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{{about|the chemical element}} | |||
{{good article}} | |||
{{Use dmy dates|date=January 2022}} | |||
{{Infobox vanadium}} | {{Infobox vanadium}} | ||
'''Vanadium''' ({{IPAEng|vəˈneɪdiəm}}) is a ] that has the symbol '''V''' and ] 23. It is a soft, silvery grey, ] ]. The formation of a oxide layer makes the metal stable agains oxidation. By anlysing the mineral ], ] 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 ]. The element was rediscovered in 1831 by ], who named the element vanadium after the goddess of beauty ]. Both names were atributed to the fact that the redox chemistry of vanadium yields compounds in a wide range of colors. | |||
'''Vanadium''' is a ]; it has ] '''V''' and ] 23. It is a hard, silvery-grey, ] ]. The elemental metal is rarely found in nature, but once isolated artificially, the formation of an ] layer (]) somewhat stabilizes the free metal against further ]. | |||
It occurs naturally in about 65 different ]s and in ] 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 ]s such as ]. The compound ] is used as catalyst for the production of ]. Vanadium is found in many organisms, and is used by some life forms as active center of enzymes. | |||
]-] scientist ] discovered compounds of vanadium in 1801 by analyzing a new ]-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 ] that the element was just ]. Then in 1830, ] generated ] of vanadium, thus proving there was a new element, and named it "vanadium" after the Scandinavian goddess of beauty and fertility, ] (Freyja). The name was based on the wide range of colors found in vanadium compounds. Del Río's lead mineral was ultimately named ] for its vanadium content. In 1867, ] obtained the pure element. | |||
==History== | |||
A new element was originally ] by ], a Spanish-born Mexican mineralogist, in ]. The element was extracted from a sample of Mexican "brown lead" ore (now named ]). 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 ] incorrectly declared that del Río's new element was only impure ]. 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 ].<ref name="Cintas">{{cite journal | title = The Road to Chemical Names and Eponyms: Discovery, Priority, and Credit | author = Pedro Cintas | journal = Angewandte Chemie International Edition | volume = 43 | issue = 44 | pages = 5888 – 5894 | year = 2004 | url = | doi = 10.1002/anie.200330074 }}</ref> | |||
Vanadium occurs naturally in about 65 ]s and ] deposits. It is produced in ] and ] from steel smelter ]. Other countries produce it either from ] directly, flue dust of heavy oil, or as a byproduct of ] mining. It is mainly used to produce specialty ] ]s such as ], and some ]s. The most important industrial vanadium compound, ], is used as a catalyst for the production of ]. The ] for energy storage may be an important application in the future. | |||
] | |||
In ], ] of ] rediscovered the element in a new oxide which he found while working with some ] ores and later that same year ] 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 = ] | volume = 97 | issue = 1 | pages = 43 – 49 | year = 1831 | url = | doi = 10.1002/andp.18310970103 }}</ref> Sefström choose a name beginning with V, which had not yet been assigned to any element, and called it vanadium after ] (another name for ], the ]n goddess of fertility), because of many the beautifully colored ]s it produces.<ref name="sefs" /> In ], the geologist ] 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 | year = 1831 | pages = 69 | title = .}}</ref> | |||
Large amounts of vanadium ] are found in a few organisms, possibly as a ]. 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 ]s, such as the ] of some ocean ]. | |||
The development of routes to pure vanadium metal spanned many years. In ], ] reported the production of the metal, but ] showed that Berzelius had in fact produced the nitride, ]. Roscoe produced the metal in ] by reduction of ], VCl<sub>3</sub>, with ].<ref name="Roscoe">{{cite journal | title = Researches on Vanadium.--Part II. | author = Henry E. Roscoe | journal = ] | volume = 18 | issue = | pages = 37–42 | year =1869 – 1870 | url = http://www.jstor.org/stable/112705 | doi =10.1098/rspl.1869.0012 }}</ref> In 1927 the pure vanadium was produced by reducing ] with ].<ref name="Marden">{{cite journal | title = Vanadium | first = J. W. | last = Marden | coauthor = Rich, M. N. | journal = Industrial and Engineering Chemistry | year = 1927 | volume = 19 | issue = 7 | pages = 786–788 | doi = 10.1021/ie50211a012}}</ref> The first large scale industrial use was in the chassis of the ], which was inspired from French race cars. Vanadium steel allowed for reduced weight while simultaneously increasing ].<ref>{{cite book|title=Managing Technological Innovation: Competitive Advantage from Change|first=Frederick|last=Betz|publisher=Wiley-IEEE|year=2003|isbn=0471225630|pages=158–159|url=http://books.google.com/books?id=KnpGtu-R77UC&pg=PA158&dq=ford+model+T+vanadium&as_brr=3#PPA159,M1}}</ref> | |||
== |
== History == | ||
Vanadium was ] in Mexico in 1801 by the Spanish mineralogist ]. Del Río extracted the element from a sample of Mexican "brown lead" ore, later named ]. 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 ], backed by del Río's friend Baron ], incorrectly declared that del Río's new element was an impure sample of ]. Del Río accepted Collet-Descotils' statement and retracted his claim.<ref name="Cintas">{{cite journal |last1=Cintas |first1=Pedro |date=12 November 2004 |title=The Road to Chemical Names and Eponyms: Discovery, Priority, and Credit |journal=Angewandte Chemie International Edition |volume=43 |issue=44 |pages=5888–5894 |doi=10.1002/anie.200330074 |pmid=15376297}}</ref> | |||
===Physical=== | |||
] for vanadium in water.<ref>{{cite journal | journal = Electrochimica Acta | volume = 42 | issue = 4 | year = 1997 | pages = 579–586 | doi = 10.1016/S0013-4686(96)00202-2 | title = Electrochemical behaviour of vanadium in aqueous solutions of different pH | first = F. M. | last = Al-Kharafi | coauthors = Badawy, W. A.}}</ref>]] | |||
In 1831 Swedish chemist ] rediscovered the element in a new oxide he found while working with ]s. Later that year, ] 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 |last=Sefström |first=N. G. |date=1831 |title=Ueber das Vanadin, ein neues Metall, gefunden im Stangeneisen von Eckersholm, einer Eisenhütte, die ihr Erz von Taberg in Småland bezieht |url=https://zenodo.org/record/1423544 |url-status=live |journal=] |volume=97 |issue=1 |pages=43–49 |bibcode=1831AnP....97...43S |doi=10.1002/andp.18310970103 |archive-url=https://web.archive.org/web/20210910010050/https://zenodo.org/record/1423544 |archive-date=10 September 2021 |access-date=27 August 2019}}</ref> Sefström chose a name beginning with V, which had not yet been assigned to any element. He called the element ''vanadium'' after ] '']'' (another name for the ] ] goddess ], whose attributes include beauty and fertility), because of the many beautifully colored ]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 |last1=Marshall |first1=James L. |last2=Marshall |first2=Virginia R. |date=2004 |title=Rediscovery of the Elements: The "Undiscovery" of Vanadium |url=https://digital.library.unt.edu/ark:/67531/metadc111200/m2/1/high_res_d/metadc111200.pdf |url-status=live |archive-url=https://web.archive.org/web/20230330044956/https://digital.library.unt.edu/ark:/67531/metadc111200/m2/1/high_res_d/metadc111200.pdf |archive-date=30 March 2023 |access-date= |website=unt.edu |publisher=The Hexagon |page=45 |quote=}}</ref> In 1831, the geologist ] suggested that vanadium should be renamed "''rionium''" after del Río, but this suggestion was not followed.<ref>{{cite journal |last=Featherstonhaugh |first=George William |year=1831 |title=New Metal, provisionally called Vanadium |url=https://archive.org/stream/monthlyamericanj11831phil#page/68/mode/2up/search/rionium |journal=The Monthly American Journal of Geology and Natural Science |page=69}}</ref><!--Featherstonhaugh, the editor of the journal cited, comments on a letter from Berzelius to ]--> | |||
Vanadium is a soft, ], silver-grey metal. It has good resistance to ] both by ]s and ] and ]s.<ref name="HollemanAF">{{cite book | publisher = Walter de Gruyter | year = 1985 | edition = 91–100 | pages = 1071–1075 | isbn = 3110075113 | title = Lehrbuch der Anorganischen Chemie | first = Arnold F. | last = Holleman | coauthors = Wiberg, Egon; Wiberg, Nils; | chapter = Vanadium| language = German}}</ref> It is ] in air at about 933 ] (660 °C). Vanadium has good structural strength. | |||
<!-- Although a metal, it shares with ] and ] the property of having valency oxides with ] properties. --> | |||
Common ]s of vanadium include +2, +3, +4 and +5. In a popular experiment, ammonium vanadate (NH<sub>4</sub>VO<sub>3</sub>) can be successively reduced with ] metal to demonstrate the different colours of vanadium in these four oxidation states. Lower oxidation states occur in compounds such as V(CO)<sub>6</sub> and {{nowrap|<sup>-</sup>}} and substituted derivatives.<ref name="HollemanAF"/> | |||
] used vanadium steel in its ].]] | |||
===Isotopes=== | |||
As vanadium is usually found combined with other elements, the isolation of vanadium metal was difficult.<ref>{{cite journal |last1=Habashi |first1=Fathi |date=January 2001 |title=Historical Introduction to Refractory Metals |journal=Mineral Processing and Extractive Metallurgy Review |volume=22 |issue=1 |pages=25–53 |bibcode=2001MPEMR..22...25H |doi=10.1080/08827509808962488 |s2cid=100370649}}</ref> In 1831, ] reported the production of the metal, but ] showed that Berzelius had produced the nitride, ] (VN). Roscoe eventually produced the metal in 1867 by reduction of ], VCl<sub>2</sub>, with ].<ref name="Roscoe">{{cite journal |date=31 December 1870 |title=XIX. Researches on vanadium |url=https://zenodo.org/record/1432055 |url-status=live |journal=Proceedings of the Royal Society of London |volume=18 |issue=114–122 |pages=37–42 |doi=10.1098/rspl.1869.0012 |s2cid=104146966 |archive-url=https://web.archive.org/web/20210909211727/https://zenodo.org/record/1432055 |archive-date=9 September 2021 |access-date=27 August 2019}}</ref> In 1927, pure vanadium was produced by reducing ] with ].<ref name="Marden">{{cite journal |last1=Marden |first1=J. W. |last2=Rich |first2=M. N. |date=July 1927 |title=Vanadium 1 |journal=Industrial & Engineering Chemistry |volume=19 |issue=7 |pages=786–788 |doi=10.1021/ie50211a012}}</ref> | |||
{{main|Isotopes of vanadium}} | |||
Naturally occurring vanadium is composed of one stable ] <sup>51</sup>V and one radioactive isotope <sup>50</sup>V with a ] of 1.5×10<sup>17</sup> years and natural abundance 0.25%. <sup>51</sup>V has a ] of 7/2.<ref name="NUBASE">{{cite journal| first = Audi| last = Georges | title = The NUBASE Evaluation of Nuclear and Decay Properties| journal = Nuclear Physics A| volume = 729| pages = 3–128| publisher = Atomic Mass Data Center| date = 2003| doi=10.1016/j.nuclphysa.2003.11.001}}</ref> | |||
The first large-scale industrial use of vanadium was in the ] alloy chassis of the ], inspired by French race cars. Vanadium steel allowed reduced weight while increasing ] ({{circa|1905}}).<ref>{{cite book |last=Betz |first=Frederick |url=https://books.google.com/books?id=KnpGtu-R77UC&pg=PA158 |title=Managing Technological Innovation: Competitive Advantage from Change |date=2003 |publisher=Wiley-IEEE |isbn=978-0-471-22563-8 |pages=158–159}}</ref> For the first decade of the 20th century, most vanadium ore were mined by the ] from the ] in Peru. Later, the demand for uranium rose, leading to increased mining of that metal's ores. One major uranium ore was ], 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 |url=http://digital.library.unt.edu/ark:/67531/metadc170746/ |title=Vanadium: A Materials Survey |date=1961 |publisher=U.S. Department of the Interior, Bureau of Mines |page=65 |oclc=934517147 |access-date=19 April 2023 |archive-url=https://web.archive.org/web/20230423075450/https://digital.library.unt.edu/ark:/67531/metadc170746/ |archive-date=23 April 2023 |url-status=live}}</ref><ref>{{cite web |last=Wise |first=James M. |date=May 2018 |title=Remarkable folded dacitic dikes at Mina Ragra, Peru |url=https://www.southamericatotheworld.com/remarkable-folded-dacitic-dikes-at-mina-ragra-peru/ |url-status=live |archive-url=https://web.archive.org/web/20210910012241/https://www.southamericatotheworld.com/remarkable-folded-dacitic-dikes-at-mina-ragra-peru/ |archive-date=10 September 2021 |access-date=21 November 2018}}</ref> | |||
