Vanadyl sulfate

Vanadyl(IV) sulfate describes a collection of inorganic compounds of vanadium with the formula, VOSO4(H2O)x where 0 ≤ x ≤ 6. The pentahydrate is common. This hygroscopic blue solid is one of the most common sources of vanadium in the laboratory, reflecting its high stability. It features the vanadyl ion, VO2+, which has been called the "most stable diatomic ion".[1]

Vanadyl sulfate
Vanadyl sulfate
Names
IUPAC name
Oxovanadium(2+) sulfate
Other names
Basic vanadium(IV) sulfate
Vanadium(IV) oxide sulfate
Vanadium(IV) oxysulfate
Identifiers
ECHA InfoCard 100.044.214
RTECS number
  • YW1925000
UNII
  • InChI=1S/H2O4S.O.V/c1-5(2,3)4;;/h(H2,1,2,3,4);;/q;;+2/p-2 ☒N
    Key: UUUGYDOQQLOJQA-UHFFFAOYSA-L ☒N
Properties
H10O10SV
Molar mass 253.07 g·mol−1
Appearance Blue solid
Melting point 105 °C (221 °F; 378 K) decomposes
Soluble
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Irritant
Flash point Non-flammble
Related compounds
Other anions
 Vanadyl chloride
Vanadyl nitrate
Other cations
 Vanadium(III) sulfate
Related compounds
 Vanadyl acetylacetonate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references
Vanadyl sulfate
Vanadyl sulfate trihydrate

Vanadyl sulfate is an intermediate in the extraction of vanadium from petroleum residues, one commercial source of vanadium.[2]

Synthesis, structure, and reactions

Vanadyl sulfate is most commonly obtained by reduction of vanadium pentoxide with sulfur dioxide:

V2O5 + 7 H2O + SO2 + H2SO4 → 2 [V(O)(H2O)4]SO4

From aqueous solution, the salt crystallizes as the pentahydrate, the fifth water is not bound to the metal in the solid. Viewed as a coordination complex, the ion is octahedral, with oxo, four equatorial water ligands, and a monodentate sulfate.[1][3] The trihydrate has also been examined by crystallography.[4] A hexahydrate exists below 13.6 °C (286.8 K).[5] Two polymorphs of anhydrous VOSO4 are known.[6]

The V=O bond distance is 160 pm, about 50 pm shorter than the V–OH2 bonds. In solution, the sulfate ion dissociates rapidly.

Being widely available, vanadyl sulfate is a common precursor to other vanadyl derivatives, such as vanadyl acetylacetonate:[7]

[V(O)(H2O)4]SO4 + 2 C5H8O2 + Na2CO3 → [V(O)(C5H7O2)2] + Na2SO4 + 5 H2O + CO2

In acidic solution, oxidation of vanadyl sulfate gives yellow-coloured vanadyl(V) derivatives. Reduction, e.g. by zinc, gives vanadium(III) and vanadium(II) derivatives, which are characteristically green and violet, respectively.

Occurrence in nature

Like most water-soluble sulfates, vanadyl sulfate is only rarely found in nature. Anhydrous form is pauflerite,[8] a mineral of fumarolic origin. Hydrated forms, also rare, include hexahydrate (stanleyite), pentahydrates (minasragrite, orthominasragrite,[9] and anorthominasragrite) and trihydrate - bobjonesite.[10]

Medical research

Vanadyl sulfate is a component of food supplements and experimental drugs. Vanadyl sulfate exhibits insulin-like effects.[11]

Vanadyl sulfate has been extensively studied in the field of diabetes research as a potential means of increasing insulin sensitivity. No evidence indicates that oral vanadium supplementation improves glycaemic control.[12][13] Treatment with vanadium often results in gastrointestinal side-effects, primarily diarrhea.

Vanadyl sulfate is also marketed as a health supplement, often for bodybuilding. Deficiencies in vanadium result in reduced growth in rats.[14] Its effectiveness for bodybuilding has not been proven; some evidence suggests that athletes who take it are merely experiencing a placebo effect.[15]

