/b302337k }}</ref> catalyzing the following reaction (R-H is hydrocarbon substrate):
 {{block indent|R-H + Br<sup>−</sup> + H<sub>2</sub>O<sub>2</sub> → R-Br + H<sub>2</sub>O + OH<sup>−</sup>}}
@@ Line 145: / Line 145: @@
 ===Fungi===
-''[[Amanita muscaria]]'' and related species of macrofungi accumulate vanadium (up to 500&nbsp;mg/kg in dry weight). Vanadium is present in the [[coordination complex]] [[amavadin]]<ref>{{cite journal |last=Kneifel |first=Helmut |author2=Bayer, Ernst |date=1997 |title=Determination of the Structure of the Vanadium Compound, Amavadine, from Fly Agaric|journal=Angewandte Chemie International Edition in English |volume=12 |issue=6 |pages=508 |issn=0570-0833 |doi=10.1002/anie.197305081}}</ref> in fungal fruit-bodies. The biological importance of the accumulation is unknown.<ref>{{cite journal |journal= Journal of Environmental Science and Health, Part A |volume= 42 |issue= 11 |date= 2007 |pages= 1615–1623|title= Selected elements in fly agaric Amanita muscaria |pmid= 17849303 |last= Falandysz|first= J.|author2= Kunito, T.|author3=Kubota, R.|author4= Lipka, K.|author5= Mazur, A.|author6= Falandysz, Justyna J.|author7= Tanabe, S. |doi= 10.1080/10934520701517853|s2cid= 26185534 }}</ref><ref>{{cite journal|volume= 38|issue= 6|pages= 795–797|last= Berry |first= Robert E.|author2=Armstrong, Elaine M. |author3=Beddoes, Roy L. |author4=Collison, David |author5=Ertok, Nigar |author6=Helliwell, Madeleine |author7= Garner, David |doi= 10.1002/(SICI)1521-3773(19990315)38:6<795::AID-ANIE795>3.0.CO;2-7|pmid= 29711812 |title= The Structural Characterization of Amavadin |date= 1999 |journal=Angewandte Chemie International Edition}}</ref> Toxic or [[peroxidase]] enzyme functions have been suggested.<ref name="da Silva Fraústo 2013">{{cite journal | last1=da Silva | first1=José A.L. | last2=Fraústo da Silva | first2=João J.R. | last3=Pombeiro | first3=Armando J.L. | title=Amavadin, a vanadium natural complex: Its role and applications | journal=Coordination Chemistry Reviews | publisher=Elsevier BV | volume=257 | issue=15–16 | year=2013 | issn=0010-8545 | doi=10.1016/j.ccr.2013.03.010 | pages=2388–2400}}</ref>
+''[[Amanita muscaria]]'' and related species of macrofungi accumulate vanadium (up to 500&nbsp;mg/kg in dry weight). Vanadium is present in the [[coordination complex]] [[amavadin]]<ref>{{cite journal |last1=Kneifel |first1=Helmut |last2=Bayer |first2=Ernst |title=Determination of the Structure of the Vanadium Compound, Amavadine, from Fly Agaric |journal=Angewandte Chemie International Edition in English |date=June 1973 |volume=12 |issue=6 |pages=508–508 |doi=10.1002/anie.197305081 }}</ref> in fungal fruit-bodies. The biological importance of the accumulation is unknown.<ref>{{cite journal |last1=Falandysz |first1=J. |last2=Kunito |first2=T. |last3=Kubota |first3=R. |last4=Lipka |first4=K. |last5=Mazur |first5=A. |last6=Falandysz |first6=Justyna J. |last7=Tanabe |first7=S. |title=Selected elements in fly agaric Amanita muscaria |journal=Journal of Environmental Science and Health, Part A |date=31 August 2007 |volume=42 |issue=11 |pages=1615–1623 |doi=10.1080/10934520701517853 |s2cid=26185534 }}</ref><ref>{{cite journal |last1=Berry |first1=Robert E. |last2=Armstrong |first2=Elaine M. |last3=Beddoes |first3=Roy L. |last4=Collison |first4=David |last5=Ertok |first5=S. Nigar |last6=Helliwell |first6=Madeleine |last7=Garner |first7=C. David |title=The Structural Characterization of Amavadin |journal=Angewandte Chemie |date=15 March 1999 |volume=38 |issue=6 |pages=795–797 |doi=10.1002/(SICI)1521-3773(19990315)38:6<795::AID-ANIE795>3.0.CO;2-7 |pmid=29711812 }}</ref> Toxic or [[peroxidase]] enzyme functions have been suggested.<ref name="da Silva Fraústo 2013">{{cite journal |last1=da Silva |first1=José A.L. |last2=Fraústo da Silva |first2=João J.R. |last3=Pombeiro |first3=Armando J.L. |title=Amavadin, a vanadium natural complex: Its role and applications |journal=Coordination Chemistry Reviews |date=August 2013 |volume=257 |issue=15-16 |pages=2388–2400 |doi=10.1016/j.ccr.2013.03.010 }}</ref>
