Vanadium

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This article is about the chemical element. For other uses, see Vanadium (disambiguation).

Vanadium, 23V
Vanadium
Pronunciation/vəˈneɪdiəm/ ​(və-NAY-dee-əm)
Appearanceblue-silver-grey metal
Standard atomic weight Ar°(V)
Vanadium in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
–
↑
V
↓
Nb
titanium ← vanadium → chromium
kJ/mol
Heat of vaporization444 kJ/mol
Molar heat capacity24.89 J/(mol·K)
Vapor pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 2101 2289 2523 2814 3187 3679
Atomic properties
Henry Enfield Roscoe (1867)
Named byNils Gabriel Sefström (1830)
Isotopes of vanadium
Main isotopes Decay
abun­dance half-life (t1/2) mode pro­duct
48V synth 16 d
β+
48Ti
49V synth 330 d ε
49Ti
50V 0.25% 2.71×1017 y β+
50Ti
51V 99.8%
stable
 Category: Vanadium
| references

Vanadium is a

oxidation
.

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

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]

Model T used vanadium steel in its chassis
.

As vanadium is usually found combined with other elements, the isolation of vanadium metal was difficult.

vanadium pentoxide with calcium.[12]

The first large-scale industrial use of vanadium was in 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

ebeam remelted
and macro-etched

Vanadium is an average-hard,

oxidized in air at about 933 K (660 °C, 1220 °F), although an oxide passivation layer forms even at room temperature.[21]
It also reacts with hydrogen peroxide.

Isotopes

Main article: Isotopes of vanadium

Naturally occurring vanadium is composed of one stable

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

Main article: Vanadium 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] 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

decavanadate
structure

In an aqueous solution, vanadium(V) forms an extensive family of

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 [VS4]3− is analogous to the orthovanadate ion.[31]

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

decavanadate
predominates, its formation from orthovanadate is represented by this condensation reaction:

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

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.

The Pourbaix diagram for vanadium in water, which shows the redox potentials between various vanadium species in different oxidation states[36]

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

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

A ball-and-stick model of VO(O2C5H7)2

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)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

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]

Organometallic compounds

Main article: Organovanadium chemistry

The organometallic chemistry of vanadium is well–developed.

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

Vanadinite

Metallic vanadium is rare in nature (known as native vanadium),[49][50] 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.

ultramafic gabbro bodies. If this titanomagnetite is used to produce iron, most of the vanadium goes to the slag and is extracted from it.[57][54]

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%.[58]

Fumaroles of Colima are known of being vanadium-rich, depositing other vanadium minerals, that include shcherbinaite (V2O5) and colimaite (K3VS4).[59][60][61]

Vanadium is also present in

alum shales in the south of Sweden.[64]

In the universe, the

liter.[65]

Production

Vanadium production trend
Vacuum sublimed vanadium dendritic crystals (99.9%)

Vanadium metal is obtained by a multistep process that begins with roasting crushed ore with

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:[68]

2 V + 3 I2 ⇌ 2 VI3
Ferrovanadium chunks

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.[67]

Applications

Tool made from vanadium steel

Alloys

Approximately 85% of the vanadium produced is used as

HRC 60 can be achieved. HSS steel is used in surgical instruments and tools.[70] 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.[71]

Vanadium stabilizes the beta form of titanium and increases the strength and temperature stability of titanium. Mixed with

Titanium 6AL-4V, a titanium alloy with 6% aluminium and 4% vanadium.[73]

Several vanadium alloys show

Nb3Ti.[75]

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.[76]

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.[77] The Third Reich was one of the most prominent users of such alloys, in armored vehicles like Tiger II or Jagdtiger.[78]

Catalysts

Vanadium(V) oxide is a catalyst in the contact process for producing sulfuric acid.

Vanadium compounds are used extensively as catalysts;

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.[81][82]

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.[83]

Other uses

The vanadium redox battery, a type of flow battery, is an electrochemical cell consisting of aqueous vanadium ions in different oxidation states.[84][85] 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.[86]

fusion reactor.[89][90]

Vanadium can be added in small quantities < 5% to LFP battery cathodes to increase ionic conductivity.[91]

Proposed

Vanadium phosphates have been proposed as the cathode in the lithium vanadium phosphate battery, another type of lithium-ion battery.[93]

Biological role

Vanadium has a more significant role in marine environments than terrestrial ones.[94]

vanabins
.
Amanita muscaria contains amavadin.

Vanadoenzymes

Several species of marine

organobromine compounds are produced by this enzyme,[96]
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.[97]

Vanadium accumulation in tunicates

Vanadium is essential to

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][98][99] than the surrounding seawater, which normally contains 1 to 2 µg/L.[100][101] 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.[102]

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[103] in fungal fruit-bodies. The biological importance of the accumulation is unknown.[104][105] Toxic or peroxidase enzyme functions have been suggested.[106]

Mammals

Deficiencies in vanadium result in reduced growth in rats.

Tolerable Upper Intake Level (UL) of dietary vanadium, beyond which adverse effects may occur, is set at 1.8 mg/day.[108]

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.[109][110] 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."[109]

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.[111][112]

Safety

All vanadium compounds should be considered toxic.[113] Tetravalent VOSO4 has been reported to be at least 5 times more toxic than trivalent V2O3.[114] 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.[115] 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.[115]

Vanadium compounds are poorly absorbed through the gastrointestinal system. Inhalation of vanadium and vanadium compounds results primarily in adverse effects on the respiratory system.[116][117][118] 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,[119][120] liver,[121] neurological development,[122] and other organs[123] 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,[117] although the interpretation of the results has been disputed a few years after the report.[124] The carcinogenicity of vanadium has not been determined by the United States Environmental Protection Agency.[125]

Vanadium traces 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.[126][127]

See also

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Further reading

External links

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