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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
Atomic number (Z)23
Groupgroup 5
Periodperiod 4
Block  d-block
Electron configuration[Ar] 3d3 4s2
Electrons per shell2, 8, 11, 2
Physical properties
Phase at STPsolid
Melting point2183 K ​(1910 °C, ​3470 °F)
Boiling point3680 K ​(3407 °C, ​6165 °F)
Density (at 20° C)6.099 g/cm3 [3]
when liquid (at m.p.)5.5 g/cm3
Heat of fusion21.5 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
Oxidation states−3, −1, 0, +1, +2, +3, +4, +5 (an amphoteric oxide)
ElectronegativityPauling scale: 1.63
Ionization energies
  • 1st: 650.9 kJ/mol
  • 2nd: 1414 kJ/mol
  • 3rd: 2830 kJ/mol
  • (more)
Atomic radiusempirical: 134 pm
Covalent radius153±8 pm
Color lines in a spectral range
Spectral lines of vanadium
Other properties
Natural occurrenceprimordial
Crystal structure ​body-centered cubic (bcc) (cI2)
Lattice constant
Body-centered cubic crystal structure for vanadium
a = 302.72 pm (at 20 °C)[3]
Thermal expansion8.77×10−6/K (at 20 °C)[3]
Thermal conductivity30.7 W/(m⋅K)
Electrical resistivity197 nΩ⋅m (at 20 °C)
Magnetic orderingparamagnetic
Molar magnetic susceptibility+255.0×10−6 cm3/mol (298 K)[4]
Young's modulus128 GPa
Shear modulus47 GPa
Bulk modulus160 GPa
Speed of sound thin rod4560 m/s (at 20 °C)
Poisson ratio0.37
Mohs hardness6.7
Vickers hardness628–640 MPa
Brinell hardness600–742 MPa
CAS Number7440-62-2
History
DiscoveryAndrés Manuel del Río[5] (1801)
First isolationHenry 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 (/vəˈneɪdiəm/) is a chemical element that has the symbol V and atomic number 23. It is a soft, silvery grey, ductile transition metal. The formation of a oxide layer makes the metal stable against oxidation. By anlysing the mineral vanadinite, Andrés Manuel del Río discovered it in 1801 and named it erythronium, but withdrew his claim four years later when it was (incorrectly) suggested that the mineral was actually lead chromate. The element was rediscovered in 1831 by Nils Gabriel Sefström, who named the element vanadium after the goddess of beauty Vanadis. Both names were attributed to the fact that the redox chemistry of vanadium yields compounds in a wide range of colors.

It occurs naturally in about 65 different minerals and in fossil fuel deposits. It is produced in China and Russia from steel smelter slag while other countries use heavy oil flue dust or produce it as byproduct of uranium mining. It is mainly used to produce speciality steel alloys such as high speed tool steels. The compound vanadium pentoxide is used as catalyst for the production of sulfuric acid. Vanadium is found in many organisms, and is used by some life forms as active center of enzymes.

History

A new element was originally discovered by Andrés Manuel del Río, a Spanish-born Mexican mineralogist, in 1801. The element was extracted from a sample of Mexican "brown lead" ore (now named vanadinite). He found that its salts exhibit a wide variety of colors, so he first named the element panchromium (Greek: all colors), but later renamed it erythronium, since most of the salts turned red when heated. The French chemist Hippolyte Victor Collet-Descotils incorrectly declared that del Río's new element was only impure chromium. Del Río thought himself to be mistaken and accepted the statement of the French chemist that was also backed by del Río's friend Baron Alexander von Humboldt.[6]

1910 Model T

In 1831, Nils Gabriel Sefström of Sweden rediscovered the element in a new oxide which he found while working with some iron ores and later that same year Friedrich Wöhler confirmed del Río's earlier work.[7] Sefström choose a name beginning with V, which had not yet been assigned to any element, and called it vanadium after Vanadis (another name for Freya, the Scandinavian goddess of fertility), because of many the beautifully colored chemical compounds it produces.[7] In 1831, the geologist George William Featherstonhaugh suggested that vanadium should be renamed "rionium" after del Río, but this suggestion was not followed.[8]