 ===Mammals===
-Deficiencies in vanadium result in reduced growth in rats.<ref>{{cite journal|title= Growth Effects of Vanadium in the Rat|first= Klaus|last= Schwarz|author2=Milne, David B. |journal= Science|volume= 174|issue= 4007|date= 1971|pages= 426–428|jstor= 1731776|doi= 10.1126/science.174.4007.426|pmid= 5112000|bibcode= 1971Sci...174..426S|s2cid= 24362265}}</ref> The U.S. Institute of Medicine has not confirmed that vanadium is an essential nutrient for humans, so neither a Recommended Dietary Intake nor an Adequate Intake have been established. Dietary intake is estimated at 6 to 18&nbsp;µg/day, with less than 5% absorbed. The [[tolerable upper intake level|Tolerable Upper Intake Level]] (UL) of dietary vanadium, beyond which adverse effects may occur, is set at 1.8&nbsp;mg/day.<ref>Nickel. IN: [https://www.nap.edu/read/10026/chapter/15 Dietary Reference Intakes for Vitamin A, Vitamin K, Arsenic, Boron, Chromium, Copper, Iodine, Iron, Manganese, Molybdenum, Nickel, Silicon, Vanadium, and Copper]. National Academy Press. 2001, PP. 532–543.</ref>
+Deficiencies in vanadium result in reduced growth in rats.<ref>{{cite journal |last1=Schwarz |first1=Klaus |last2=Milne |first2=David B. |title=Growth Effects of Vanadium in the Rat |journal=Science |date=22 October 1971 |volume=174 |issue=4007 |pages=426–428 |doi=10.1126/science.174.4007.426 }}</ref> The U.S. Institute of Medicine has not confirmed that vanadium is an essential nutrient for humans, so neither a Recommended Dietary Intake nor an Adequate Intake have been established. Dietary intake is estimated at 6 to 18&nbsp;µg/day, with less than 5% absorbed. The [[tolerable upper intake level|Tolerable Upper Intake Level]] (UL) of dietary vanadium, beyond which adverse effects may occur, is set at 1.8&nbsp;mg/day.<ref>Nickel. IN: [https://www.nap.edu/read/10026/chapter/15 Dietary Reference Intakes for Vitamin A, Vitamin K, Arsenic, Boron, Chromium, Copper, Iodine, Iron, Manganese, Molybdenum, Nickel, Silicon, Vanadium, and Copper]. National Academy Press. 2001, PP. 532–543.</ref>
 ===Research===
-[[Vanadyl sulfate]] as a dietary supplement has been researched as a means of increasing insulin sensitivity or otherwise improving glycemic control in people who are diabetic. Some of the trials had significant treatment effects but were deemed as being of poor study quality. The amounts of vanadium used in these trials (30 to 150&nbsp;mg) far exceeded the safe upper limit.<ref name="Smith2008">{{cite journal |vauthors=Smith DM, Pickering RM, Lewith GT |title=A systematic review of vanadium oral supplements for glycaemic control in type 2 diabetes mellitus |journal=QJM |volume=101 |issue=5 |pages=351–8 |year=2008 |pmid=18319296 |doi=10.1093/qjmed/hcn003 |doi-access=free }}</ref><ref>{{cite journal |title=Vanadium (vanadyl sulfate). Monograph |journal=Altern Med Rev |volume=14 |issue=2 |pages=177–80 |year=2009 |pmid=19594227 }}</ref> The conclusion of the systemic review was "There is no rigorous evidence that oral vanadium supplementation improves glycaemic control in type 2 diabetes. The routine use of vanadium for this purpose cannot be recommended."<ref name="Smith2008" />