24 artificial ]s have been characterized (in the range of ] between 40 and 65). The most stable of these isotopes are <sup>49</sup>V with a half-life of 330 days and <sup>48</sup>V with a half-life of 15.9735 days. All of the remaining ] isotopes have half-lives shorter than an hour, the majority of them below 10 seconds. 4 isotopes have ].<ref name="NUBASE"/><!-- Unintelligible! | |||
The primary ] before the most abundant stable isotope <sup>51</sup>V is ]. The next most common mode is ]. The primary ]s before <sup>51</sup>V are element 22 (]) isotopes and the primary products after are element 24 (]) isotopes. --> | |||
In 1911, German chemist ] discovered vanadium in the ] proteins found in ]s (or ]ic cells) of ] (sea squirts).<ref>{{cite journal |last=Henze |first=M. |author-link=Friedrich Wolfgang Martin Henze |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}}</ref><ref name="michibata2002">{{cite journal |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 |url=http://ir.lib.hiroshima-u.ac.jp/files/public/0/22/20141016115442843522/MicroscopResTech_56_421-434_2002.pdf |url-status=live |journal=Microscopy Research and Technique |volume=56 |issue=6 |pages=421–434 |doi=10.1002/jemt.10042 |pmid=11921344 |s2cid=15127292 |archive-url=https://web.archive.org/web/20200317132408/https://ir.lib.hiroshima-u.ac.jp/files/public/0/22/20141016115442843522/MicroscopResTech_56_421-434_2002.pdf |archive-date=17 March 2020 |access-date=27 August 2019}}</ref> | |||
===Chemistry=== | |||
{{seealsocat|Vanadium compounds}} | |||
] | |||
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, VO<sub>4</sub><sup>3−</sup>, is replaced by the blue color of <sup>2+</sup>, followed by the green color of <sup>3+</sup> and then violet, due to <sup>2+</sup>.<ref name="HollemanAF"/> | |||
== Characteristics == | |||
The most commercially important compound is ], which is used as a catalyst for the production of ].<ref name="HollemanAF"/> This compound oxidizes sulfur dioxide to the trioxide. In this ], sulfur is oxidized from +4 to +6, and vanadium is reduced from +5 to +3: | |||
] and macro-etched]] | |||
: V<sub>2</sub>O<sub>5</sub> + 2 SO<sub>2</sub> → V<sub>2</sub>O<sub>3</sub> + 2 SO<sub>3</sub> | |||
Vanadium is an average-hard, ], steel-blue metal. Vanadium is usually described as "soft", because it is ductile, ], and not ].<ref>{{cite book |author=George F. Vander Voort |url=https://books.google.com/books?id=GRQC8zYqtBIC&pg=PA137 |title=Metallography, principles and practice |date=1984 |publisher=ASM International |isbn=978-0-87170-672-0 |pages=137– |access-date=17 September 2011}}</ref><ref>{{cite book |last=Cardarelli |first=François |url=https://books.google.com/books?id=PvU-qbQJq7IC&pg=PA338 |title=Materials handbook: a concise desktop reference |date=2008 |publisher=Springer |isbn=978-1-84628-668-1 |pages=338– |access-date=17 September 2011}}</ref> Vanadium is harder than most metals and steels (see ] and ]). It has good resistance to ] and it is stable against ]s and ] and ]s.<ref name="HollemanAF">{{cite book |last=Holleman |first=Arnold F. |title=Lehrbuch der Anorganischen Chemie |author2=Wiberg, Egon |author3=Wiberg, Nils |date=1985 |publisher=Walter de Gruyter |isbn=978-3-11-007511-3 |edition=91–100 |pages=1071–1075 |language=de |chapter=Vanadium}}</ref> It is ] in air at about 933 ] (660 °C, 1220 °F), although an oxide ] layer forms even at room temperature.<ref>{{Cite journal |last1=Klinser |first1=Gregor |last2=Zettl |first2=Roman |last3=Wilkening |first3=Martin |last4=Krenn |first4=Heinz |last5=Hanzu |first5=Ilie |last6=Würschum |first6=Roland |date=2019 |title=Redox processes in sodium vanadium phosphate cathodes – insights from operando magnetometry |url=https://xlink.rsc.org/?DOI=C9CP04045E |journal=Physical Chemistry Chemical Physics |language=en |volume=21 |issue=36 |pages=20151–20155 |doi=10.1039/C9CP04045E |issn=1463-9076|doi-access=free |pmid=31482877 |bibcode=2019PCCP...2120151K }}</ref> It also reacts with hydrogen peroxide. | |||
The catalyst us regenerated by oxidation with air. | |||
: V<sub>2</sub>O<sub>3</sub> + O<sub>2</sub> → V<sub>2</sub>O<sub>5</sub> | |||
=== Isotopes === | |||
Several ] are known for oxidation states 2, 3 and 4. ] is the most important commercially. This liquid is mainly used as a catalyst for polymerization of dienes. | |||
{{Main|Isotopes of vanadium}} | |||
<!-- ] --> | |||
Vanadium(II) compounds are reducing agents, and vanadium(V) derivatives are oxidizing agents. Vanadium(IV) compounds often exist as vanadyl derivatives which contain the VO<sup>2+</sup> center.<ref name="HollemanAF"/> <!--Vanadyl suphate, VOSO<sub>4</sub>, also called ], is the main intermediate in the extraction of vanadium from its ores. {{Fact|date=January 2009}}--> | |||
Naturally occurring vanadium is composed of one stable ], <sup>51</sup>V, and one radioactive isotope, <sup>50</sup>V. The latter has a ] of 2.71×10<sup>17</sup> years and a natural abundance of 0.25%. <sup>51</sup>V has a ] of {{frac|7|2}}, which is useful for ].<ref name="Rehder">{{cite book |last1=Rehder |first1=D. |title=Vanadium-51 NMR |last2=Polenova |first2=T. |last3=Bühl |first3=M. |year=2007 |isbn=978-0-12-373919-3 |series=Annual Reports on NMR Spectroscopy |volume=62 |pages=49–114 |doi=10.1016/S0066-4103(07)62002-X}}</ref> Twenty-four artificial ]s have been characterized, ranging in ] from 40 to 65. The most stable of these isotopes are <sup>49</sup>V with a half-life of 330 days, and <sup>48</sup>V with a half-life of 16.0 days. The remaining ] isotopes have half-lives shorter than an hour, most below 10 seconds. At least four isotopes have ].<ref>{{NUBASE 2003}}</ref> ] is the main ] for isotopes lighter than <sup>51</sup>V. For the heavier ones, the most common mode is ].{{NUBASE2020|ref}} The electron capture reactions lead to the formation of element 22 (]) isotopes, while beta decay leads to element 24 (]) isotopes. | |||
The oxyanion chemistry of vanadium(V) is complex. The vanadate ion, VO<sub>4</sub><sup>3−</sup>, is present in dilute solutions at high ]. On lowering the pH, HVO<sub>4</sub><sup>2-</sup> and H<sub>2</sub>VO<sub>4</sub><sup>-</sup> are formed, analogous to HPO<sub>4</sub><sup>2-</sup> and H<sub>2</sub>PO<sub>4</sub><sup>-</sup>. The acid dissociation constants for the vanadium and phosphorus series are ]. In more concentrated solutions many ] are formed. Chains, rings and clusters involving tetrahedral vanadium, analogous to the ]s, are known. In addition, clusters such as the decavanadates V<sub>10</sub>O<sub>28</sub><sup>4−</sup> and HV<sub>10</sub>O<sub>28</sub><sup>3−</sup>, which predominate in the pH range 4-6, are formed in which the vanadium is octahedral.<ref name="HollemanAF"/> | |||
<center> | |||
{|align="center" | |||
|<center>]</center> | |||
||<center>]</center> | |||
||<center>]</center> | |||
|- | |||
|<center>metavanadate chains</center> | |||
||<center>V<sub>5</sub>O<sub>14</sub> | |||
||<center>decavanadate ion | |||
|} | |||
</center> | |||
The correspondence between vanadate and phosphate chemistry can be attributed to the similarity in size and charge of phosphorus(V) and vanadium(V). ] VO<sub>4</sub><sup>3−</sup> is used in ] to study the ] of phosphate.<!--it forms pentacoordinate centers, highlighting the fact that vanadate is only a modest analogue of phosphate because it tends to form higher coordination numbers. It is not used for phasing--> | |||
== Compounds == | |||
====Coordination compounds==== | |||
{{Main|Vanadium compounds}} | |||
] of VO(acac)<sub>2</sub>]] | |||
<sup>2+</sup> (lilac), <sup>3+</sup> (green), <sup>2+</sup> (blue) and <sup>3+</sup> (yellow)]] | |||
Three factors are rather unusual in the coordination chemistry of vanadium, due its position early on in the ] series. Firstly, metallic vanadium has the electronic configuration 4s<sup>2</sup>3d<sup>3</sup>, so compounds of vanadium are relatively electron-poor. In consequence, most binary compounds are ]s (electron pair acceptors). For example all the halides form octahedral adducts with the formula VX<sub>n</sub>L<sub>6-n</sub> (X = halide; L = other ligand). Secondly the vanadium ion is rather large and can achieve coordination numbers higher than 6, as in <sup>4−</sup>. Thirdly, the vanadyl ion, VO<sup>2+</sup>, features in many complexes of vanadium(IV). ] 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 ] for that process is small. Many vanadyl complexes are 5-coordinate, but not all of them are square pyramidal. For example, VO(Cl<sub>2</sub>(NMe<sub>3</sub>)<sub>2</sub> is trigonal bypyramidal. | |||
The chemistry of vanadium is noteworthy for the accessibility of the four adjacent ]s 2–5. In an ], vanadium forms ]es of which the colors are lilac <sup>2+</sup>, green <sup>3+</sup>, blue <sup>2+</sup>, yellow-orange oxides <sup>3+</sup>, 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 ] derivatives, which contain the VO<sup>2+</sup> center.<ref name="HollemanAF" /> | |||
] (NH<sub>4</sub>VO<sub>3</sub>) can be successively reduced with elemental ] to obtain the different colors of vanadium in these four oxidation states. Lower oxidation states occur in compounds such as ], {{chem||-}} and substituted derivatives.<ref name="HollemanAF" /> | |||
Organometallic chemistry of vanadium is well developed, but organometallic compounds are of minor commercial significance. ] is a versatile starting reagent and even finds minor applications in organic chemistry.<ref name = wilkinson>{{cite journal | author=G. Wilkinson and J.G. Birmingham | title=Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta|journal=] | volume=76| issue=17| year=1954| pages=4281–4284 | doi = 10.1021/ja01646a008}}</ref> ], V(CO)<sub>6</sub>, is a rare example of an metal carbonyl that has an unpaired electron, but does not dimerize. Addition of an electron yields V(CO)<sub>6</sub><sup>−</sup> which is isoelectronic with Cr(CO)<sub>6</sub>. Further reduction with sodium in liquid ammonia yields V(CO)<sub>5</sub><sup>3−</sup>, isoelectronic with Fe(CO)<sub>5</sub>.<ref>{{cite journal | last = Bellard | first = S. | coauthors = Rubinson, K. A.; Sheldrick, G. M. | title = Crystal and molecular structure of vanadium hexacarbonyl | journal = Acta Crystallographica | year = 1979 | volume = B35 | pages = 271–274 | doi = 10.1107/S0567740879003332}}</ref><ref>{{cite book | first = C. | last = Elschenbroich | coauthor = Salzer A. | title = Organometallics : A Concise Introduction | year =1992 | publisher = Wiley-VCH | isbn = 3527281657}}</ref> | |||
] is a commercially important catalyst for the production of sulfuric acid, a reaction that exploits the ability of vanadium oxides to undergo redox reactions.<ref name="HollemanAF" /> | |||
===Occurrence=== | |||
{{seealsocat|Vanadate minerals}} | |||
] | |||
Metallic vanadium is not found in nature, but about 65 different ]s are known. Economically significant examples include ] (VS<sub>4</sub>),<ref>{{cite web | url = http://www.mindat.org/min-3131.html | title = mineralogical data about Patrónite | accessdate = 2009-01-19 | publisher = mindata.org}}</ref> ] ({{nowrap|Pb<sub>5</sub>(VO<sub>4</sub>)<sub>3</sub>Cl}}), and ] ({{nowrap|K<sub>2</sub>(UO<sub>2</sub>)<sub>2</sub>(VO<sub>4</sub>)<sub>2</sub>·3H<sub>2</sub>O}}). Much of the world's vanadium production is sourced from vanadium-bearing ] found in ] ] bodies. Vanadium is mined mostly in ], north west ] and eastern ]. In 2007 these three countries mined more than 95 % of the 58,600 ] of vanadium produced.<ref>{{cite web | publisher = ] | first = Michael J.| last = Magyar| url = http://minerals.usgs.gov/minerals/pubs/commodity/vanadium/mcs-2008-vanad.pdf| accessdate = 2009-01-15 | title = Mineral Commodity Summaries 2008: Vanadium}}</ref> <!-- {{Fact|date=January 2009}} of ], and ]. the ], ], ], ], ],--> | |||