The development of routes to pure vanadium metal spanned many years. In 1831, Berzelius reported the production of the metal, but Henry Enfield Roscoe showed that Berzelius had in fact produced the nitride, VN. Roscoe produced the metal in 1867 by reduction of vanadium(III) chloride, VCl3, with hydrogen.[9] In 1927 the pure vanadium was produced by reducing vanadium pentoxide with calcium.[10] The first large scale industrial use was in the chassis of the Ford Model T, which was inspired from French race cars. Vanadium steel allowed for reduced weight while simultaneously increasing tensile strength.[11]

Characteristics

Physical

The Pourbaix diagram for vanadium in water.[12]

Vanadium is a soft, ductile, silver-grey metal. It has good resistance to corrosion both by alkalis and sulfuric and hydrochloric acids.[13] It is oxidized in air at about 933 K (660 °C). Vanadium has good structural strength. Common oxidation states of vanadium include +2, +3, +4 and +5. In a popular experiment, ammonium vanadate (NH4VO3) can be successively reduced with zinc metal to demonstrate the different colours of vanadium in these four oxidation states. Lower oxidation states occur in compounds such as V(CO)6 and [V(CO)6]- and substituted derivatives.[13]

Isotopes

Main article: Isotopes of vanadium

Naturally occurring vanadium is composed of one stable isotope 51V and one radioactive isotope 50V with a half-life of 1.5×1017 years and natural abundance 0.25%. 51V has a nuclear spin of 7/2.[14]

24 artificial radioisotopes have been characterized (in the range of mass number between 40 and 65). The most stable of these isotopes are 49V with a half-life of 330 days and 48V with a half-life of 15.9735 days. All of the remaining radioactive isotopes have half-lives shorter than an hour, the majority of them below 10 seconds. 4 isotopes have metastable excited states.[14]

Chemistry

See also: Category:Vanadium compounds
Vanadium(V) oxide

The chemistry of vanadium is noteworthy for the ready accessibility of four adjacent oxidation states. Conversions of these oxidation states is illustrated by the reduction of a strongly acidic solution of a vanadium(V) compound with zinc dust. The initial yellow color characteristic of the vanadate ion, VO43−, is replaced by the blue color of [VO(H2O)5]2+, followed by the green color of [V(H2O)6]3+ and then violet, due to [V(H2O)6]2+.[13]

The most commercially important compound is vanadium pentoxide, which is used as a catalyst for the production of sulfuric acid.[13] This compound oxidizes sulfur dioxide to the trioxide. In this redox reaction, sulfur is oxidized from +4 to +6, and vanadium is reduced from +5 to +3:

V2O5 + 2 SO2 → V2O3 + 2 SO3

The catalyst us regenerated by oxidation with air.

V2O3 + O2 → V2O5

Several halides are known for oxidation states 2, 3 and 4. VCl4 is the most important commercially. This liquid is mainly used as a catalyst for polymerization of dienes. Vanadium(II) compounds are reducing agents, and vanadium(V) derivatives are oxidizing agents. Vanadium(IV) compounds often exist as vanadyl derivatives which contain the VO2+ center.[13]

The oxyanion chemistry of vanadium(V) is complex. The vanadate ion, VO43−, is present in dilute solutions at high pH. On lowering the pH, HVO42- and H2VO4- are formed, analogous to HPO42- and H2PO4-. The acid dissociation constants for the vanadium and phosphorus series are remarkably similar. In more concentrated solutions many polyvanadates are formed. Chains, rings and clusters involving tetrahedral vanadium, analogous to the polyphosphates, are known. In addition, clusters such as the decavanadates V10O284− and HV10O283−, which predominate in the pH range 4-6, are formed in which the vanadium is octahedral.[13]

metavanadate chains
V5O14
decavanadate ion

The correspondence between vanadate and phosphate chemistry can be attributed to the similarity in size and charge of phosphorus(V) and vanadium(V). Orthovanadate VO43− is used in protein crystallography to study the biochemistry of phosphate.