+[[Vanadyl sulfate]] as a dietary supplement has been researched as a means of increasing insulin sensitivity or otherwise improving glycemic control in people who are diabetic. Some of the trials had significant treatment effects but were deemed as being of poor study quality. The amounts of vanadium used in these trials (30 to 150&nbsp;mg) far exceeded the safe upper limit.<ref name="Smith2008">{{cite journal |last1=Smith |first1=D.M. |last2=Pickering |first2=R.M. |last3=Lewith |first3=G.T. |title=A systematic review of vanadium oral supplements for glycaemic control in type 2 diabetes mellitus |journal=QJM |date=31 January 2008 |volume=101 |issue=5 |pages=351–358 |doi=10.1093/qjmed/hcn003 }}</ref><ref>{{cite journal |title=Vanadium (vanadyl sulfate). Monograph |journal=Altern Med Rev |volume=14 |issue=2 |pages=177–80 |year=2009 |pmid=19594227 }}</ref> The conclusion of the systemic review was "There is no rigorous evidence that oral vanadium supplementation improves glycaemic control in type 2 diabetes. The routine use of vanadium for this purpose cannot be recommended."<ref name="Smith2008" />
 In [[astrobiology]], it has been suggested that discrete vanadium accumulations on [[Mars]] could be a potential microbial [[biosignature]] when used in conjunction with [[Raman spectroscopy]] and morphology.<ref name="Biosignature Vanadium">{{cite news |last=Lynch |first=Brendan M. |url=https://phys.org/news/2017-09-life-mars-element-vanadium.html |title=Hope to discover sure signs of life on Mars? New research says look for the element vanadium |work=PhysOrg |date=21 September 2017 |access-date=2017-10-14}}</ref><ref name="Vanadium Craig">{{cite journal|doi=10.1089/ast.2017.1709|pmid=28910135|year=2017|last1=Marshall|first1=C. P|title=Imaging of Vanadium in Microfossils: A New Potential Biosignature|journal=Astrobiology|volume=17|issue=11|pages=1069–1076|last2=Olcott Marshall|first2=A|last3=Aitken|first3=J. B|last4=Lai|first4=B|last5=Vogt|first5=S|last6=Breuer|first6=P|last7=Steemans|first7=P|last8=Lay|first8=P. A|bibcode=2017AsBio..17.1069M|osti=1436103}}</ref>
@@ Line 158: / Line 158: @@
 All vanadium compounds should be considered toxic.<ref>{{cite journal |last=Srivastava |first=A. K. |title=Anti-diabetic and toxic effects of vanadium compounds |journal=Molecular and Cellular Biochemistry |issue=206 |pages=177–182 |year=2000 |volume=206 |doi=10.1023/A:1007075204494|pmid=10839208 |s2cid=8871862 }}</ref> Tetravalent [[vanadyl sulfate|VOSO<sub>4</sub>]] has been reported to be at least 5 times more toxic than trivalent V<sub>2</sub>O<sub>3</sub>.<ref>{{cite journal |last=Roschin |first= A. V. |date=1967 |title=Toksikologiia soedineniĭ vanadiia, primeneniaemykh<!--sic: should probably be primeniaemykh--> v sovremennoĭ promyshlennosti |language=ru |trans-title=Toxicology of vanadium compounds used in modern industry |journal=Gigiena i Sanitariia (Water Res.) |volume= 32 |issue= 6|pages= 26–32|pmid= 5605589}}<!--Russian title given only in Latin script. Cyrillic presumably would be: Токсикология соединений ванадия, применяемых в современной промышленности, and journal Гигиена и санитария --></ref> The US [[Occupational Safety and Health Administration]] (OSHA) has set an exposure limit of 0.05&nbsp;mg/m<sup>3</sup> for vanadium pentoxide dust and 0.1&nbsp;mg/m<sup>3</sup> for vanadium pentoxide fumes in workplace air for an 8-hour workday, 40-hour work week.