The ] 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 <sup>+</sup> is replaced by the blue color of <sup>2+</sup>, followed by the green color of <sup>3+</sup> and then the violet color of <sup>2+</sup>.<ref name="HollemanAF" /> Another potential vanadium battery based on VB<sub>2</sub> uses multiple oxidation state to allow for 11 electrons to be released per VB<sub>2</sub>, giving it higher energy capacity by order of compared to Li-ion and gasoline per unit volume.<ref name=":0">{{Cite journal |last1=Licht |first1=Stuart |last2=Wu |first2=Huiming |last3=Yu |first3=Xingwen |last4=Wang |first4=Yufei |date=2008-07-11 |title=Renewable highest capacity VB2/air energy storage |url=https://pubs.rsc.org/en/content/articlelanding/2008/cc/b807929c |journal=Chemical Communications |language=en |issue=28 |pages=3257–3259 |doi=10.1039/B807929C |pmid=18622436 |issn=1364-548X}}</ref> VB<sub>2</sub> 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. <ref name=":0" /> | |||
Vanadium is also present in ] and in ] deposits such as ], ], ] and ] sands. In crude oil, concentrations up to 1200 ppm have been reported.<ref>{{cite journal | title = Vanadium and nickel complexes in petroleum resid acid, base, and neutral fractions | first = C. D. | last = Pearson | coauthors = Green J. B.| journal = Energy Fuels | year = 1993 | volume = 7 | issue =3 pages = 338–346 | doi = 10.1021/ef00039a001 | pages = 338}}</ref> An estimated 110,000 tonnes per year enter the atmosphere by burning fussile fuel.<ref>{{cite journal | journal =Anal. Real Acad. Nac. Farm. | year = 2004 | volume = 70 | pages = 961–999 | |||
| title = Vanadium - An element both essential and toxic to plants, animals and humans? | first = Manfred | last = Anke | url = http://www.ranf.com/pdf/anales/2004/0406.pdf}}</ref> Vanadium has been detected spectroscopically in light from the ] and some other ]s. | |||
== |
=== Oxyanions === | ||
] structure]] | |||
Industrially, most vanadium is used as ], an additive to improve ]s. ] is produced directly by reducing a mixture of vanadium oxide, iron oxides and iron in an electric furnace. Vanadium-bearing ] iron ore is the main source for vanadium production.<ref name="Moskalyk"/> The vanadium ends in ] produced from vanadium bearing magnetite. During ], oxygen is blown into the pig iron, oxidizing the carbon and most of the other impurities, forming ]. Depending on the used ore, the slag contains up to 25% of vanadium.<ref name="Moskalyk"/> | |||
<!-- ] -->In an aqueous solution, vanadium(V) forms an extensive family of ]s as established by ].<ref name="Rehder" /> The interrelationships in this family are described by the ], 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. ] V{{chem|O|4|3−}} is used in ]<ref>{{cite journal |last1=Sinning |first1=Irmgard |last2=Hol |first2=Wim G. J. |date=2004 |title=The power of vanadate in crystallographic investigations of phosphoryl transfer enzymes |journal=FEBS Letters |volume=577 |issue=3 |pages=315–21 |doi=10.1016/j.febslet.2004.10.022 |pmid=15556602 |s2cid=8328704 |doi-access=free|bibcode=2004FEBSL.577..315D }}</ref> to study the ] of phosphate.<ref>{{cite journal |last1=Seargeant |first1=L E |last2=Stinson |first2=R A |date=1 July 1979 |title=Inhibition of human alkaline phosphatases by vanadate |journal=Biochemical Journal |volume=181 |issue=1 |pages=247–250 |doi=10.1042/bj1810247 |pmc=1161148 |pmid=486156}}</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=9 July 1991 |title=Nonreductive interaction of vanadate with an enzyme containing a thiol group in the active site: glycerol-3-phosphate dehydrogenase |journal=Biochemistry |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. |date=November 1979 |title=Vanadate inhibits (Na+ + K+)ATPase by blocking a conformational change of the unphosphorylated form |journal=Nature |volume=282 |issue=5736 |pages=333–335 |bibcode=1979Natur.282..333K |doi=10.1038/282333a0 |pmid=228199 |s2cid=4341480}}</ref> The tetrathiovanadate <sup>3−</sup> is analogous to the orthovanadate ion.<ref>{{Greenwood&Earnshaw|page=988}}</ref> | |||
At lower pH values, the monomer <sup>2−</sup> and dimer <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 ] ion.<ref>{{cite journal |last1=Crans |first1=Debbie C. |date=18 December 2015 |title=Antidiabetic, Chemical, and Physical Properties of Organic Vanadates as Presumed Transition-State Inhibitors for Phosphatases |journal=The Journal of Organic Chemistry |volume=80 |issue=24 |pages=11899–11915 |doi=10.1021/acs.joc.5b02229 |pmid=26544762|doi-access=free }}</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 ] occur: at pH 4–6 <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 |volume=49 |pages=127–182 |editor-last=Sykes |editor-first=A. G. |access-date=2023-04-16 |series=Advances in Inorganic Chemistry |publisher=Academic Press |language=en |doi=10.1016/S0898-8838(08)60270-6 |isbn=978-0-12-023649-7}}</ref> Between pH 2–4 ] predominates, its formation from orthovanadate is represented by this condensation reaction: | |||
Vanadium metal is obtained via a multistep process that begins with the roasting of crushed ore with ] or ] at about 850 °C to give ] (NaVO<sub>3</sub>). An aqueous extract of this solid is acidified to give "red cake", a polyvanadate salt, which is reduced with ] metal. As an alternative for small scale production, vanadium pentoxide is reduced with ] or ]. Many other methods are also in use, in all of which vanadium is produced as a ] of other processes.<ref name="Moskalyk"/> | |||
:10 <sup>3−</sup> + 24 H<sup>+</sup> → <sup>6−</sup> + 12 H<sub>2</sub>O | |||
] | |||
Purification of vanadium is possible by the ] developed by ] and ] in 1925. It involves the formation of the metal iodide, in this example ], and the subsequent decomposition to yield pure metal. | |||
In decavanadate, each V(V) center is surrounded by six oxide ]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 <sup>−</sup> results in the preferential formation of the octahedral <sup>+</sup> species.<ref>{{Cite book |last1=Tracey |first1=Alan S. |url=https://books.google.com/books?id=vkMGP3PiuyYC&dq=+protonation+of+the+tetrahedral+species+%5BH2VO4%5D%E2%88%92+results+in+the+preferential+formation+of+the+octahedral+%5BVO2(H2O)4%5D++species&pg=PP1 |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 < 2, <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 ] of vanadic acid. The structures of many ] compounds have been determined by X-ray crystallography. | |||
] for vanadium in water, which shows the ] potentials between various vanadium species in different oxidation states<ref>{{cite journal |last1=Al-Kharafi |first1=F.M. |last2=Badawy |first2=W.A. |date=January 1997 |title=Electrochemical behaviour of vanadium in aqueous solutions of different pH |journal=Electrochimica Acta |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 ] 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 |author=Strukul, Giorgio |url=https://books.google.com/books?id=Lmt3x9CyfLgC&pg=PA128 |title=Catalytic oxidations with hydrogen peroxide as oxidant |date=1992 |publisher=Springer |isbn=978-0-7923-1771-5 |page=128}}</ref> | |||
=== Halide derivatives === | |||
Twelve binary ], 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, ] is used as a catalyst for the polymerization of ]s. Like all binary halides, those of vanadium are ]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 ]s (formula VO<sub>m</sub>X<sub>n</sub>) are known.<ref>{{Greenwood&Earnshaw|page=993}}</ref> The oxytrichloride and oxytrifluoride (] and ]) 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. |date=1 August 1975 |title=Thermochemistry of vanadium oxytrichloride and vanadium oxytrifluoride by mass spectrometry |journal=Inorganic Chemistry |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. |date=March 1994 |title=Transition Metal-Promoted Free-Radical Reactions in Organic Synthesis: The Formation of Carbon-Carbon Bonds |journal=Chemical Reviews |volume=94 |issue=2 |pages=519–564 |doi=10.1021/cr00026a008}}</ref> | |||
=== Coordination compounds === | |||
] of ]]] | |||
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 <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 ] center, VO<sup>2+</sup>, which binds four other ligands strongly and one weakly (the one trans to the vanadyl center). An example is ] (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 ] 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 |date=April 2007 |title=Structural characterization and electrochemical behavior of oxovanadium(V) complexes with N-salicylidene hydrazides |journal=Inorganica Chimica Acta |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. ] 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. |date=September 1954 |title=Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta |journal=Journal of the American Chemical Society |volume=76 |issue=17 |pages=4281–4284 |doi=10.1021/ja01646a008|bibcode=1954JAChS..76.4281W }}</ref> ], V(CO)<sub>6</sub>, is a rare example of a paramagnetic ]. Reduction yields V{{chem|(CO)|6|−}} (] with ]), 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. |date=15 February 1979 |title=Crystal and molecular structure of vanadium hexacarbonyl |journal=Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry |volume=35 |issue=2 |pages=271–274 |doi=10.1107/S0567740879003332|bibcode=1979AcCrB..35..271B }}</ref><ref>{{cite book |last=Elschenbroich |first=C. |title=Organometallics: A Concise Introduction |author2=Salzer A. |date=1992 |publisher=Wiley-VCH |isbn=978-3-527-28165-7}}</ref> | |||
== Occurrence == | |||
]]] | |||
Metallic vanadium is rare in nature (known as '''native vanadium'''),<ref>{{cite journal |author1=Ostrooumov, M. |author2=Taran, Y. |year=2015 |title=Discovery of Native Vanadium, a New Mineral from the Colima Volcano, State of Colima (Mexico) |url=https://www.uhu.es/fexp/sem2015/arc/macla/macla_20_109-110.pdf |url-status=live |journal=Revista de la Sociedad Española de Mineralogía |volume=20 |pages=109–110 |archive-url=https://web.archive.org/web/20230207070847/https://www.uhu.es/fexp/sem2015/arc/macla/macla_20_109-110.pdf |archive-date=7 February 2023 |access-date=7 February 2023}}</ref><ref>{{cite web |title=Vanadium: Vanadium mineral information and data |url=https://www.mindat.org/min-43604.html |url-status=live |archive-url=https://web.archive.org/web/20210716205934/https://www.mindat.org/min-43604.html |archive-date=16 July 2021 |access-date=2016-03-02 |website=Mindat.org}}</ref> having been found among fumaroles of the ], but vanadium compounds occur naturally in about 65 different ]s. | |||