Coordination compounds

File:Vanadyl-acetoacetonate-3D-balls.png
A ball-and-stick model of VO(acac)2

Three factors are rather unusual in the coordination chemistry of vanadium, due its position early on in the transition metal series. Firstly, metallic vanadium has the electronic configuration [Ar]4s23d3, so compounds of vanadium are relatively electron-poor. In consequence, most binary compounds are Lewis acids (electron pair acceptors). For example all the halides form octahedral adducts with the formula VXnL6-n (X = halide; L = other ligand). Secondly the vanadium ion is rather large and can achieve coordination numbers higher than 6, as in [V(CN)7]4−. Thirdly, the vanadyl ion, VO2+, features in many complexes of vanadium(IV). Vanadyl acetylacetonate is just one example. Interestingly, the vanadium is 5-coordinate, square pyramidal in this complex; a sixth ligand, such as pyridine, can be attached, but the equilibrium constant for that process is small. Many vanadyl complexes are 5-coordinate, but not all of them are square pyramidal. For example, VO(Cl2(NMe3)2 is trigonal bypyramidal.

Organometallic chemistry of vanadium is well developed, but organometallic compounds are of minor commercial significance. Vanadocene dichloride is a versatile starting reagent and even finds minor applications in organic chemistry.[15] Vanadium carbonyl, V(CO)6, is a rare example of an metal carbonyl that has an unpaired electron, but does not dimerize. Addition of an electron yields V(CO)6− which is isoelectronic with Cr(CO)6. Further reduction with sodium in liquid ammonia yields V(CO)53−, isoelectronic with Fe(CO)5.[16][17]

Occurrence

See also: Category:Vanadate minerals
Vanadinite

Metallic vanadium is not found in nature, but about 65 different minerals are known. Economically significant examples include patronite (VS4),[18] vanadinite (Pb5(VO4)3Cl), and carnotite (K2(UO2)2(VO4)2·3H2O). Much of the world's vanadium production is sourced from vanadium-bearing magnetite found in ultramafic gabbro bodies. Vanadium is mined mostly in South Africa, north west China and eastern Russia. In 2007 these three countries mined more than 95 % of the 58,600 tonnes of vanadium produced.[19]

Vanadium is also present in bauxite and in fossil fuel deposits such as crude oil, coal, oil shale and tar sands. In crude oil, concentrations up to 1200 ppm have been reported.[20] An estimated 110,000 tonnes per year enter the atmosphere by burning fussile fuel.[21] Vanadium has been detected spectroscopically in light from the Sun and some other stars.

Production

Industrially, most vanadium is used as ferrovanadium, an additive to improve steels. Ferrovanadium is produced directly by reducing a mixture of vanadium oxide, iron oxides and iron in an electric furnace. Vanadium-bearing magnetite iron ore is the main source for vanadium production.[22] The vanadium ends in pig iron produced from vanadium bearing magnetite. During steel production, oxygen is blown into the pig iron, oxidizing the carbon and most of the other impurities, forming slag. Depending on the used ore, the slag contains up to 25% of vanadium.[22]

Vanadium metal is obtained via a multistep process that begins with the roasting of crushed ore with NaCl or Na2CO3 at about 850 °C to give sodium metavanadate (NaVO3). An aqueous extract of this solid is acidified to give "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 in use, in all of which vanadium is produced as a byproduct of other processes.[22]

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.