<ref name="OSHA">{{cite web |url=http://www.osha.gov/SLTC/healthguidelines/vanadiumpentoxidedust/recognition.html |title=Occupational Safety and Health Guidelines for Vanadium Pentoxide |publisher=Occupational Safety and Health Administration |access-date=29 January 2009 |url-status=dead |archive-url=https://web.archive.org/web/20090106063227/http://www.osha.gov/SLTC/healthguidelines/vanadiumpentoxidedust/recognition.html |archive-date= 6 January 2009}}</ref> The US [[National Institute for Occupational Safety and Health]] (NIOSH) has recommended that 35&nbsp;mg/m<sup>3</sup> of vanadium be considered immediately dangerous to life and health, that is, likely to cause permanent health problems or death.<ref name="OSHA" />
-Vanadium compounds are poorly absorbed through the gastrointestinal system. Inhalation of vanadium and vanadium compounds results primarily in adverse effects on the respiratory system.<ref>{{cite book |last=Sax |first=N. I. |date=1984 |title=Dangerous Properties of Industrial Materials |edition=6th |publisher=Van Nostrand Reinhold |pages=2717–2720}}</ref><ref name="ress" /><ref>{{cite journal |title=Nanoparticulate Vanadium Oxide Potentiated Vanadium Toxicity in Human Lung Cells |last1=Wörle-Knirsch |first1=Jörg M. |last2=Kern |first2=Katrin |last3=Schleh |first3=Carsten |last4=Adelhelm |first4=Christel |last5=Feldmann |first5=Claus |last6=Krug |first6=Harald F. |name-list-style=amp |journal=Environmental Science and Technology |date=2007 |volume=41 |pages=331–336 |doi=10.1021/es061140x |pmid=17265967 |issue=1 |bibcode=2007EnST...41..331W}}</ref> Quantitative data are, however, insufficient to derive a subchronic or chronic inhalation reference dose. Other effects have been reported after oral or inhalation exposures on blood parameters,<ref>{{cite journal |last1=Ścibior |first1=A. |last2=Zaporowska |first2=H. |last3=Ostrowski |first3=J. |date=2006 |title=Selected haematological and biochemical parameters of blood in rats after subchronic administration of vanadium and/or magnesium in drinking water |journal=Archives of Environmental Contamination and Toxicology |volume=51 |issue=2 |pages=287–295 |doi=10.1007/s00244-005-0126-4 |pmid=16783625|s2cid=43805930 }}</ref><ref>{{cite journal |last=Gonzalez-Villalva |first=A. |display-authors=etal |date= 2006 |title=Thrombocytosis induced in mice after subacute and subchronic V2O5 inhalation |journal=Toxicology and Industrial Health |volume=22 |issue=3 |pages=113–116 |doi=10.1191/0748233706th250oa |pmid=16716040|s2cid=9986509}}</ref> liver,<ref>{{cite journal |journal=Toxicology |volume=228 |date=2006 |pages=162–170 |doi=10.1016/j.tox.2006.08.022 |title=Pentavalent vanadium induces hepatic metallothionein through interleukin-6-dependent and -independent mechanisms |last1=Kobayashi |first1=Kazuo |pmid=16987576 |issue=2–3 |last2=Himeno |first2=Seiichiro |last3=Satoh |first3=Masahiko |last4=Kuroda |first4=Junji |last5=Shibata |first5=Nobuo |last6=Seko |first6=Yoshiyuki |last7=Hasegawa |first7=Tatsuya}}</ref> neurological development,<ref>{{cite journal |last1=Soazo |first1=Marina |last2=Garcia |first2=Graciela Beatriz |date=2007 |title=Vanadium exposure through lactation produces behavioral alterations and CNS myelin deficit in neonatal rats |journal=Neurotoxicology and Teratology |volume=29 |issue=4 |pages=503–510 |doi=10.1016/j.ntt.2007.03.001 |pmid=17493788}}</ref> and other organs<ref>{{cite journal |last1=Barceloux |first1=Donald G. |year=1999 |title=Vanadium |journal= Clinical Toxicology |volume=37 |issue=2 |pages=265–278 |doi=10.1081/CLT-100102425 |pmid=10382561}}</ref> in rats.
