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.
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 NorseVanadís (another name for the
NorseVanir 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]
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 (
c. 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]
Naturally occurring vanadium is composed of one stable
isotope, 51V, and one radioactive isotope, 50V. The latter has a
half-life of 2.71×1017 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.
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)62+, green [V(H2O)63+, blue [VO(H2O)52+, yellow-orange oxides [VO(H2O)53+, 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)52+, followed by the green color of [V(H2O)63+ and then the violet color of [V(H2O)62+.[20] Another potential vanadium battery based on VB2 uses multiple oxidation state to allow for 11 electrons to be released per VB2, giving it higher energy capacity by order of compared to Li-ion and gasoline per unit volume.[25] VB2 batteries can be further enhanced as air batteries, allowing for even higher energy density and lower weight than lithium battery or gasoline, even though recharging remains a challenge. [25]
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.[26] 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[27] to study the
biochemistry of phosphate.[28] Besides that, this anion also has been shown to interact with the activity of some specific enzymes.[29][30] The tetrathiovanadate [VS43− is analogous to the orthovanadate ion.[31]
At lower pH values, the monomer [HVO42− and dimer [V2O74− 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.[32][33] 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.[34] Between pH 2–4
decavanadate predominates, its formation from orthovanadate is represented by this condensation reaction:
10 [VO43− + 24 H+ → [V10O286− + 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.[35] 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.
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.[37][38]
Halide derivatives
Twelve binary
halides, compounds with the formula VXn (n=2..5), are known.[39] 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).[39] Many of the halides form octahedral complexes with the formula VXnL6−n (X= halide; L= other ligand).
Many vanadium
oxyhalides (formula VOmXn) are known.[40] The oxytrichloride and oxytrifluoride (
VOCl3 and
VOF3) are the most widely studied. Akin to POCl3, they are volatile,[41] adopt tetrahedral structures in the gas phase, and are Lewis acidic.[42]
Coordination compounds
Complexes of vanadium(II) and (III) are reducing, while 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)74−. 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.[43] The coordination chemistry of V5+ is dominated by the relatively stable dioxovanadium coordination complexes[44] 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.[45]
The organometallic chemistry of vanadium is well–developed.
Vanadocene dichloride is a versatile starting reagent and has applications in organic chemistry.[46]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).[47][48]
Occurrence
Vanadium is the 22nd most abundant element in the Earth's crust;[49] metallic vanadium is rare in nature (known as native vanadium),[50][51] having been found among fumaroles of the
Colima Volcano, but vanadium compounds occur naturally in about 65 different
minerals.
Vanadium began to be used in the manufacture of special steels in 1896. At that time, very few deposits of vanadium ores were known. Between 1899 and 1906, the main deposits exploited were the mines of Santa Marta de los Barros (Badajoz), Spain.
Vanadinite was extracted from these mines.[52] 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.[53][54][55] For several years this
patrónite (VS4)[56] 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.[57] 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
ultramaficgabbro bodies. If this
titanomagnetite is used to produce iron, most of the vanadium goes to the
slag and is extracted from it.[58][55]
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%.[59]
Fumaroles of Colima are known of being vanadium-rich, depositing other vanadium minerals, that include shcherbinaite (V2O5) and
colimaite (K3VS4).[60][61][62]
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.[63] An estimated 110,000 tons of vanadium per year are released into the atmosphere by burning
fossil fuels.[64]Black shales are also a potential source of vanadium. During WW II some vanadium was extracted from
alum shales in the south of Sweden.[65]
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.[68] 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:[69]
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.[68]
Applications
Alloys
Approximately 85% of the vanadium produced is used as
ferrovanadium or as a
steel additive.[68] 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.[70] 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 0.15–0.25% vanadium, and
high-speed tool steels (HSS) have a vanadium content of 1–5%. For high-speed tool steels, a hardness above
HRC 60 can be achieved. HSS steel is used in
surgical instruments and
tools.[71]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.[72]
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.[73] Another common alloy, primarily produced in sheets, is
Titanium 6AL-4V, a titanium alloy with 6% aluminium and 4% vanadium.[74]
Several vanadium alloys show
superconducting behavior. The first
A15 phase superconductor was a vanadium compound, V3Si, which was discovered in 1952.[75]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.[76]
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.[77]
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.[78] The Third Reich was one of the most prominent users of such alloys, in armored vehicles like
Tiger II or
Jagdtiger.[79]
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.[82][83]
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.[84]
Other uses
The
vanadium redox battery, a type of
flow battery, is an electrochemical cell consisting of aqueous vanadium ions in different oxidation states.[85][86] 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.[87]
Vanadate can be used for protecting steel against rust and corrosion by
conversion coating.[88] Vanadium foil is used in
cladding titanium to steel because it is compatible with both iron and titanium.[89] 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.[90][91]
Vanadium can be added in small quantities < 5% to
LFP battery cathodes to increase ionic conductivity.[92]
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][99][100] than the surrounding seawater, which normally contains 1 to 2 µg/L.[101][102] 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.[103]
Fungi
Amanita muscaria and related species of macrofungi accumulate vanadium (up to 500 mg/kg in dry weight). Vanadium is present in the
coordination complexamavadin[104] in fungal fruit-bodies. The biological importance of the accumulation is unknown.[105][106] Toxic or
peroxidase enzyme functions have been suggested.[107]
Mammals
Deficiencies in vanadium result in reduced growth in rats.[108] 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.[109]
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.[110][111] 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."[110]
All vanadium compounds should be considered toxic.[114] Tetravalent
VOSO4 has been reported to be at least 5 times more toxic than trivalent V2O3.[115] 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.[116] 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.[116]
Vanadium compounds are poorly absorbed through the gastrointestinal system. Inhalation of vanadium and vanadium compounds results primarily in adverse effects on the respiratory system.[117][118][119] 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,[120][121] liver,[122] neurological development,[123] and other organs[124] 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,[118] although the interpretation of the results has been disputed a few years after the report.[125] The carcinogenicity of vanadium has not been determined by the
United States Environmental Protection Agency.[126]
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 (986 °F), which attack the
passivation layer on steel and render it susceptible to corrosion. The solid vanadium compounds also abrade engine components.[127][128]
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Archived from the original on 6 October 2021. Retrieved 8 November 2008.