1s² 2s²p⁶ 3s²p⁶d³ 4s²

History

Vanadium was originally discovered by Andres Manuel de Rio (a Spanish-born Mexican mineralogist) in Mexico City, in 1801.  He called it "brown lead" (now named vanadinite).  Through experimentation, its colors reminded him of chromium, so he named the element panchromium.  Rio sent samples of vanadium ore and a letter describing his methods to the Institute de France in Paris, France, for analysis and confirmation.  Unfortunately for Rio, his letter was lost in a shipwreck and the Institute only received his samples, which contained a brief note describing this new element, which Rio had renamed erythronium, since most of the salts turned red when heated. 

The French chemist Hippolyte Victor Collet-Descotils incorrectly declared that del Rio's new element was only impure chromium.   Del Rio thought himself to be mistaken and accepted the statement of the French chemist that was also backed by Del Rio's friend Baron Alexander von Humboldt.

In 1831, Nils Gabriel Sefstrôm of Sweden rediscovered vanadium in a new oxide he found while working with some iron ores and later that same year Friedrich Wohler confirmed del Rio's earlier work.  Later, George William Fetherstonhaugh, one of the first US geologists, suggested that the element should be named "rionium" after Del Rio, but this never happened.

Metallic vanadium was isolated by  Sir Henry Enfield Roscoe an English chemist,   in 1867, who reduced vanadium (III) chloride, VCl₃, with hydrogen gas, H₂.  The name vanadium comes from Vanadis, a goddess in Scandinavian mythology, because the element has beautiful multicolored chemical compounds.

Characteristics

Vanadium is a soft and ductile, silver-grey metal. It has good resistance to corrosion by alkalis, sulfuric and hydrochloric acid.  It oxidizes readily at about 933^oK.   Vanadium has good structural strength and a low fission neutron cross section, making it useful in nuclear applications.  Although a metal, it shares with chromium and manganese the property of having valency oxides with acid properties.

Common oxidation states of vanadium include +2, +3, +4 and +5.  A popular experiment with ammonium vanadate, NH₄VO₃, reducing the compound with zinc metal, can demonstrate colorimetrically all four of these vanadium oxidation states. A +1 oxidation state is rarely seen.

Occurrence

Vanadium is never found unbound in nature but it does occur in about 65 different minerals among which are patronite VS₄, vanadnite, Pb₅(VO₄)₃Cl, and carnotite, K₂(UO₂)₂(VO₄)₂·3H₂O.   Vanadium is also present in bauxite, and in carbon containing deposits such as crude oil, coal, oil shale and tar sands.  Vanadium has also been detected spectroscopically in light from the Sun and some other stars.

Much of the vanadium metal being produced is now made by calcium reduction V₂O₅ in a pressure vessel.  Vanadium is usually recovered as a by-product or co-product, and so world resources of the element are not really indicative of available supply.

Applications

Approximately 80% of vanadium produced is used as ferrovanadium or as a steel additive.   Other uses:

• In such alloys as:
  • specialty stainless steel, e.g. for use in surgical instruments and tools. 
  • rust resistant and high speed tool steels.
  • mixed with aluminum and titanium alloys used in jet engines and high-speed airframes
• Vanadium steel alloys are used in axles, crankshafts, gears, and other critical components.
• It is an important carabide stabilizer in making steels.
• Because of its low fission neutron cross section, vanadium has nuclear applications.
• Vanadium foil is used in cladding titanium to steel.
• Vanadium-gallium tape is used in superconducting magnets (175,000 gauss).
• Vanadium pentoxide, V₂O₅, is used as a catalyst in manufacturing sulfuric acid (via the contact process) and maleic anhydride.  It is also used in making ceramics.
• Glass coated with vanadium dioxide, VO₂, can block infrared radiation (and not visible light) at a specific temperature.
• Electrical fuel cells and storage batteries such as vanadium redox batteries. 
• Added to corundum to make simulated Alexandrite jewelry.
• Vanadate electrochemical conversion coatings for protecting steel against rust and corrosion
• Used to make lacrosse shafts. 

Biological

In biology, a vanadium atom is an essential component of some enzymes, particularly the vanadium nitrogenase used by some nitrogen-fixing micro-organisms.  Vanadium is essential to ascidians or sea squirts in vanadium chromogen 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.

Administration of oxovanadium compounds has been shown to alleviate diabetes mellitus symptoms in certain animal models and humans.  Much like the chromium effect on sugar metabolism, the mechanism of this effect is unknown.