2 V + 3 I2 ⇌ 2 VI3

Applications

Alloys

Tool made from vanadium steel
Electron beam–melted vanadium

Approximately 85% of vanadium produced is used as ferrovanadium or as a steel additive.[22] The considerable increase of strength in steel containing small amounts of vanadium was discovered in the beginning of 20th century,[23] and from that time vanadium steel was used for applications in axles, bicycle frames, crankshafts, gears, and other critical components. Vanadium forms stable nitrides and carbides, resulting in a significant increase in the strength of the steel. There are two groups of vanadium containing steel alloy groups. Vanadium high-carbon steel alloys containing 0.15 to 0.25 percent vanadium and high speed tool steels (HSS) with a vanadium content ranges from 1 % to 5 %. For the HSS after hardening a hardness above HRC60) can be achieved. HSS steel is used in surgical instruments and tools.[24]

Vanadium stabilizes the beta form of titanium and increases the strength and temperature stability. Mixed with aluminium in titanium alloys it is used in jet engines and high-speed airframes. One of the common alloys is Ti 6Al 4V a titanium alloy with 6% aluminium and 4% of vanadium.[25]

Other uses

Biological role

Ascidiacea contain vanadium.
Amanita muscaria contains amavadine.

Vanadium plays very limited role in biology. A vanadium-containing nitrogenase is used by some nitrogen-fixing micro-organisms. Vanadium is essential to ascidians or sea squirts in vanadium chromagen proteins. The concentration of vanadium in their blood is more than 100 times higher than the concentration of vanadium in the seawater around them. Rats and chickens are also known to require vanadium in very small amounts and deficiencies result in reduced growth and impaired reproduction.[40] Vanadium is a relatively controversial dietary supplement, primarily for increasing insulin sensitivity[41] and body-building. Whether it works for the latter purpose has not been proven, and there is some evidence that athletes who take it are merely experiencing a placebo effect.[42]

Ten percent of the blood cell pigment of the sea cucumber is vanadium. Just as the horseshoe crab has blue blood rather than red blood (colored by iron in hemoglobin) because of copper in the hemocyanin pigment, the blood of the sea cucumber is yellow because of the vanadium in the vanabin pigment.[43] Nonetheless, there is no evidence that vanabins carry oxygen, in contrast to hemoglobin and hemocyanin.

Vanadyl sulfate may improve glucose control in people with type 2 diabetes.[44][45][46][47][48]

Several species of macrofungi, namely Amanita muscaria and related species, accumulate vanadium (up to 500 mg/kg in dry weight). Vanadium is present in the coordination complex amavadine in fungal fruit-bodies. However, the biological importance of the accumulation process is unknown.[49][50]

Health and safety

All vanadium compounds should be considered to be toxic. Tetravalent VOSO4 has been reported to be over 5 times more toxic than trivalent V2O3.[51] The most dangerous compound is vanadium pentoxide. The 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. The National Institute for Occupational Safety and Health (NIOSH) has recommended that 35 mg/m3 of vanadium be considered immediately dangerous to life and health. This is the exposure level of a chemical that is likely to cause permanent health problems or death.

Vanadium compounds are poorly absorbed through the gastrointestinal system. Inhalation exposures to vanadium and vanadium compounds result primarily in adverse effects on the respiratory system.[52][53][54] 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,[55][56] on liver,[57] on neurological development in rats,[58] and other organs.

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 male and female mice by inhalation in an NTP study,[59] although the interpretation of the results has recently been disputed.[60] Vanadium has not been classified as to carcinogenicity by the U.S. EPA.[61]

Metallic vanadium is potentially a fire hazard, particularly when in a finely-divided state.

Vanadium in literature

Vanadium naphthenate has a curious place in literature. It features in the short story, entitled “Vanadium” in Primo Levi’s book, The Periodic Table.[62] It was instrumental in bringing Levi into correspondence, after the war, with a German chemist he had encountered when working as a slave-labourer in the Buna-Monowitz factory at Auschwitz.

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