Vanadyl perchlorate

Last updated
Vanadyl perchlorate
Vanadyl perchlorate.png
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
Appearancegolden 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).

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]

Contents

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]

Related Research Articles

<span class="mw-page-title-main">Vanadium</span> Chemical element, symbol V and atomic number 23

Vanadium is a chemical element with the 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.

<span class="mw-page-title-main">Perchloric acid</span> Chemical compound

Perchloric acid is a mineral acid with the formula HClO4. Usually found as an aqueous solution, this colorless compound is a stronger acid than sulfuric acid, nitric acid and hydrochloric acid. It is a powerful oxidizer when hot, but aqueous solutions up to approximately 70% by weight at room temperature are generally safe, only showing strong acid features and no oxidizing properties. Perchloric acid is useful for preparing perchlorate salts, especially ammonium perchlorate, an important rocket fuel component. Perchloric acid is dangerously corrosive and readily forms potentially explosive mixtures.

<span class="mw-page-title-main">Dichlorine heptoxide</span> Chemical compound

Dichlorine heptoxide is the chemical compound with the formula Cl2O7. This chlorine oxide is the anhydride of perchloric acid. It is produced by the careful distillation of perchloric acid in the presence of the dehydrating agent phosphorus pentoxide:

<span class="mw-page-title-main">Dichlorine monoxide</span> Chemical compound

Dichlorine monoxide is an inorganic compound with the molecular formula Cl2O. It was first synthesised in 1834 by Antoine Jérôme Balard, who along with Gay-Lussac also determined its composition. In older literature it is often referred to as chlorine monoxide, which can be a source of confusion as that name now refers to the ClO radical.

<span class="mw-page-title-main">Vanadium(V) oxide</span> Precursor to vanadium alloys and industrial catalyst

Vanadium(V) oxide (vanadia) is the inorganic compound with the formula V2O5. Commonly known as vanadium pentoxide, it is a brown/yellow solid, although when freshly precipitated from aqueous solution, its colour is deep orange. Because of its high oxidation state, it is both an amphoteric oxide and an oxidizing agent. From the industrial perspective, it is the most important compound of vanadium, being the principal precursor to alloys of vanadium and is a widely used industrial catalyst.

<span class="mw-page-title-main">Vanadate</span> Coordination complex of vanadium

In chemistry, a vanadate is an anionic coordination complex of vanadium. Often vanadate refers to oxoanions of vanadium, most of which exist in its highest oxidation state of +5. The complexes [V(CN)6]3− and [V2Cl9]3− are referred to as hexacyanovanadate(III) and nonachlorodivanadate(III), respectively.

<span class="mw-page-title-main">Vanadium oxytrichloride</span> Chemical compound

Vanadium oxytrichloride is the inorganic compound with the formula VOCl3. This yellow distillable liquid hydrolyzes readily in air. It is an oxidizing agent. It is used as a reagent in organic synthesis. Samples often appear red or orange owing to an impurity of vanadium tetrachloride.

<span class="mw-page-title-main">Ammonium metavanadate</span> Chemical compound

Ammonium metavanadate is the inorganic compound with the formula NH4VO3. It is a white salt, although samples are often yellow owing to impurities of V2O5. It is an important intermediate in the purification of vanadium.

<span class="mw-page-title-main">Vanadyl sulfate</span> Chemical compound

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".

<span class="mw-page-title-main">Vanadium compounds</span>

Vanadium compounds are compounds formed by the element vanadium (V). The chemistry of vanadium is noteworthy for the accessibility of the four adjacent oxidation states 2–5, whereas the chemistry of the other group 5 elements, niobium and tantalum, are somewhat more limited to the +5 oxidation state. In aqueous solution, vanadium forms metal aquo complexes of which the colours are lilac [V(H2O)6]2+, green [V(H2O)6]3+, blue [VO(H2O)5]2+, yellow-orange oxides [VO(H2O)5]3+, 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 VO2+ center.

<span class="mw-page-title-main">Vanadyl ion</span>

The vanadyl or oxovanadium(IV) cation, VO2+, is a functional group that is common in the coordination chemistry of vanadium. Complexes containing this functional group are characteristically blue and paramagnetic. A triple bond is proposed to exist between the V4+ and O2− centers. The description of the bonding in the vanadyl ion was central to the development of modern ligand-field theory.

Metal acetylacetonates are coordination complexes derived from the acetylacetonate anion (CH
3
COCHCOCH
3
) and metal ions, usually transition metals. The bidentate ligand acetylacetonate is often abbreviated acac. Typically both oxygen atoms bind to the metal to form a six-membered chelate ring. The simplest complexes have the formula M(acac)3 and M(acac)2. Mixed-ligand complexes, e.g. VO(acac)2, are also numerous. Variations of acetylacetonate have also been developed with myriad substituents in place of methyl (RCOCHCOR). Many such complexes are soluble in organic solvents, in contrast to the related metal halides. Because of these properties, acac complexes are sometimes used as catalyst precursors and reagents. Applications include their use as NMR "shift reagents" and as catalysts for organic synthesis, and precursors to industrial hydroformylation catalysts. C
5
H
7
O
2
in some cases also binds to metals through the central carbon atom; this bonding mode is more common for the third-row transition metals such as platinum(II) and iridium(III).

