Vanadyl perchlorate

Vanadyl perchlorate or vanadyl triperchlorate is a golden yellow coloured liquid or crystalline compound of vanadium, oxygen and perchlorate group. The substance consists of molecules covalently bound and is quite volatile; it ignites organic solvents on contact and explodes at temperatures above 80 °C.[1]

Vanadyl perchlorate
Names
Other names
tripercloratooxovanadium
Identifiers
3D model (JSmol)
  • InChI=1S/3ClHO4.O.V/c3*2-1(3,4)5;;/h3*(H,2,3,4,5);;/q;;;;+3/p-3
    Key: XTDRROXTBUWEJW-UHFFFAOYSA-K
  • O=[V](OCl(=O)(=O)=O)(OCl(=O)(=O)=O)OCl(=O)(=O)=O
Properties
VO(ClO4)3
Molar mass 356.29 g/mol
Appearance golden yellow liquid or crystals.
Melting point 21-22 °C
Boiling point 33.5 °C in vacuum
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 oxidant
Related compounds
Related compounds
 niobium perchlorate, vanadyl nitrate, chromyl perchlorate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

Formation

Vanadyl perchlorate can be made by reacting vanadium pentoxide with dichlorine heptoxide at 5 °C. It is purified by distillation under a vacuum and recrystallisation at 21 °C.[1]

A solution of vanadium(V) perchlorate can be made by dissolving vanadium pentoxide in perchloric acid.[2]

The reaction of vanadium pentoxide and dichlorine hexoxide could produce VO(ClO4)3:[3]

2 V2O5 + 12 Cl2O6 → 4 VO(ClO4)3 + 12 ClO2 + 3 O2

Properties

It can react with vanadium oxychloride to form another vanadyl perchlorate (VO2ClO4): [3]

4 VO(ClO4)3 + 2 VOCl3 → 6 VO2ClO4 + 6 ClO2 + 3 Cl2 + 3 O2

Other perchlorates include pervanadyl perchlorate, also known as dioxovanadium perchlorate, which contains VO2+ ions,[4] vanadyl diperchlorate, oxovanadium perchlorate or vanadium(IV) perchlorate, and VO(ClO4)2, which dissolves in water.[5][6] Vanadic perchlorate, also known as vanadium(III) perchlorate solution in water, is a green-tinged blue colour, significantly different to most other V(III) solutions, which are complexed.[7]

References
  1. Fedoroff, Basil T; Sheffield, Oliver E. Encyclopedia of Explosives and Related Items Vol 10 of 10- U to Z, Page V5 (PDF). Vol. 10. p. 136.
  2. Kustin, Kenneth; Toppen, David L. (June 1973). "Reduction of vanadium(V) by L-ascorbic acid". Inorganic Chemistry. 12 (6): 1404–1407. doi:10.1021/ic50124a038.
  3. Schmeisser, Martin (1955). "Die Chemie der anorganischen Acylnitrate (ein Problem des Nitrylchlorids) und Acylperchlorate (ein Problem des Dichlorhexoxyds)". Angewandte Chemie. 67 (17–18): 493–501. Bibcode:1955AngCh..67..493S. doi:10.1002/ange.19550671708. ISSN 0044-8249.
  4. Ramsey, J. B.; Heldman, M. J. (July 1936). "Kinetics of the Trivalent Vanadium—Iodine Reaction". Journal of the American Chemical Society. 58 (7): 1153–1157. doi:10.1021/ja01298a026.
  5. Iannuzzi, Melanie M.; Rieger, Philip H. (December 1975). "Nature of vanadium(IV) in basic aqueous solution". Inorganic Chemistry. 14 (12): 2895–2899. doi:10.1021/ic50154a006.
  6. Wuethrich, K.; Connick, Robert E. (March 1967). "Nuclear magnetic resonance relaxation of oxygen-17 in aqueous solutions of vanadyl perchlorate and the rate of elimination of water molecules from the first coordination sphere". Inorganic Chemistry. 6 (3): 583–590. doi:10.1021/ic50049a035.
  7. Furman, Sydney C.; Garner, Clifford S. (April 1950). "Absorption Spectra of Vanadium(III) and Vanadium(IV) Ions in Complexing and Non-complexing Media". Journal of the American Chemical Society. 72 (4): 1785–1789. doi:10.1021/ja01160a105.
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