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. ] was extracted from these mines.<ref>{{Cite book |last=Calvo Rebollar |first=Miguel |title=Construyendo la Tabla Periódica |publisher=Prames |year=2019 |isbn=978-84-8321-908-9 |location=Zaragoza, Spain |pages=161–165 |language=es |trans-title=Building the Periodic Table}}</ref> At the beginning of the 20th century, a large deposit of vanadium ore was discovered near Junín, ], ] (now the ] vanadium mine).<ref>{{cite journal |last1=Hillebrand |first1=W. F. |year=1907 |title=The Vanadium Sulphide, Patronite, and ITS Mineral Associates from Minasragra, Peru |url=https://zenodo.org/record/1450154 |url-status=live |journal=Journal of the American Chemical Society |volume=29 |issue=7 |pages=1019–1029 |doi=10.1021/ja01961a006 |bibcode=1907JAChS..29.1019H |archive-url=https://web.archive.org/web/20210911093143/https://zenodo.org/record/1450154 |archive-date=11 September 2021 |access-date=6 September 2020}}</ref><ref>{{cite journal |last1=Hewett |first1=F. |year=1906 |title=A New Occurrence of Vanadium in Peru |journal=The Engineering and Mining Journal |volume=82 |issue=9 |pages=385}}</ref><ref name="scielo">{{cite journal |last1=Steinberg |first1=W.S. |last2=Geyser |first2=W. |last3=Nell |first3=J. |year=2011 |title=The history and development of the pyrometallurgical processes at Evraz Highveld Steel & Vanadium |url=http://www.scielo.org.za/pdf/jsaimm/v111n10/v111n10a09.pdf |url-status=live |journal=The Journal of the Southern African Institute of Mining and Metallurgy |volume=111 |pages=705–710 |archive-url=https://web.archive.org/web/20210911093146/http://www.scielo.org.za/pdf/jsaimm/v111n10/v111n10a09.pdf |archive-date=11 September 2021 |access-date=17 December 2018}}</ref> For several years this ] (VS<sub>4</sub>)<ref>{{cite web |title=mineralogical data about Patrónite |url=https://www.mindat.org/min-3131.html |url-status=live |archive-url=https://web.archive.org/web/20210430004309/https://www.mindat.org/min-3131.html |archive-date=30 April 2021 |access-date=19 January 2009 |publisher=mindata.org}}</ref> 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.<ref>{{cite journal |last1=Allen |first1=M. A. |last2=Butler |first2=G. M. |date=1921 |title=Vanadium |url=https://repository.arizona.edu/bitstream/handle/10150/630042/b-115_vanadium.pdf |url-status=live |journal=University of Arizona |archive-url=https://web.archive.org/web/20210427182032/https://repository.arizona.edu/bitstream/handle/10150/630042/b-115_vanadium.pdf |archive-date=27 April 2021 |access-date=20 January 2020}}</ref> With the production of uranium in the 1910s and 1920s from ] ({{nowrap|K<sub>2</sub>(UO<sub>2</sub>)<sub>2</sub>(VO<sub>4</sub>)<sub>2</sub>·3H<sub>2</sub>O}}) vanadium became available as a side product of uranium production. ] ({{nowrap|Pb<sub>5</sub>(VO<sub>4</sub>)<sub>3</sub>Cl}}) 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 ] found in ] ] bodies. If this ] is used to produce iron, most of the vanadium goes to the ] and is extracted from it.<ref>{{cite journal |last1=Hukkanen |first1=E. |last2=Walden |first2=H. |year=1985 |title=The production of vanadium and steel from titanomagnetites |journal=International Journal of Mineral Processing |volume=15 |issue=1–2 |pages=89–102 |bibcode=1985IJMP...15...89H |doi=10.1016/0301-7516(85)90026-2}}</ref><ref name="scielo" /> | |||
Vanadium is mined mostly in ], ] and eastern ]. In 2022 these three countries mined more than 96% of the 100,000 ] of produced vanadium, with China providing 70%.<ref name="usgs">{{cite web |last=Polyak |first=Désirée E. |title=Mineral Commodity Summaries 2023: Vanadium |url=https://pubs.usgs.gov/periodicals/mcs2023/mcs2023-vanadium.pdf |url-status=live |archive-url=https://web.archive.org/web/20230207070837/https://pubs.usgs.gov/periodicals/mcs2023/mcs2023-vanadium.pdf |archive-date=7 February 2023 |access-date=7 February 2023 |publisher=]}}</ref> | |||
Fumaroles of Colima are known of being vanadium-rich, depositing other vanadium minerals, that include shcherbinaite (V<sub>2</sub>O<sub>5</sub>) and ] (K<sub>3</sub>VS<sub>4</sub>).<ref>Ostrooumov, M., and Taran, Y., 2015. Discovery of Native Vanadium, a New Mineral from the Colima Volcano, State of Colima (Mexico). Revista de la Sociedad Española de Mineralogía 20, 109-110</ref><ref>{{cite web|url=http://www.mindat.org/min-43604.html |title=Vanadium: Vaandium mineral information and data |website=Mindat.org |accessdate=2016-03-02}}</ref><ref>{{cite web|url=http://www.mindat.org/min-43604.html |title=Colima volcano (Volcan de Fuego; Volcan de Colima), Colima volcanic complex, Jalisco, Mexico |website=Mindat.org |accessdate=2016-03-02}}</ref> | |||
Vanadium is also present in ] and deposits of ], ], ], and ]s. In crude oil, concentrations up to 1200 ppm have been reported. When such oil products are burned, traces of vanadium may cause ] in engines and boilers.<ref>{{cite journal |last1=Pearson |first1=C. D. |last2=Green |first2=J. B. |date=1 May 1993 |title=Vanadium and nickel complexes in petroleum resid acid, base, and neutral fractions |url=https://digital.library.unt.edu/ark:/67531/metadc1198139/ |url-status=live |journal=Energy & Fuels |volume=7 |issue=3 |pages=338–346 |doi=10.1021/ef00039a001 |archive-url=https://web.archive.org/web/20210911093151/https://digital.library.unt.edu/ark:/67531/metadc1198139/ |archive-date=11 September 2021 |access-date=10 August 2018}}</ref> An estimated 110,000 tons of vanadium per year are released into the atmosphere by burning ].<ref>{{cite journal |last1=Anke |first1=Manfred |date=2004 |title=Vanadium: An element both essential and toxic to plants, animals and humans? |url=https://analesranf.com/wp-content/uploads/2004/70_04/7004_06.pdf |url-status=live |journal=Anales de la Real Academia Nacional de Farmacia |volume=70 |issue=4 |pages=961–999 |archive-url=https://web.archive.org/web/20230419220209/https://analesranf.com/wp-content/uploads/2004/70_04/7004_06.pdf |archive-date=19 April 2023 |access-date=19 April 2023}}</ref> ]s are also a potential source of vanadium. During WWII some vanadium was extracted from ]s in the south of Sweden.<ref>{{cite book |last1=Dyni |first1=John R. |title=Scientific Investigations Report |year=2006 |page=22 |chapter=Geology and resources of some world oil-shale deposits |doi=10.3133/sir29955294 |s2cid=19814608}}</ref> | |||
In the universe, the ] of vanadium is 0.0001%, making the element nearly as common as ] or ].<ref name="Dieter">{{cite book |last1=Rehder |first1=Dieter |title=Bioinorganic Vanadium Chemistry |date=2008 |publisher=John Wiley & Sons, Ltd |isbn=978-0-470-06509-9 |edition=1st |series=Inorganic Chemistry |location=Hamburg, Germany |pages=5 & 9–10 |doi=10.1002/9780470994429}}</ref> Vanadium is the 19th most abundant element in the crust.<ref>{{Cite book |last=Emsley |first=John |url=https://books.google.com/books?id=j-Xu07p3cKwC&dq=%2219th+most+abundant+element%22&pg=PA486 |title=Nature's Building Blocks: An A-Z Guide to the Elements |date=2003 |publisher=Oxford University Press |isbn=978-0-19-850340-8 |language=en}}</ref> It is detected ] in light from the ] and sometimes in the light from other ]s.<ref>{{cite journal |last1=Cowley |first1=C. R. |last2=Elste |first2=G. H. |last3=Urbanski |first3=J. L. |date=October 1978 |title=Vanadium abundances in early A stars |journal=Publications of the Astronomical Society of the Pacific |volume=90 |pages=536 |bibcode=1978PASP...90..536C |doi=10.1086/130379 |s2cid=121428891|doi-access=free }}</ref> The ] is also abundant in ], having an average concentration of 30 ] (1.5 mg/m<sup>3</sup>).<ref name="Dieter" /> Some ] ] also contain the ion in high concentrations. For example, springs near ] contain as much as 54 ] per ].<ref name="Dieter" /> | |||
== Production == | |||
] | |||
] crystals (99.9%)]] | |||
Vanadium metal is obtained by a multistep process that begins with roasting crushed ore with ] or ] at about 850 °C to give ] (NaVO<sub>3</sub>). An aqueous extract of this solid is acidified to produce "red cake", a polyvanadate salt, which is reduced with ] metal. As an alternative for small-scale production, vanadium pentoxide is reduced with ] or ]. Many other methods are also used, in all of which vanadium is produced as a ] of other processes.<ref name="Moskalyk">{{cite journal |last1=Moskalyk |first1=R.R |last2=Alfantazi |first2=A.M |date=September 2003 |title=Processing of vanadium: a review |journal=Minerals Engineering |volume=16 |issue=9 |pages=793–805 |bibcode=2003MiEng..16..793M |doi=10.1016/S0892-6875(03)00213-9}}</ref> Purification of vanadium is possible by the ] developed by ] and ] in 1925. It involves the formation of the metal iodide, in this example ], and the subsequent decomposition to yield pure metal:<ref>{{cite journal |last1=Carlson |first1=O. N. |last2=Owen |first2=C. V. |date=1961 |title=Preparation of High-Purity Vanadium Metalb by the Iodide Refining Process |journal=Journal of the Electrochemical Society |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> | :2 V + 3 I<sub>2</sub> {{eqm}} 2 VI<sub>3</sub> | ||
] | |||
==Applications== | |||
===Alloys=== | |||
] | |||
] | |||
Approximately 85% of vanadium produced is used as ] or as a ] additive.<ref name="Moskalyk">{{cite journal | journal =Minerals Engineering | volume = 16| issue = 9, September 2003| pages = 793–805 | doi = 10.1016/S0892-6875(03)00213-9 | first= R. R. | last = Moskalyk | coauthor = Alfantazi, A. M.| title = Processing of vanadium: a review | year =2003 }}</ref> | |||
The considerable increase of strength in steel containing small amounts of vanadium was discovered in the beginning of 20th century,<ref name="Chandler">{{cite book | title = Metallurgy for the Non-metallurgist | first = Harry | last = Chandler | publisher = ASM International | yera = 1998 | isbn = 9780871706522 | pages = 6–7 | url = http://books.google.de/books?id=arupok8PTBEC | year = 1998}}</ref> and from that time vanadium steel was used for applications in ]s, bicycle frames, ]s, 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 ] (HSS) with a vanadium content ranges from 1 % to 5 %. For the HSS after hardening a hardness above ]60) can be achieved. HSS steel is used in ]s and ]s.<ref>{{cite book | url = http://books.google.de/books?id=Kws7x68r_aUC&pg=PA11 | title = Tool Materials: Tool Materials | first = Joseph R. | last = Davis | publisher = ASM International | year = 1995 | isbn = 9780871705457}}</ref> | |||
Vanadium stabilizes the beta form of titanium and increases the strength and temperature stability. Mixed with ] in ] alloys it is used in ]s and high-speed airframes. One of the common alloys is Ti 6Al 4V a titanium alloy with 6% aluminium and 4% of vanadium.<ref>{{cite book | title = Titan und Titanlegierungen | chapter = Metastabile β-Legierungen | first = Manfred | last = Peters | coauthors = Leyens, C. | publisher = Wiley-VCH | year = 2002 | url = http://books.google.de/books?id=sxdR882jQpYC&pg=PA23 | isbn = 9783527305391 | pages = 23–24}}</ref> | |||
Most vanadium is used as a ] alloy called ]. Ferrovanadium is produced directly by reducing a mixture of vanadium oxide, iron oxides and iron in an electric furnace. The vanadium ends up in ] produced from vanadium-bearing magnetite. Depending on the ore used, the slag contains up to 25% of vanadium.<ref name="Moskalyk" /> | |||
===Other uses=== | |||
== Applications == | |||
*Vanadium foil is used in ] titanium to steel.<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 | year = 1966 | doi = 10.1007/BF01146317 | pages = 854–856 | first = N. T. | last = Lositskii | coauthor = Grigor'ev A. A.; Khitrova, G. V.}}</ref> | |||
] | |||
* ], V<sub>2</sub>O<sub>5</sub>, is used as a ] in manufacturing ] by the ]<ref>{{cite journal | journal = Journal of Catalysis | volume = 155 | issue = 1 | year = 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. | coauthors = Karydis, D. A.; Boghosian, S.; Fehrmann, R.}}</ref> and as an oxidizer in ] production.<ref>{{cite journal | journal = Applied Catalysis A: General | volume = 157 | issues = 1–2 | year = 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 | coauthors = Volta, Jean-Claude}}</ref> It is also used in making ]s.<ref name="rubber">{{cite book | title =CRC Handbook of Chemistry and Physics | first = David R. | last = Lide | CRC Press | year = 2004 | isbn = 9780849304859 | pages = 4—34| chapter = vanadium}}</ref> | |||
* Because of its moderate ] and the short half-life of the isotopes produced by neutron capture, vanadium has been proposed as the material to be used for the inner structure of a ].<ref>{{cite journal | journal = Journal of Nuclear Materials | volume = 233–237 | issue = 1 | year = 1996 | pages = 92–99 | doi = 10.1016/S0022-3115(96)00331-5 | title = Status of vanadium alloys for fusion reactors | first = H. | last = Matsui | coauthor = Fukumoto, K.; Smith, D. L.; Chung, Hee M.; Witzenburg, W. van; Votinov, S. N.}}</ref><ref>{{cite web | url = http://www.wahchang.com/pages/products/data/pdf/Vanadium.pdf | title = Vanadium Data Sheet | accessdate = 2009-01-16 | publisher = Allegheny Technologies – Wah Chang}}</ref> | |||