Supplements

Vanadium pentoxide, V₂O₅, is marketed in Japan as a good mineral health supplement naturally occurring in drinking water.  The source of this drinking water is mainly the slopes of Mount Fuji.  The water's vanadium pentoxide content ranges from about 60 to 130 µg/liter. It is marketed as being effective against diabetes, eczema, and obesity.  There is no mention of its toxicity in the marketing of these products.

Isolation

Vanadium is available commercially and production of a sample in the laboratory is not normally required.  Commercially, routes leading to metallic vanadium as main product are not usually required as enough is produced as byproduct in other processes.

In industry, heating of vanadium ore or residues from other processes with salt, NaCl,   or sodium carbonate,  Na₂CO₃, at about 850°C gives sodium vanadate, NaVO₃.  This is dissolved in water and acidified to give a red solid which in turn is melted to form a crude form of vanadium pentoxide, V₂O₅.   Reduction of vanadium pentoxide with calcium gives pure vanadium. An alternative suitable for small scales is the reduction of vanadium pentachloride, VCl₅, with hydrogen or magnesium.  Many other methods are also in use.

Industrially, most vanadium is used as an additive to improve steels.  Rather than proceed via pure vanadium metal it is often sufficient to react the crude of vanadium pentoxide, V₂O₅, with crude iron.  This produces ferrovanadium suitable for further work.

Compounds

Vanadium pentoxide, V₂O₅, is used as a catalyst principally in the production of sulfuric acid.  It is the source of vanadium used in the manufacture of ferrovanadium.  It can be used as a dye and color-fixer.

Vanadyl sulfate, VOSO₄, also called vanadium (IV) sulfate oxide hydrate, is used as a relatively controversial dietary supplement, primarily for increasing insulin levels 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.

Vanadium (IV) chloride, VCl₄,  is a soluble form of vanadium that is commonly used in the laboratory.  Vanadium (IV) is the reduced form of Vanadium (V), and commonly occurs after anaerobic respiration by dissimilatory metal reducing bacteria.   VCl₄ reacts violently with water.

Oxidation States

It is known that vanadium gets the oxidation states +2, +3, +4, +5.  To observe the colours of these states, ammonium metavanadate, NH₄VO₃, can be used as a starting agent.  It must be acidified beforehand so dioxovanadium (V) ion, VO₂⁺ (yellow +5 oxidation number) is produced.  In alkaline medium, the stable form of vanadium(V) state is VO₃^-.

Adding zinc powder and concentrated hydrochloric acid continuously, VO₂⁺ is reduced into blue VO²⁺.

It can be seen that during the reaction, the mixture is green in colour as the original yellow of the +5 state and the blue of the +4 are present.

Continuously adding Zn powder and concentrated HCl, blue VO²⁺ is reduced to green V³⁺.  V³⁺ is then reduced to violet V²⁺ by Zn powder and concentrated HCl again.

Isotopes

Naturally occurring vanadium is composed of one stable isotope ⁵¹V and one radioactive isotope ⁵⁰V with a half-life of 1.5×10¹⁷ years.   25 artificial radioisotopes have been characterized (in the range of mass number between 40 and 65) with the most stable being 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. In 4 isotopes, metastable excited states were found (including 2 metastable states for ⁶⁰V).

The primary decay mode before the most abundant stable isotope ⁵¹V is electron capture.  The next most common mode is beta decay.  The primary decay products before ⁵¹V are element 22 (titanium) isotopes and the primary products after are element 24 (chromium) isotopes.

Precautions

Powdered metallic vanadium is a fire hazard, and unless known otherwise, all vanadium compounds should be considered highly toxic.   Generally, the higher the oxidation state of vanadium, the more toxic the compound is. he 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.

There is little evidence that vanadium or vanadium compounds are reproductive toxins or teratogens.  There is also no evidence that any vanadium compound is carcinogenic; however, very few adequate studies are available for evaluation. Vanadium has not been classified as to carcinogenicity by the U.S. EPA (1991a).

The toxicity of vanadium depends on its physico-chemical state; particularly on its valence state and solubility.  Pentavalent VOSO4 has been reported to be more than 5 times as toxic as trivalent V2O3 (Roschin, 1967).

Vanadium compounds are poorly absorbed through the gastrointestinal system.   Inhalation exposures to vanadium and vanadium compounds result primarily in adverse effects to the respiratory system (Sax, 1984; ATSDR, 1990). Quantitative data are, however, insufficient to derive a subchronic or chronic inhalation.