References
  1. Greenwood, Norman N.; Earnshaw, Alan (1984). Chemistry of the Elements. Oxford: Pergamon Press. p. 1157. ISBN 978-0-08-022057-4.
  2. Günter Bauer; Volker Güther; Hans Hess; Andreas Otto; Oskar Roidl; Heinz Roller; Siegfried Sattelberger (2005). "Vanadium and Vanadium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a27_367. ISBN 3-527-30673-0.
  3. Tachez, M.; Theobald, F.R. (1980). "Structure du Sulfate de Vanadyle Pentahydrate VO(H2O)5SO4 beta (variete orthorhombique)". Acta Crystallographica B. B36 (8): 1757–p1761. doi:10.1107/S0567740880007170.
  4. Tachez, M.; Theobald, F. R. (1980). "Liaisons hydrogene dans les cristaux de sulfate de vanadyle trihydrate VOSO4(H2O)3: Comparaison structurale de quatre sulfates de vanadyle hydrate". Acta Crystallographica B. 36: 2873–2880. doi:10.1107/S056774088001045X.
  5. M. Tachez, F. Theobald, G. Trouillot. Crystal data for vanadyl sulphate hexahydrate VOSO4.6H2O. J. Appl. Crystallogr. (1976). 9, 246
  6. Boghosian, S.; Eriksen, K.M.; Fehrmann, R.; Nielsen, K. (1995). "Synthesis, Crystal Structure Redetermination and Vibrational Spectra of beta- VOSO4". Acta Chemica Scandinavica. 49: 703–708. doi:10.3891/acta.chem.scand.49-0703.Longo, J. M.; Arnott, R. J. (1970). "Structure and magnetic properties of VOSO4". Journal of Solid State Chemistry. 1 (3–4): 394–p398. Bibcode:1970JSSCh...1..394L. doi:10.1016/0022-4596(70)90121-0.
  7. Bryant, Burl E.; Fernelius, W. Conard (1957), "Vanadium(IV) Oxy(acetylacetonate)", Inorg. Synth., Inorganic Syntheses, 5: 113–16, doi:10.1002/9780470132364.ch30, ISBN 978-0-470-13236-4
  8. Krivovichev, S. V.; Vergasova, L. P.; Britvin, S. N.; Filatov, S. K.; Kahlenberg, V.; Ananiev, V. V. (1 August 2007). "Pauflerite, -VO(SO4), a New Mineral Species from the Tolbachik Volcano, Kamchatka Peninsula, Russia". The Canadian Mineralogist. 45 (4): 921–927. doi:10.2113/gscanmin.45.4.921.
  9. Hawthorne, F. C.; Schindler, M.; Grice, J. D.; Haynes, P. (1 October 2001). "Orthominasragrite, V4+O(SO4)(H2O)5, A New Mineral Species from Temple Mountain, Emery County, Utah, U.A.A.". The Canadian Mineralogist. 39 (5): 1325–1331. doi:10.2113/gscanmin.39.5.1325.
  10. Schindler, M.; Hawthorne, F. C.; Huminicki, D. M.C.; Haynes, P.; Grice, J. D.; Evans, H. T. (1 February 2003). "Bobjonesite, V4+ O (So4) (H2O)3, A New Mineral Species from Temple Mountain, Emery County, Utah, U.s.a.". The Canadian Mineralogist. 41 (1): 83–90. doi:10.2113/gscanmin.41.1.83.
  11. Crans, D. C.; Trujillo, A. M.; Pharazyn, P. S.; Cohen, M. D. (2011). "How environment affects drug activity: Localization, compartmentalization and reactions of a vanadium insulin-enhancing compound, dipicolinatooxovanadium(V)". Coord. Chem. Rev. 255 (19–20): 2178–2192. doi:10.1016/j.ccr.2011.01.032.
  12. Yeh, Gloria Y.; Eisenberg, David M.; Kaptchuk, Ted J.; Phillips, Russell S. (2003). "Systematic Review of Herbs and Dietary Supplements for Glycemic Control in Diabetes". Diabetes Care. 26 (4): 1277–1294. doi:10.2337/diacare.26.4.1277. PMID 12663610.
  13. Smith, D.M.; Pickering, R.M.; Lewith, G.T. (31 January 2008). "A systematic review of vanadium oral supplements for glycaemic control in type 2 diabetes mellitus". QJM. 101 (5): 351–358. doi:10.1093/qjmed/hcn003. PMID 18319296.
  14. Schwarz, Klaus; Milne, David B. (1971). "Growth Effects of Vanadium in the Rat". Science. 174 (4007): 426–428. Bibcode:1971Sci...174..426S. doi:10.1126/science.174.4007.426. JSTOR 1731776. PMID 5112000. S2CID 24362265.
  15. Talbott, Shawn M.; Hughes, Kerry (2007). "Vanadium". The Health Professional's Guide to Dietary Supplements. Lippincott Williams & Wilkins. pp. 419–422. ISBN 978-0-7817-4672-4.
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