* Vanadium-gallium tape is used in ] magnets (17.5 ]s or 175,000 ]). The structure of the superconducting ] of V<sub>3</sub>Ga is similar to that of the more common ] and ].<ref>{{cite journal| journal = IEEE Transactions on Magnetics| volume = 13| issue = 1| year = 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.| url = | format = | accessdate =| coauthors = Mains, E.; Vankeuren, R.; Wilcox, R.; Rosner, C.; Inoue, H.; Hayashi, C.; Tachikawa, K. | doi = 10.1109/TMAG.1977.1059431}}</ref> The first A15 phase superconductor was also a vanadium compound. V<sub>3</sub>Si, which was discovered in 1952.<ref>{{cite journal| journal = Physical Reviews | volume = 89 | pages = 884–884 | year = 1953 | title = Superconducting Silicides and Germanides | first = George F. | last = Hardy | coauthor = Hulm, John K. | doi = 10.1103/PhysRev.89.884}}</ref> | |||
* Glass coated with ] VO<sub>2</sub> can block ] (and not visible light) at a specific temperature.<ref>{{cite journal | journal = Journal of Materials Chemistry | year = 2002 | volume = 12 | pages = 2936–2939 | title = Intelligent window coatings: atmospheric pressure chemical vapour | |||
deposition of vanadium oxides | first = Troy D. | last = Manning | coauthors = Parkin,Ivan P.; Clark, Robin J. H.; Sheel, David; Pemble, Martyn E.; Vernadou, Dimitra | doi = 10.1039/b205427m}}</ref> | |||
*] employ vanadium redox couples in both half-cells, thereby eliminating the problem of cross contamination by diffusion of ions across the membrane.<ref>{{cite journal | journal = Journal of Power Sources | volume = 127 | issues = 1–2 | year = 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 | coauthors = Garche, Juergen; Fabjan, Ch.; Tomazic G.}}</ref> | |||
* Simulated ] jewelry can be made by adding vanadium oxide to ].<ref>{{cite journal | url = http://www.minsocam.org/ammin/AM52/AM52_867.pdf | journal = American Mineralogist | volume = 52 | year = 1962 | last = White | coauthor = Roy, Rustum; McKay, Chrichton | title = The ''Alexandrite'' Effect: And Optical Study | pages = 867–871 | first = Willam B.}}</ref> | |||
* ] ]s are used for protecting steel against rust and corrosion.<ref>{{cite journal | title = Corrosion Protection of Aluminum Alloy 2024-T3 by Vanadate Conversion Coatings | first = H. | last =Guan | coauthors = Buchheit R. G. | journal = Corrosion | year = 2004 | volume = 60 | issue = 3 | pages = 284–296}}</ref> | |||
* ] has been proposed for use as a high energy density anode for lithium ion batteries, at 745 Wh/l when paired with a ] cathode.<ref>{{cite web | url = http://techon.nikkeibp.co.jp/article/HONSHI/20080129/146549/ | title = Li-Ion Rechargeable Batteries Made Safer | first = Koji | last = Kariatsumari | publisher = Nikkei Business Publications, Inc. | accessdate = 10-12-2008 |date=February 2008}}</ref> | |||
*A small amount, 40 to 270 ppm, of vanadium in ] and ], significantly improves the strength of the material.<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 | coauthors = Pendray, A. H.; Dauksch, W. E. |year = 1998}}</ref> | |||
== |
=== Alloys === | ||
Approximately 85% of the vanadium produced is used as ] or as a ] additive.<ref name="Moskalyk" /> 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 |last=Chandler |first=Harry |url=https://books.google.com/books?id=arupok8PTBEC |title=Metallurgy for the Non-metallurgist |date=1998 |publisher=ASM International |isbn=978-0-87170-652-2 |pages=6–7}}</ref> From that time on, vanadium steel was used for applications in ]s, bicycle frames, ]s, 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 ] (HSS) have a vanadium content of 1–5%. For high-speed tool steels, a hardness above ] 60 can be achieved. HSS steel is used in ]s and ]s.<ref>{{cite book |last=Davis |first=Joseph R. |url=https://books.google.com/books?id=Kws7x68r_aUC&pg=PA11 |title=Tool Materials: Tool Materials |date=1995 |publisher=ASM International |isbn=978-0-87170-545-7}}</ref> ] 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 |author1=Oleg D. Neikov |url=https://books.google.com/books?id=6aP3te2hGuQC&pg=PA490 |title=Handbook of Non-Ferrous Metal Powders: Technologies and Applications |last2=Naboychenko |first2=Stanislav |last3=Mourachova |first3=Irina |author4=Victor G. Gopienko |author5=Irina V. Frishberg |author6=Dina V. Lotsko |date=2009-02-24 |isbn=978-0-08-055940-7 |page=490 | publisher=Elsevier |access-date=17 October 2013}}</ref><!--http://www.wujii.com.tw/PDF/CPM%2015V.pdf--> | |||
] contain vanadium.]] | |||
] | |||
Vanadium plays very limited role in ]. A vanadium-containing ] is used by some ] micro-organisms. Vanadium is essential to ] or ]s in ]. The concentration of vanadium in their blood is more than 100 times higher than the concentration of vanadium in the seawater around them. ]s and ]s are also known to require vanadium in very small amounts and deficiencies result in reduced growth and impaired ].<ref>{{cite journal | title = Growth Effects of Vanadium in the Rat | first = Klaus | last = Schwarz | coauthor = Milne, David B. | journal = Science | volume = 174 | number = 4007 | year = 1971 | pages = 426–428 | url = http://www.jstor.org/stable/1731776}}</ref> Vanadium is a relatively controversial ], primarily for increasing ] sensitivity<ref>{{cite journal | journal = Diabetes Care | volume = 26 | pages = 1277–1294 | year = 2003 | title = Systematic Review of Herbs and Dietary Supplements for Glycemic Control in Diabetes | first = Gloria Y. | last = Yeh | coauthors = Eisenberg, David M.; Kaptchuk, Ted J.; Phillips, Russell S. | url = http://care.diabetesjournals.org/cgi/content/full/26/4/1277 }}</ref> and ]. 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 ].<ref>{{cite book | title = The Health Professional's Guide to Dietary Supplements | first = Shawn M. | last = Talbott, | coauthors = Hughes, Kerry | publisher = Lippincott Williams & Wilkins | year = 2007 | isbn = 9780781746724 | url = http://books.google.com/books?id=hV2_TdmoDo8C&pg=PA419 | chapter = Vanadium | pages = 419–422}}</ref> | |||
Vanadium stabilizes the beta form of titanium and increases the strength and temperature stability of titanium. Mixed with ] in ] alloys, it is used in ]s, high-speed airframes and ]s. The most common alloy for seamless tubing is ] 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 |url-status=dead |archive-url=https://web.archive.org/web/20161103173648/http://www.sevencycles.com/buildingbike/techsupplement/ti.php |archive-date=3 November 2016 |access-date=1 November 2016 |website=Seven Cycles}}</ref> Another common alloy, primarily produced in sheets, is ], a titanium alloy with 6% aluminium and 4% vanadium.<ref>{{cite book |last1=Zwicker |first1=Ulrich |title=Titan und Titanlegierungen |year=1974 |isbn=978-3-642-80588-2 |pages=4–29 |chapter=Herstellung des Metalls |doi=10.1007/978-3-642-80587-5_2}}</ref> | |||
Ten percent of the ] pigment of the ] is vanadium. Just as the ] has blue blood rather than ] (colored by iron in ]) because of ] in the ] pigment, the blood of the sea cucumber is yellow because of the vanadium in the ] pigment.<ref>{{cite web | last = Natkin | first = Michael | title = Blood Color | work = Science Facts | publisher = Soak (Source Of All Knowledge) | date = 2007 | url = http://www.soak.com/topic/sciencefacts/article/tshow/98556/blood+color | accessdate = 2007-11-16 }}</ref> Nonetheless, there is no evidence that vanabins carry oxygen, in contrast to hemoglobin and hemocyanin. | |||
Several vanadium alloys show ] behavior. The first ] 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. |date=15 February 1953 |title=Superconducting Silicides and Germanides |journal=Physical Review |volume=89 |issue=4 |pages=884 |bibcode=1953PhRv...89Q.884H |doi=10.1103/PhysRev.89.884}}</ref> ] tape is used in ] magnets (17.5 ] or 175,000 ]). The structure of the superconducting A15 phase of V<sub>3</sub>Ga is similar to that of the more common ] and ].<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. |date=January 1977 |title=A 17.5 Tesla superconducting concentric {{chem|Nb|3|Sn}} and {{chem|V|3|Ga}} magnet system |journal=IEEE Transactions on Magnetics |volume=13 |issue=1 |pages=35–37 |doi=10.1109/TMAG.1977.1059431}}</ref> | |||
] may improve glucose control in people with ].<ref name="Halberstam">{{cite journal| journal = Diabetes | volume = 45| issue = | year = 1996| pages = 659–66| title = Oral vanadyl sulfate improves insulin sensitivity in NIDDM but not in obese nondiabetic subjects.| last = Halberstam| first = M, et al| url = | format = | accessdate =| doi = 10.2337/diabetes.45.5.659| pmid = 8621019 }}</ref><ref name="Boden">{{cite journal| journal = Metabolism | volume = 45| issue = | year = 1996;| pages = 1130–5| title = Effects of vanadyl sulfate on carbohydrate and lipid metabolism in patients with non-insulin dependent diabetes mellitus.| last = Boden| first = G, et al| url = | format = | accessdate =| doi = 10.1016/S0026-0495(96)90013-X }}</ref><ref name="Goldfine">{{cite journal| journal = Metabolism | volume = 49| issue = | year = 2000| pages = 400–10| title = Metabolic effects of vanadyl sulfate in humans with non-insulin-dependent diabetes mellitus: in vivo and in vitro studies.| last = Goldfine | first = AB, et al| url = | format = | accessdate =| doi = 10.1016/S0026-0495(00)90418-9 }}</ref><ref name="Badmaev">{{cite journal| journal = Altern Complement Med.| volume = 5| issue = | year = 1999| pages = 273–291| title = Vanadium: a review of its potential role in the fight against diabetes.| last = Badmaev| first = V, et al| url = | format = | accessdate =| doi = 10.1089/acm.1999.5.273 }}</ref><ref name="Goldwaser">{{cite journal| journal = J Biol Chem| volume = 274| issue = | year = 1999| pages = 26617–26624 | title = L-Glutamic Acid gamma -Monohydroxamate. A Potentiator of Vanadium-Evoked Glucose Metabolism in vitro and in vivo| last = Goldwaser| first = I, et al| url = | format = | accessdate = | doi = 10.1074/jbc.274.37.26617 | pmid = 10473627 }}</ref> | |||
It has been found that a small amount, 40 to 270 ppm, of vanadium in ] 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. |date=September 1998 |title=The key role of impurities in ancient damascus steel blades |journal=JOM |volume=50 |issue=9 |pages=58–64 |bibcode=1998JOM....50i..58V |doi=10.1007/s11837-998-0419-y |s2cid=135854276}}</ref> | |||
Several species of macrofungi, namely '']'' and related species, accumulate vanadium (up to 500 mg/kg in dry weight). Vanadium is present in the ] amavadine in fungal fruit-bodies. However, the biological importance of the accumulation process is unknown.<ref>{{cite journal| journal = Journal of Environmental Science and Health, Part A| volume = 42| issue = 11| year = 2007| pages = 1615–1623 | title = Selected elements in fly agaric Amanita muscaria| last = Falandysz | first = J. | coauthors = Kunito, T., Kubota, R.; Lipka, K.; Mazur, A.; Falandysz, Justyna J.; Tanabe, S.|url = | format = | accessdate =| doi = 10.1080/10934520701517853 }}</ref><ref>{{cite journal| journal = Angewandte Chemie | volume = 111| issue = 6 | year = 1999| pages = 871–873 | title = Die Struktur von Amavadin | last = Berry| first = Robert E.| coauthors= Armstrong, Elaine M.; Beddoes, Roy L.; Collison, David; Ertok, Nigar; Helliwell, Madeleine; Garner, David | url = | format = | accessdate =| doi = 10.1002/(SICI)1521-3757(19990315)111:6<871::AID-ANGE871>3.0.CO;2-# }}</ref> | |||