+Vanadium compounds are poorly absorbed through the gastrointestinal system. Inhalation of vanadium and vanadium compounds results primarily in adverse effects on the respiratory system.<ref>{{cite book |last=Sax |first=N. I. |date=1984 |title=Dangerous Properties of Industrial Materials |edition=6th |publisher=Van Nostrand Reinhold |pages=2717–2720}}</ref><ref name="ress" /><ref>{{cite journal |title=Nanoparticulate Vanadium Oxide Potentiated Vanadium Toxicity in Human Lung Cells |last1=Wörle-Knirsch |first1=Jörg M. |last2=Kern |first2=Katrin |last3=Schleh |first3=Carsten |last4=Adelhelm |first4=Christel |last5=Feldmann |first5=Claus |last6=Krug |first6=Harald F. |name-list-style=amp |journal=Environmental Science and Technology |date=2007 |volume=41 |pages=331–336 |doi=10.1021/es061140x |pmid=17265967 |issue=1 |bibcode=2007EnST...41..331W}}</ref> Quantitative data are, however, insufficient to derive a subchronic or chronic inhalation reference dose. Other effects have been reported after oral or inhalation exposures on blood parameters,<ref>{{cite journal |last1=Ścibior |first1=A. |last2=Zaporowska |first2=H. |last3=Ostrowski |first3=J. |date=2006 |title=Selected haematological and biochemical parameters of blood in rats after subchronic administration of vanadium and/or magnesium in drinking water |journal=Archives of Environmental Contamination and Toxicology |volume=51 |issue=2 |pages=287–295 |doi=10.1007/s00244-005-0126-4 |pmid=16783625|s2cid=43805930 }}</ref><ref>{{cite journal |last1=González-Villalva |first1=Adriana |last2=Fortoul |first2=Teresa I |last3=Avila-Costa |first3=Maria Rosa |last4=Piñón-Zarate |first4=Gabriela |last5=Rodriguez-Lara |first5=Vianey |last6=Martínez-Levy |first6=Gabriela |last7=Rojas-Lemus |first7=Marcela |last8=Bizarro-Nevarez |first8=Patricia |last9=Díaz-Bech |first9=Patricia |last10=Mussali-Galante |first10=Patricia |last11=Colin-Barenque |first11=Laura |title=Thrombocytosis induced in mice after subacute and subchronic V2O5 inhalation |journal=Toxicology and Industrial Health |date=April 2006 |volume=22 |issue=3 |pages=113–116 |doi=10.1191/0748233706th250oa }}</ref> liver,<ref>{{cite journal |journal=Toxicology |volume=228 |date=2006 |pages=162–170 |doi=10.1016/j.tox.2006.08.022 |title=Pentavalent vanadium induces hepatic metallothionein through interleukin-6-dependent and -independent mechanisms |last1=Kobayashi |first1=Kazuo |pmid=16987576 |issue=2–3 |last2=Himeno |first2=Seiichiro |last3=Satoh |first3=Masahiko |last4=Kuroda |first4=Junji |last5=Shibata |first5=Nobuo |last6=Seko |first6=Yoshiyuki |last7=Hasegawa |first7=Tatsuya}}</ref> neurological development,<ref>{{cite journal |last1=Soazo |first1=Marina |last2=Garcia |first2=Graciela Beatriz |date=2007 |title=Vanadium exposure through lactation produces behavioral alterations and CNS myelin deficit in neonatal rats |journal=Neurotoxicology and Teratology |volume=29 |issue=4 |pages=503–510 |doi=10.1016/j.ntt.2007.03.001 |pmid=17493788}}</ref> and other organs<ref>{{cite journal |last1=Barceloux |first1=Donald G. |year=1999 |title=Vanadium |journal= Clinical Toxicology |volume=37 |issue=2 |pages=265–278 |doi=10.1081/CLT-100102425 |pmid=10382561}}</ref> in rats.