<span class="mw-page-title-main">Vanadyl acetylacetonate</span> Chemical compound

Vanadyl acetylacetonate is the chemical compound with the formula VO(acac)2, where acac is the conjugate base of acetylacetone. It is a blue-green solid that dissolves in polar organic solvents. The coordination complex consists of the vanadyl group, VO2+, bound to two acac ligands via the two oxygen atoms on each. Like other charge-neutral acetylacetonate complexes, it is not soluble in water.

A metal ion in aqueous solution or aqua ion is a cation, dissolved in water, of chemical formula [M(H2O)n]z+. The solvation number, n, determined by a variety of experimental methods is 4 for Li+ and Be2+ and 6 for most elements in periods 3 and 4 of the periodic table. Lanthanide and actinide aqua ions have higher solvation numbers (often 8 to 9), with the highest known being 11 for Ac3+. The strength of the bonds between the metal ion and water molecules in the primary solvation shell increases with the electrical charge, z, on the metal ion and decreases as its ionic radius, r, increases. Aqua ions are subject to hydrolysis. The logarithm of the first hydrolysis constant is proportional to z2/r for most aqua ions.

<span class="mw-page-title-main">Calcium perchlorate</span> Chemical compound

Calcium perchlorate is classified as a metal perchlorate salt with the molecular formula Ca(ClO4)2. It is an inorganic compound that is a yellow-white crystalline solid in appearance. As a strong oxidizing agent, it reacts with reducing agents when heated to generate heat and products that may be gaseous. Calcium perchlorate has been categorized as having explosive reactivity. Ca(ClO4)2 is a common chemical on the soil of planet Mars, counting for almost 1% of the Martian dust, by weight.

<span class="mw-page-title-main">Titanium(IV) nitrate</span> Chemical compound

Titanium nitrate is the inorganic compound with formula Ti(NO3)4. It is a colorless, diamagnetic solid that sublimes readily. It is an unusual example of a volatile binary transition metal nitrate. Ill defined species called titanium nitrate are produced upon dissolution of titanium or its oxides in nitric acid.

<span class="mw-page-title-main">Titanium perchlorate</span> Chemical compound

Titanium perchlorate is a molecular compound of titanium and perchlorate groups with formula Ti(ClO4)4. Anhydrous titanium perchlorate decomposes explosively at 130 °C and melts at 85 °C with a slight decomposition. It can sublime in a vacuum as low as 70 °C, and can form vapour at up to 120°. Titanium perchlorate is quite volatile. It has density 2.35. It decomposes to TiO2, ClO2 and dioxygen O2 Also TiO(ClO4)2 is formed during decomposition.

<span class="mw-page-title-main">Vanadyl nitrate</span> Chemical compound

Vanadyl nitrate, also called vanadium oxytrinitrate or vanadium oxynitrate is an inorganic compound of vanadium in the +5 oxidation state with nitrate ligands and oxygen. The formula is VO(NO3)3. It is a pale yellow viscous liquid.

Vanadium phosphates are inorganic compounds with the formula VOxPO4 as well related hydrates with the formula VOxPO4(H2O)n. Some of these compounds are used commercially as catalysts for oxidation reactions.

<span class="mw-page-title-main">Chlorine trifluoride oxide</span> Chemical compound

Chlorine oxide trifluoride or chlorine trifluoride oxide is a corrosive liquid molecular compound with formula ClOF3. It was developed secretly as a rocket fuel oxidiser.

References

  1. 1 2 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. 1 2 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.
HClO4 He
LiClO4 Be(ClO4)2 B(ClO4)4
B(ClO4)3
ROClO3 N(ClO4)3
NH4ClO4
NOClO4
H3OClO4 FClO4 Ne
NaClO4 Mg(ClO4)2 Al(ClO4)3
Al(ClO4)4
Al(ClO4)2−5
Al(ClO4)3−6
SiPS ClO4
ClOClO3
Cl2O7
Ar
KClO4 Ca(ClO4)2 Sc(ClO4)3 Ti(ClO4)4 VO(ClO4)3
VO2(ClO4)
Cr(ClO4)3 Mn(ClO4)2 Fe(ClO4)2
Fe(ClO4)3
Co(ClO4)2,
Co(ClO4)3
Ni(ClO4)2 Cu(ClO4)2 Zn(ClO4)2 Ga(ClO4)3 GeAsSeBrKr
RbClO4 Sr(ClO4)2 Y(ClO4)3 Zr(ClO4)4 Nb(ClO4)5 MoTcRu Rh(ClO4)3 Pd(ClO4)2 AgClO4 Cd(ClO4)2 In(ClO4)3 Sn(ClO4)4 Sb TeO(ClO4)2 IXe
CsClO4 Ba(ClO4)2   Lu(ClO4)3 Hf(ClO4)4 Ta(ClO4)5
TaO(ClO4)3
TaO2ClO4
WReOsIrPtAu Hg2(ClO4)2,
Hg(ClO4)2
Tl(ClO4),
Tl(ClO4)3
Pb(ClO4)2 Bi(ClO4)3 PoAtRn
FrClO4 Ra LrRfDbSgBhHsMtDsRgCnNhFlMcLvTsOg
La Ce(ClO4)x Pr(ClO4)3 Nd(ClO4)3 Pm Sm(ClO4)3 Eu(ClO4)3 Gd(ClO4)3 Tb(ClO4)3 Dy(ClO4)3 Ho(ClO4)3 Er(ClO4)3 Tm(ClO4)3 Yb(ClO4)3
Ac Th(ClO4)4 Pa UO2(ClO4)2 NpPuAmCmBkCfEsFmMdNo