Vanadium can be used as a substitute for molybdenum in armor steel, though the alloy produced is far more brittle and prone to ] on non-penetrating impacts.<ref>{{cite journal |last=Rohrmann |first=B. |year=1985 |title=Vanadium in South Africa (Metal Review Series no. 2) |journal=Journal of the Southern African Institute of Mining and Metallurgy |volume=85 |issue=5 |pages=141–150 |hdl=10520/AJA0038223X_1959}}</ref> The Third Reich was one of the most prominent users of such alloys, in armored vehicles like ] or ].<ref>{{cite journal |last=Overy |first=R. J. |year=1973 |title=Transportation and Rearmament in the Third Reich |journal=The Historical Journal |volume=16 |issue=2 |pages=389–409 |doi=10.1017/s0018246x00005926 |s2cid=153437214}}</ref> | |||
==Health and safety== | |||
All vanadium compounds should be considered to be toxic. Tetravalent VOSO<sub>4</sub> has been reported to be over 5 times more toxic than trivalent V<sub>2</sub>O<sub>3</sub>.<ref>{{cite journal | last = Roschin | first = A. V. | year = 1967 | title = Toxicology of vanadium compounds used in modern industry | journal = Gig Sanit. (Water Res.) | volume = 32 | pages = 26–32 | pimid = 5605589}}</ref> The most dangerous compound is ]. The ] (OSHA) has set an exposure limit of 0.05 mg/m<sup>3</sup> for vanadium pentoxide dust and 0.1 mg/m<sup>3</sup> for vanadium pentoxide fumes in workplace air for an 8-hour workday, 40-hour work week. The ] (NIOSH) has recommended that 35 mg/m<sup>3</sup> 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. | |||
=== Catalysts === | |||
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.<ref>{{cite book | last = Sax | first = N. I. | year = 1984 | title = Dangerous Properties of Industrial Materials, 6th ed. | publisher = Van Nostrand Reinhold Company | pages =2717–2720}}</ref><ref>{{cite journal | journal = Toxicological Sciences | volume = 74 | pages = 2876–296 | year = 2003| title = Carcinogenicity of Inhaled Vanadium Pentoxide in F344/N Rats and B6C3F1 Mice | author = N. B. Ress*, B. J. Chou, R. A. Renne, J. A. Dill, R. A. Miller, J. H. Roycroft, J. R. Hailey, J. K. Haseman and J. R. Bucher | pmid = 12773761}}</ref><ref>{{cite journal | title = Nanoparticulate Vanadium Oxide Potentiated Vanadium Toxicity in Human Lung Cells | author = Jörg M. Wörle-Knirsch, Katrin Kern, Carsten Schleh, Christel Adelhelm, Claus Feldmann, and Harald F. Krug | journal = Environ. Sci. Technol.| year = 2007 | volume = 41 | issues = 1 | pages = 331–336 | doi= 10.1021/es061140x}}</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 |last=Ścibior |first=A. |authorlink= |coauthors=Zaporowska, H.; Ostrowski, J. |year=2006 |month= |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 |url= |accessdate= |quote= }}</ref><ref>{{cite journal |last=Gonzalez-Villalva |first=A. |authorlink= |coauthors=''et al.'' |year= 2006|month= |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 |url= |accessdate= |quote= |pmid=16716040 }}</ref> on liver,<ref>{{cite journal | journal = Toxicology | volume = 228 | issues = 2-3 | year = 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 | author = Kazuo Kobayashia, Seiichiro Himeno, Masahiko Satoh, Junji Kuroda, Nobuo Shibata, Yoshiyuki Seko and Tatsuya Hasegawa}}</ref> on neurological development in rats,<ref>{{cite journal |last=Soazo |first=Marina |authorlink= |coauthors=Garcia, Graciela Beatriz |year=2007 |month= |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 |url= |accessdate= |quote= }}</ref> and other organs. | |||
] is a catalyst in the ] 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 |date=8 October 2018 |title=Catalytic Applications of Vanadium: A Mechanistic Perspective |journal=Chemical Reviews |volume=119 |issue=4 |pages=2128–2191 |doi=10.1021/acs.chemrev.8b00245 |osti=1509906 |pmid=30296048 |s2cid=52943647}}</ref> ] V<sub>2</sub>O<sub>5</sub>, is used as a ] in manufacturing sulfuric acid by the ]<ref>{{cite journal |last1=Eriksen |first1=K.M. |last2=Karydis |first2=D.A. |last3=Boghosian |first3=S. |last4=Fehrmann |first4=R. |date=August 1995 |title=Deactivation and Compound Formation in Sulfuric-Acid Catalysts and Model Systems |journal=Journal of Catalysis |volume=155 |issue=1 |pages=32–42 |doi=10.1006/jcat.1995.1185}}</ref> In this process ] ({{chem|SO|2}}) is oxidized to the ] ({{chem|SO|3}}):<ref name="HollemanAF" /> In this ], sulfur is oxidized from +4 to +6, and vanadium is reduced from +5 to +4: | |||
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,<ref>{{cite journal |last=Ress |first=N. B. |authorlink= |coauthors=''et al.'' |year=2003 |month= |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 |url= |accessdate= |quote= |pmid=12773761 }}</ref> although the interpretation of the results has recently been disputed.<ref>{{cite journal |last=Duffus |first=J. H. |authorlink= |coauthors= |year=2007 |month= |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 |url= |accessdate= |quote= }}</ref> Vanadium has not been classified as to carcinogenicity by the U.S. EPA.<ref>{{cite web | url = http://rais.ornl.gov/tox/profiles/old/vanadium_f_V1.htm | title = Toxicity Summary for Vanadium | date = 1991 | first = Dennis M. | last = Opreskos | accessdate = 2008-11-08 | publisher = Oak Ridge National Laboratory}}</ref> | |||
:V<sub>2</sub>O<sub>5</sub> + SO<sub>2</sub> → 2 VO<sub>2</sub> + SO<sub>3</sub> | |||
The catalyst is regenerated by oxidation with air: | |||
Metallic vanadium is potentially a fire hazard, particularly when in a finely-divided state. | |||
:4 VO<sub>2</sub> + O<sub>2</sub> → 2 V<sub>2</sub>O<sub>5</sub> | |||
Similar oxidations are used in the production of ]: | |||
: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 | |||
] and several other bulk organic compounds are produced similarly. These ] 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=3-527-30673-0}}</ref><ref>{{cite journal |last1=Abon |first1=Michel |last2=Volta |first2=Jean-Claude |date=September 1997 |title=Vanadium phosphorus oxides for n-butane oxidation to maleic anhydride |journal=Applied Catalysis A: General |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 ], acrylic acid or the ammoxidation of propylene to ].<ref>{{cite book |title=Metal Oxides, Chemistry and Applications |date=2006 |publisher=CRC Press |isbn=978-0-8247-2371-2 |editor1-last=Fierro |editor1-first=J. G. L. |pages=415–455}}</ref> | |||
== Vanadium in literature == | |||
Vanadium naphthenate has a curious place in literature. It features in the short story, entitled “Vanadium” in ]’s book, ].<ref>{{cite book|last=Levi|first=P.|others=Rosenthal, R. (translator)|title=The Periodic table|publisher=Penguin Classics|date=2000|isbn=0141185147 }}</ref> 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 ] factory at ]. | |||
== |
=== Other uses === | ||
The ], a type of ], 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. |date=March 2004 |title=Possible use of vanadium redox-flow batteries for energy storage in small grids and stand-alone photovoltaic systems |journal=Journal of Power Sources |volume=127 |issue=1–2 |pages=98–104 |bibcode=2004JPS...127...98J |doi=10.1016/j.jpowsour.2003.09.066}}</ref><ref name="RychcikSkyllas-Kazacos1988">{{cite journal |last1=Rychcik |first1=M. |last2=Skyllas-Kazacos |first2=M. |date=January 1988 |title=Characteristics of a new all-vanadium redox flow battery |journal=Journal of Power Sources |volume=22 |issue=1 |pages=59–67 |bibcode=1988JPS....22...59R |doi=10.1016/0378-7753(88)80005-3}}</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. | |||
{{reflist|colwidth=30em}} | |||
Vanadium redox batteries are used commercially for ].<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 |bibcode=2011AdEnM...1..394L |s2cid=33277301}}</ref> | |||
] can be used for protecting steel against rust and corrosion by ].<ref>{{cite journal |last1=Guan |first1=H. |last2=Buchheit |first2=R. G. |date=1 March 2004 |title=Corrosion Protection of Aluminum Alloy 2024-T3 by Vanadate Conversion Coatings |journal=Corrosion |volume=60 |issue=3 |pages=284–296 |doi=10.5006/1.3287733}}</ref> Vanadium foil is used in ] 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. |date=December 1966 |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 |pages=854–856 |doi=10.1007/BF01146317 |bibcode=1966CPE.....2..854L |s2cid=108903737}}</ref> The moderate ] and the short half-life of the isotopes produced by neutron capture makes vanadium a suitable material for the inner structure of a ].<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. |date=October 1996 |title=Status of vanadium alloys for fusion reactors |url=https://zenodo.org/record/1259631 |url-status=live |journal=Journal of Nuclear Materials |volume=233-237 |pages=92–99 |bibcode=1996JNuM..233...92M |doi=10.1016/S0022-3115(96)00331-5 |archive-url=https://web.archive.org/web/20210215013608/https://zenodo.org/record/1259631 |archive-date=15 February 2021 |access-date=10 August 2018}}</ref><ref>{{cite web |title=Vanadium Data Sheet |url=http://www.wahchang.com/pages/products/data/pdf/Vanadium.pdf |archive-url=https://web.archive.org/web/20090225153938/http://www.wahchang.com/pages/products/data/pdf/Vanadium.pdf |archive-date=25 February 2009 |access-date=16 January 2009 |publisher=]}}</ref> | |||
==External links== | |||
Vanadium can be added in small quantities < 5% to ] cathodes to increase ionic conductivity.<ref>{{Cite patent|number=US7842420B2|title=Electrode material with enhanced ionic transport properties|gdate=2010-11-30|invent1=Wixom|invent2=Xu|inventor1-first=Michael R.|inventor2-first=Chuanjing|url=https://patents.google.com/patent/US7842420B2/en?oq=7842420}}</ref> | |||
==== Proposed ==== | |||
] has been proposed for use as a high energy density anode for ], at 745 Wh/L when paired with a ] cathode.<ref>{{cite web |last=Kariatsumari |first=Koji |date=February 2008 |title=Li-Ion Rechargeable Batteries Made Safer |url=http://techon.nikkeibp.co.jp/article/HONSHI/20080129/146549/ |url-status=dead |archive-url=https://web.archive.org/web/20110912020554/http://techon.nikkeibp.co.jp/article/HONSHI/20080129/146549/ |archive-date=12 September 2011 |access-date=10 December 2008 |publisher=Nikkei Business Publications, Inc.}}</ref> ]s have been proposed as the cathode in the ], another type of lithium-ion battery.<ref>{{citation |last1=Saıdi |first1=M.Y. |title=Performance characteristics of lithium vanadium phosphate as a cathode material for lithium-ion batteries |date=1 June 2003 |journal=Journal of Power Sources |volume=119–121 |pages=266–272 |bibcode=2003JPS...119..266S |doi=10.1016/S0378-7753(03)00245-3 |last2=Barker |first2=J. |last3=Huang |first3=H. |last4=Swoyer |first4=J.L. |last5=Adamson |first5=G.}} Selected papers presented at the 11th International Meeting on Lithium Batteries</ref> | |||
== Biological role == | |||
Vanadium has a more significant role in marine environments than terrestrial ones.<ref>{{cite book |title=Vanadium and Its Role in Life |publisher=CRC |year=1995 |isbn=978-0-8247-9383-8 |editor1-last=Sigel |editor1-first=Astrid |series=Metal Ions in Biological Systems |volume=31 |editor2-last=Sigel |editor2-first=Helmut}}</ref> | |||
]s such as this bluebell tunicate contain vanadium as ].]] | |||
]'' contains ].]] | |||
=== Vanadoenzymes === | |||
Several species of marine ] produce ] as well as the closely related ] (which may use a ] or vanadium cofactor) and ]s. The bromoperoxidase produces an estimated 1–2 million tons of ] and 56,000 tons of ] 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 ]s are produced by this enzyme,<ref>{{cite journal |last1=Butler |first1=Alison |last2=Carter-Franklin |first2=Jayme N. |date=2004 |title=The role of vanadium bromoperoxidase in the biosynthesis of halogenated marine natural products |journal=Natural Product Reports |volume=21 |issue=1 |pages=180–188 |doi=10.1039/b302337k |pmid=15039842}}</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>}} | |||
A ] is used by some ] micro-organisms, such as '']''. In this role, vanadium serves in place of the more common ] or ], and gives the ] slightly different properties.<ref>{{cite journal |last1=Robson |first1=R. L. |last2=Eady |first2=R. R. |last3=Richardson |first3=T. H. |last4=Miller |first4=R. W. |last5=Hawkins |first5=M. |last6=Postgate |first6=J. R. |date=1986 |title=The alternative nitrogenase of Azotobacter chroococcum is a vanadium enzyme |journal=Nature |volume=322 |issue=6077 |pages=388–390 |bibcode=1986Natur.322..388R |doi=10.1038/322388a0 |s2cid=4368841}}</ref> | |||