-There is little evidence that vanadium or vanadium compounds are reproductive toxins or [[teratogen]]s. Vanadium pentoxide was reported to be carcinogenic in male rats and in male and female mice by inhalation in an NTP study,<ref name="ress">{{cite journal |last=Ress |first=N. B. |display-authors=etal |date=2003 |title=Carcinogenicity of inhaled vanadium pentoxide in F344/N rats and B6C3F1 mice |journal=Toxicological Sciences |volume=74 |issue=2 |pages=287–296 |doi=10.1093/toxsci/kfg136 |pmid=12773761|doi-access=free }}</ref> although the interpretation of the results has been disputed a few years after the report.<ref>{{cite journal |last=Duffus |first=J. H. |date=2007 |title=Carcinogenicity classification of vanadium pentoxide and inorganic vanadium compounds, the NTP study of carcinogenicity of inhaled vanadium pentoxide, and vanadium chemistry |journal=[[Regulatory Toxicology and Pharmacology]] |volume=47 |issue=1 |pages=110–114 |doi=10.1016/j.yrtph.2006.08.006 |pmid=17030368}}</ref> The carcinogenicity of vanadium has not been determined by the [[United States Environmental Protection Agency]].<ref>{{cite web |url=https://rais.ornl.gov/tox/profiles/vanadium_f_V1.html |title=Toxicity Summary for Vanadium |date=1991 |first=Dennis M. |last=Opreskos |access-date=8 November 2008 |publisher=Oak Ridge National Laboratory}}</ref>
+There is little evidence that vanadium or vanadium compounds are reproductive toxins or [[teratogen]]s. Vanadium pentoxide was reported to be carcinogenic in male rats and in male and female mice by inhalation in an NTP study,<ref name="ress">{{cite journal |last1=Ress |first1=N. B. |last2=Chou |first2=B. J. |last3=Renne |first3=R. A. |last4=Dill |first4=J. A. |last5=Miller |first5=R. A. |last6=Roycroft |first6=J. H. |last7=Hailey |first7=J. R. |last8=Haseman |first8=J. K. |last9=Bucher |first9=J. R. |title=Carcinogenicity of Inhaled Vanadium Pentoxide in F344/N Rats and B6C3F1 Mice |journal=Toxicological Sciences |date=1 August 2003 |volume=74 |issue=2 |pages=287–296 |doi=10.1093/toxsci/kfg136 }}</ref> although the interpretation of the results has been disputed a few years after the report.<ref>{{cite journal |last=Duffus |first=J. H. |date=2007 |title=Carcinogenicity classification of vanadium pentoxide and inorganic vanadium compounds, the NTP study of carcinogenicity of inhaled vanadium pentoxide, and vanadium chemistry |journal=[[Regulatory Toxicology and Pharmacology]] |volume=47 |issue=1 |pages=110–114 |doi=10.1016/j.yrtph.2006.08.006 |pmid=17030368}}</ref> The carcinogenicity of vanadium has not been determined by the [[United States Environmental Protection Agency]].<ref>{{cite web |url=https://rais.ornl.gov/tox/profiles/vanadium_f_V1.html |title=Toxicity Summary for Vanadium |date=1991 |first=Dennis M. |last=Opreskos |access-date=8 November 2008 |publisher=Oak Ridge National Laboratory}}</ref>
 Vanadium traces in [[diesel fuel]]s are the main fuel component in [[high temperature corrosion]]. During combustion, vanadium oxidizes and reacts with sodium and sulfur, yielding [[vanadate]] compounds with melting points as low as 530&nbsp;°C, which attack the [[passivation (chemistry)|passivation layer]] on steel and render it susceptible to corrosion. The solid vanadium compounds also abrade engine components.<ref>{{cite book |page=92 |url=https://books.google.com/books?id=RC_k4q6y-JIC&pg=PA92 |title=Pounder's Marine Diesel Engines and Gas Turbines |isbn=9780080943619 |last1=Woodyard |first1=Doug |date=2009-08-18}}</ref><ref>{{cite book |page=152 |url=https://books.google.com/books?id=J_AkNu-Y1wQC&pg=PA152 |title=Fuels and Lubricants Handbook: Technology, Properties, Performance, and Testing |isbn=9780803120969 |last1=Totten |first1=George E. |last2=Westbrook |first2=Steven R. |last3=Shah |first3=Rajesh J. |date=2003-06-01}}</ref>

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