=== Vanadium accumulation in tunicates === | |||
Vanadium is essential to ]s, where it is stored in the highly acidified ]s of certain blood cell types, designated ]s. ] (vanadium-binding proteins) have been identified in the cytoplasm of such cells. The concentration of vanadium in the blood of ] tunicates is as much as ten million times higher{{specify|date=April 2014}}<ref>{{cite journal |last1=Smith |first1=M. J. |date=1989 |title=Vanadium biochemistry: The unknown role of vanadium-containing cells in ascidians (sea squirts) |journal=Experientia |volume=45 |issue=5 |pages=452–7 |doi=10.1007/BF01952027 |pmid=2656286 |s2cid=43534732}}</ref><ref>{{cite journal |last1=MacAra |first1=Ian G. |last2=McLeod |first2=G. C. |last3=Kustin |first3=Kenneth |date=1979 |title=Tunichromes and metal ion accumulation in tunicate blood cells |journal=Comparative Biochemistry and Physiology B |volume=63 |issue=3 |pages=299–302 |doi=10.1016/0305-0491(79)90252-9}}</ref> than the surrounding seawater, which normally contains 1 to 2 μg/L.<ref>{{cite journal |last1=Trefry |first1=John H. |last2=Metz |first2=Simone |date=1989 |title=Role of hydrothermal precipitates in the geochemical cycling of vanadium |journal=Nature |volume=342 |issue=6249 |pages=531–533 |bibcode=1989Natur.342..531T |doi=10.1038/342531a0 |s2cid=4351410}}</ref><ref>{{cite journal |last1=Weiss |first1=H. |last2=Guttman |first2=M. A. |last3=Korkisch |first3=J. |last4=Steffan |first4=I. |date=1977 |title=Comparison of methods for the determination of vanadium in sea-water |journal=Talanta |volume=24 |issue=8 |pages=509–11 |doi=10.1016/0039-9140(77)80035-0 |pmid=18962130}}</ref> 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 ].<ref>{{cite book |last1=Ruppert |first1=Edward E. |title=Invertebrate Zoology |last2=Fox |first2=Richard, S. |last3=Barnes |first3=Robert D. |date=2004 |publisher=Cengage Learning |isbn=978-81-315-0104-7 |edition=7th |pages=947}}</ref> | |||
=== Fungi === | |||
'']'' and related species of macrofungi accumulate vanadium (up to 500 mg/kg in dry weight). Vanadium is present in the ] ]<ref>{{cite journal |last1=Kneifel |first1=Helmut |last2=Bayer |first2=Ernst |date=June 1973 |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 |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. |date=31 August 2007 |title=Selected elements in fly agaric Amanita muscaria |journal=Journal of Environmental Science and Health, Part A |volume=42 |issue=11 |pages=1615–1623 |doi=10.1080/10934520701517853 |pmid=17849303 |bibcode=2007JESHA..42.1615F |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 |date=15 March 1999 |title=The Structural Characterization of Amavadin |journal=Angewandte Chemie |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|doi-access=free }}</ref> Toxic or ] 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. |date=August 2013 |title=Amavadin, a vanadium natural complex: Its role and applications |journal=Coordination Chemistry Reviews |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 |last1=Schwarz |first1=Klaus |last2=Milne |first2=David B. |date=22 October 1971 |title=Growth Effects of Vanadium in the Rat |journal=Science |volume=174 |issue=4007 |pages=426–428 |bibcode=1971Sci...174..426S |doi=10.1126/science.174.4007.426 |pmid=5112000 |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 μg/day, with less than 5% absorbed. The ] (UL) of dietary vanadium, beyond which adverse effects may occur, is set at 1.8 mg/day.<ref>Nickel. IN: {{Webarchive|url=https://web.archive.org/web/20170922174144/https://www.nap.edu/read/10026/chapter/15|date=22 September 2017}}. National Academy Press. 2001, PP. 532–543.</ref> | |||
=== Research === | |||
] 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.<ref name="Smith2008">{{cite journal |last1=Smith |first1=D.M. |last2=Pickering |first2=R.M. |last3=Lewith |first3=G.T. |date=31 January 2008 |title=A systematic review of vanadium oral supplements for glycaemic control in type 2 diabetes mellitus |journal=QJM |volume=101 |issue=5 |pages=351–358 |doi=10.1093/qjmed/hcn003 |pmid=18319296}}</ref><ref>{{cite journal |year=2009 |title=Vanadium (vanadyl sulfate). Monograph |journal=Altern Med Rev |volume=14 |issue=2 |pages=177–80 |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 ], it has been suggested that discrete vanadium accumulations on ] could be a potential microbial ] when used in conjunction with ] and morphology.<ref name="Biosignature Vanadium">{{cite news |last=Lynch |first=Brendan M. |date=21 September 2017 |title=Hope to discover sure signs of life on Mars? New research says look for the element vanadium |work=PhysOrg |url=https://phys.org/news/2017-09-life-mars-element-vanadium.html |url-status=live |access-date=2017-10-14 |archive-url=https://web.archive.org/web/20211011173212/https://phys.org/news/2017-09-life-mars-element-vanadium.html |archive-date=11 October 2021}}</ref><ref name="Vanadium Craig">{{cite journal |last1=Marshall |first1=C. P |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 |year=2017 |title=Imaging of Vanadium in Microfossils: A New Potential Biosignature |journal=Astrobiology |volume=17 |issue=11 |pages=1069–1076 |bibcode=2017AsBio..17.1069M |doi=10.1089/ast.2017.1709 |osti=1436103 |pmid=28910135}}</ref> | |||
== Safety == | |||
All vanadium compounds should be considered toxic.<ref>{{cite journal |last=Srivastava |first=A. K. |year=2000 |title=Anti-diabetic and toxic effects of vanadium compounds |journal=Molecular and Cellular Biochemistry |volume=206 |issue=206 |pages=177–182 |doi=10.1023/A:1007075204494 |pmid=10839208 |s2cid=8871862}}</ref> Tetravalent ] 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 |trans-title=Toxicology of vanadium compounds used in modern industry |journal=Gigiena i Sanitariia (Water Res.) |language=ru |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 ] (OSHA) has set an exposure limit of 0.05 mg/m<sup>3</sup> for vanadium pentoxide dust and 0.1 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 |title=Occupational Safety and Health Guidelines for Vanadium Pentoxide |url=http://www.osha.gov/SLTC/healthguidelines/vanadiumpentoxidedust/recognition.html |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 |access-date=29 January 2009 |publisher=Occupational Safety and Health Administration}}</ref> The US ] (NIOSH) has recommended that 35 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. |title=Dangerous Properties of Industrial Materials |date=1984 |publisher=Van Nostrand Reinhold |edition=6th |pages=2717–2720}}</ref><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. |date=1 August 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><ref>{{cite journal |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 |date=2007 |title=Nanoparticulate Vanadium Oxide Potentiated Vanadium Toxicity in Human Lung Cells |journal=Environmental Science and Technology |volume=41 |issue=1 |pages=331–336 |bibcode=2007EnST...41..331W |doi=10.1021/es061140x |pmid=17265967}}</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 |bibcode=2006ArECT..51..287S |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 |date=April 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 |bibcode=2006ToxIH..22..113G |s2cid=9986509}}</ref> liver,<ref>{{cite journal |last1=Kobayashi |first1=Kazuo |last2=Himeno |first2=Seiichiro |last3=Satoh |first3=Masahiko |last4=Kuroda |first4=Junji |last5=Shibata |first5=Nobuo |last6=Seko |first6=Yoshiyuki |last7=Hasegawa |first7=Tatsuya |date=2006 |title=Pentavalent vanadium induces hepatic metallothionein through interleukin-6-dependent and -independent mechanisms |journal=Toxicology |volume=228 |issue=2–3 |pages=162–170 |doi=10.1016/j.tox.2006.08.022 |pmid=16987576|bibcode=2006Toxgy.228..162K }}</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|bibcode=2007NTxT...29..503S }}</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 ]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" /> 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=] |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 ].<ref>{{cite web |last=Opreskos |first=Dennis M. |date=1991 |title=Toxicity Summary for Vanadium |url=https://rais.ornl.gov/tox/profiles/vanadium_f_V1.html |url-status=live |archive-url=https://web.archive.org/web/20211006060858/https://rais.ornl.gov/tox/profiles/vanadium_f_V1.html |archive-date=6 October 2021 |access-date=8 November 2008 |publisher=Oak Ridge National Laboratory}}</ref> | |||
Vanadium traces in ]s are the main fuel component in ]. During combustion, vanadium oxidizes and reacts with sodium and sulfur, yielding ] compounds with melting points as low as {{Cvt|530|C}}, which attack the ] on steel and render it susceptible to corrosion. The solid vanadium compounds also abrade engine components.<ref>{{cite book |last1=Woodyard |first1=Doug |url=https://books.google.com/books?id=RC_k4q6y-JIC&pg=PA92 |title=Pounder's Marine Diesel Engines and Gas Turbines |date=2009-08-18 |isbn=978-0-08-094361-9 |page=92|publisher=Butterworth-Heinemann }}</ref><ref>{{cite book |last1=Totten |first1=George E. |url=https://books.google.com/books?id=J_AkNu-Y1wQC&pg=PA152 |title=Fuels and Lubricants Handbook: Technology, Properties, Performance, and Testing |last2=Westbrook |first2=Steven R. |last3=Shah |first3=Rajesh J. |date=2003-06-01 |isbn=978-0-8031-2096-9 |page=152}}</ref> | |||
== See also == | |||
*{{annotated link|Flow battery}} | |||
*{{annotated link|Green Giant mine}} | |||
*{{annotated link|Grid energy storage}} | |||
*{{annotated link|Vanadium carbide}} | |||
*{{annotated link|Vanadium redox battery}} | |||
*{{annotated link|Vanadium tetrachloride}} | |||
*{{annotated link|Vanadium(V) oxide}} | |||
*{{annotated link|International Vanadium Symposium}} | |||
*{{annotated link|Vanadium cycle}} | |||
== References == | |||
{{Reflist}} | |||
== Further reading == | |||
*{{cite book|chapter=Modeling the Biological Chemistry of Vanadium: Structural and Reactivity Studies Elucidating Biological Function|editor=Hill, Hugh A.O.|display-editors=etal|title=Metal sites in proteins and models: phosphatases, Lewis acids, and vanadium|publisher=Springer|date=1999|isbn=978-3-540-65553-4|chapter-url=https://books.google.com/books?id=ZF5aNOeHd5sC&pg=PA51|author=Slebodnick, Carla|display-authors=etal}} | |||
== External links == | |||
{{Commons|Vanadium}} | {{Commons|Vanadium}} | ||
{{ |
{{Wiktionary|vanadium}} | ||
* {{cite EB9 |wstitle = Vanadium |volume= XXIV | page=54 |short=1 }} | |||
* videos of the chemistry of the elements | |||
* at '']'' (University of Nottingham) | |||
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Latest revision as of 19:24, 31 December 2024
This article is about the chemical element. For other uses, see Vanadium (disambiguation).Chemical element with atomic number 23 (V)
Vanadium is a chemical element; it has 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 Río'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.
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. 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. 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. In 1831, the geologist George William Featherstonhaugh suggested that vanadium should be renamed "rionium" after del Río, but this suggestion was not followed.
As vanadium is usually found combined with other elements, the isolation of vanadium metal was difficult. 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. In 1927, pure vanadium was produced by reducing vanadium pentoxide with calcium.
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). 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.
In 1911, German chemist Martin Henze discovered vanadium in the hemovanadin proteins found in blood cells (or coelomic cells) of Ascidiacea (sea squirts).
Characteristics
Vanadium is an average-hard, ductile, steel-blue metal. Vanadium is usually described as "soft", because it is ductile, malleable, and not brittle. 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. It is oxidized in air at about 933 K (660 °C, 1220 °F), although an oxide passivation layer forms even at room temperature. It also reacts with hydrogen peroxide.
Isotopes
Main article: Isotopes of vanadiumNaturally occurring vanadium is composed of one stable isotope, V, and one radioactive isotope, V. The latter has a half-life of 2.71×10 years and a natural abundance of 0.25%. V has a nuclear spin of 7⁄2, which is useful for NMR spectroscopy. Twenty-four artificial radioisotopes have been characterized, ranging in mass number from 40 to 65. The most stable of these isotopes are V with a half-life of 330 days, and V 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. Electron capture is the main decay mode for isotopes lighter than V. For the heavier ones, the most common mode is beta decay. 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 compoundsThe 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 , green , blue , yellow-orange oxides , 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 VO center.
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,
and substituted derivatives.
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.
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 is replaced by the blue color of , followed by the green color of and then the violet color of . 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. 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.
Oxyanions
In an aqueous solution, vanadium(V) forms an extensive family of oxyanions as established by V NMR spectroscopy. The interrelationships in this family are described by the predominance diagram, which shows at least 11 species, depending on pH and concentration. The tetrahedral orthovanadate ion, VO
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 VO
4 is used in protein crystallography to study the biochemistry of phosphate. Besides that, this anion also has been shown to interact with the activity of some specific enzymes. The tetrathiovanadate is analogous to the orthovanadate ion.
At lower pH values, the monomer and dimer are formed, with the monomer predominant at a vanadium concentration of less than c. 10M (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. As the pH is reduced, further protonation and condensation to polyvanadates occur: at pH 4–6 is predominant at pV greater than ca. 4, while at higher concentrations trimers and tetramers are formed. Between pH 2–4 decavanadate predominates, its formation from orthovanadate is represented by this condensation reaction:
- 10 + 24 H → + 12 H2O
In decavanadate, each V(V) center is surrounded by six oxide ligands. Vanadic acid, H3VO4, exists only at very low concentrations because protonation of the tetrahedral species results in the preferential formation of the octahedral species. In strongly acidic solutions, pH < 2, 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.
Halide derivatives
Twelve binary halides, compounds with the formula VXn (n=2..5), are known. 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). Many of the halides form octahedral complexes with the formula VXnL6−n (X= halide; L= other ligand).
Many vanadium oxyhalides (formula VOmXn) are known. The oxytrichloride and oxytrifluoride (VOCl3 and VOF3) are the most widely studied. Akin to POCl3, they are volatile, adopt tetrahedral structures in the gas phase, and are Lewis acidic.
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 . 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 is dominated by the vanadyl center, VO, 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. The coordination chemistry of V is dominated by the relatively stable dioxovanadium coordination complexes 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.
Organometallic compounds
Main article: Organovanadium chemistryThe organometallic chemistry of vanadium is well–developed. Vanadocene dichloride is a versatile starting reagent and has applications in organic chemistry. 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)
5 (isoelectronic with Fe(CO)5).
Occurrence
Metallic vanadium is rare in nature (known as native vanadium), 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. At the beginning of the 20th century, a large deposit of vanadium ore was discovered near Junín, Cerro de Pasco, Peru (now the Minas Ragra vanadium mine). For several years this patrónite (VS4) 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. 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.
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%.
Fumaroles of Colima are known of being vanadium-rich, depositing other vanadium minerals, that include shcherbinaite (V2O5) and colimaite (K3VS4).
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. An estimated 110,000 tons of vanadium per year are released into the atmosphere by burning fossil fuels. Black shales are also a potential source of vanadium. During WWII some vanadium was extracted from alum shales in the south of Sweden.
In the universe, the cosmic abundance of vanadium is 0.0001%, making the element nearly as common as copper or zinc. Vanadium is the 19th most abundant element in the crust. It is detected spectroscopically in light from the Sun and sometimes in the light from other stars. The vanadyl ion is also abundant in seawater, having an average concentration of 30 nM (1.5 mg/m). 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.
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. 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
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.
Applications
Alloys
Approximately 85% of the vanadium produced is used as ferrovanadium or as a steel additive. 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. 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. 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.
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. Another common alloy, primarily produced in sheets, is Titanium 6AL-4V, a titanium alloy with 6% aluminium and 4% vanadium.
Several vanadium alloys show superconducting behavior. The first A15 phase superconductor was a vanadium compound, V3Si, which was discovered in 1952. 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.
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.
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. The Third Reich was one of the most prominent users of such alloys, in armored vehicles like Tiger II or Jagdtiger.
Catalysts
Vanadium compounds are used extensively as catalysts; Vanadium pentoxide V2O5, is used as a catalyst in manufacturing sulfuric acid by the contact process In this process sulfur dioxide (SO
2) is oxidized to the trioxide (SO
3): 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.
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.
Other uses
The vanadium redox battery, a type of flow battery, is an electrochemical cell consisting of aqueous vanadium ions in different oxidation states. 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.
Vanadate can be used for protecting steel against rust and corrosion by conversion coating. Vanadium foil is used in cladding titanium to steel because it is compatible with both iron and titanium. 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.
Vanadium can be added in small quantities < 5% to LFP battery cathodes to increase ionic conductivity.
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. Vanadium phosphates have been proposed as the cathode in the lithium vanadium phosphate battery, another type of lithium-ion battery.
Biological role
Vanadium has a more significant role in marine environments than terrestrial ones.
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. Most naturally occurring organobromine compounds are produced by this enzyme, catalyzing the following reaction (R-H is hydrocarbon substrate):
R-H + Br + H2O2 → R-Br + H2O + OHA 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.
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 than the surrounding seawater, which normally contains 1 to 2 μg/L. 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.
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 in fungal fruit-bodies. The biological importance of the accumulation is unknown. Toxic or peroxidase enzyme functions have been suggested.
Mammals
Deficiencies in vanadium result in reduced growth in rats. 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.
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. 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."
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.
Safety
All vanadium compounds should be considered toxic. Tetravalent VOSO4 has been reported to be at least 5 times more toxic than trivalent V2O3. The US Occupational Safety and Health Administration (OSHA) has set an exposure limit of 0.05 mg/m for vanadium pentoxide dust and 0.1 mg/m for vanadium pentoxide fumes in workplace air for an 8-hour workday, 40-hour work week. The US National Institute for Occupational Safety and Health (NIOSH) has recommended that 35 mg/m of vanadium be considered immediately dangerous to life and health, that is, likely to cause permanent health problems or death.
Vanadium compounds are poorly absorbed through the gastrointestinal system. Inhalation of vanadium and vanadium compounds results primarily in adverse effects on the respiratory system. 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, liver, neurological development, and other organs 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, although the interpretation of the results has been disputed a few years after the report. The carcinogenicity of vanadium has not been determined by the United States Environmental Protection Agency.
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.
See also
- Flow battery – Type of electrochemical cell
- Green Giant mine – Vanadium mine in Madagascar
- Grid energy storage – Large scale electricity supply management
- Vanadium carbide – Extremely hard refractory ceramic material
- Vanadium redox battery – Type of rechargeable flow battery
- Vanadium tetrachloride – Chemical reagent used to produce other vanadium compounds
- Vanadium(V) oxide – Precursor to vanadium alloys and industrial catalyst
- International Vanadium Symposium – Biennial interdisciplinary event
- Vanadium cycle – Exchange of vanadium between continental crust and seawater
References
- "Standard Atomic Weights: Vanadium". CIAAW. 1977.
- Prohaska, Thomas; Irrgeher, Johanna; Benefield, Jacqueline; Böhlke, John K.; Chesson, Lesley A.; Coplen, Tyler B.; Ding, Tiping; Dunn, Philip J. H.; Gröning, Manfred; Holden, Norman E.; Meijer, Harro A. J. (4 May 2022). "Standard atomic weights of the elements 2021 (IUPAC Technical Report)". Pure and Applied Chemistry. doi:10.1515/pac-2019-0603. ISSN 1365-3075.
- ^ Arblaster, John W. (2018). Selected Values of the Crystallographic Properties of Elements. Materials Park, Ohio: ASM International. ISBN 978-1-62708-155-9.
- V(–3) is known in V(CO)3−5; see John E. Ellis (2006). "Adventures with Substances Containing Metals in Negative Oxidation States". Inorganic Chemistry. 45 (8). doi:10.1021/ic052110i.
- ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 28. ISBN 978-0-08-037941-8.
- V(0) is known in V(CO)6; see John E. Ellis (2006). "Adventures with Substances Containing Metals in Negative Oxidation States". Inorganic Chemistry. 45 (8). doi:10.1021/ic052110i.
- Weast, Robert (1984). CRC, Handbook of Chemistry and Physics. Boca Raton, Florida: Chemical Rubber Company Publishing. pp. E110. ISBN 0-8493-0464-4.
- "Vanadium". Royal Society of Chemistry. Royal Society of Chemistry. Retrieved 5 December 2022.
- Cintas, Pedro (12 November 2004). "The Road to Chemical Names and Eponyms: Discovery, Priority, and Credit". Angewandte Chemie International Edition. 43 (44): 5888–5894. doi:10.1002/anie.200330074. PMID 15376297.
- ^ Sefström, N. G. (1831). "Ueber das Vanadin, ein neues Metall, gefunden im Stangeneisen von Eckersholm, einer Eisenhütte, die ihr Erz von Taberg in Småland bezieht". Annalen der Physik und Chemie. 97 (1): 43–49. Bibcode:1831AnP....97...43S. doi:10.1002/andp.18310970103. Archived from the original on 10 September 2021. Retrieved 27 August 2019.
- Marshall, James L.; Marshall, Virginia R. (2004). "Rediscovery of the Elements: The "Undiscovery" of Vanadium" (PDF). unt.edu. The Hexagon. p. 45. Archived (PDF) from the original on 30 March 2023.
- Featherstonhaugh, George William (1831). "New Metal, provisionally called Vanadium". The Monthly American Journal of Geology and Natural Science: 69.
- Habashi, Fathi (January 2001). "Historical Introduction to Refractory Metals". Mineral Processing and Extractive Metallurgy Review. 22 (1): 25–53. Bibcode:2001MPEMR..22...25H. doi:10.1080/08827509808962488. S2CID 100370649.
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- Kobayashi, Kazuo; Himeno, Seiichiro; Satoh, Masahiko; Kuroda, Junji; Shibata, Nobuo; Seko, Yoshiyuki; Hasegawa, Tatsuya (2006). "Pentavalent vanadium induces hepatic metallothionein through interleukin-6-dependent and -independent mechanisms". Toxicology. 228 (2–3): 162–170. Bibcode:2006Toxgy.228..162K. doi:10.1016/j.tox.2006.08.022. PMID 16987576.
- Soazo, Marina; Garcia, Graciela Beatriz (2007). "Vanadium exposure through lactation produces behavioral alterations and CNS myelin deficit in neonatal rats". Neurotoxicology and Teratology. 29 (4): 503–510. Bibcode:2007NTxT...29..503S. doi:10.1016/j.ntt.2007.03.001. PMID 17493788.
- Barceloux, Donald G. (1999). "Vanadium". Clinical Toxicology. 37 (2): 265–278. doi:10.1081/CLT-100102425. PMID 10382561.
- Duffus, J. H. (2007). "Carcinogenicity classification of vanadium pentoxide and inorganic vanadium compounds, the NTP study of carcinogenicity of inhaled vanadium pentoxide, and vanadium chemistry". Regulatory Toxicology and Pharmacology. 47 (1): 110–114. doi:10.1016/j.yrtph.2006.08.006. PMID 17030368.
- Opreskos, Dennis M. (1991). "Toxicity Summary for Vanadium". Oak Ridge National Laboratory. Archived from the original on 6 October 2021. Retrieved 8 November 2008.
- Woodyard, Doug (18 August 2009). Pounder's Marine Diesel Engines and Gas Turbines. Butterworth-Heinemann. p. 92. ISBN 978-0-08-094361-9.
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Further reading
- Slebodnick, Carla; et al. (1999). "Modeling the Biological Chemistry of Vanadium: Structural and Reactivity Studies Elucidating Biological Function". In Hill, Hugh A.O.; et al. (eds.). Metal sites in proteins and models: phosphatases, Lewis acids, and vanadium. Springer. ISBN 978-3-540-65553-4.
External links
- "Vanadium" . Encyclopædia Britannica. Vol. XXIV (9th ed.). 1888. p. 54.
- Vanadium at The Periodic Table of Videos (University of Nottingham)
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