Vanadyl nitrate

Last updated
Vanadyl nitrate
VO(NO3)3Code420596.png
Names
Other names
trinitratooxovanadium
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/3NO3.O.V/c3*2-1(3)4;;/q3*-1;;+3
    Key: NRKQBMOGOKEWPX-UHFFFAOYSA-N
  • [V](O[N+]([O-])=O)(O[N+]([O-])=O)(O[N+]([O-])=O)=O
Properties
VO(NO3)3
Molar mass 252.953 g/mol
Appearanceyellow liquid.
Melting point 2 °C (36 °F; 275 K) [1]
Boiling point 86 to 91 °C (187 to 196 °F; 359 to 364 K) at 0.7mm Hg
Hydrolysis
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
oxidant
Related compounds
Related compounds
titanium nitrate, vanadyl perchlorate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

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. [2]

Contents

Production

It is made by soaking vanadium pentoxide in liquid dinitrogen pentoxide for durations around two days at room temperature. The yield for this method is about 85%. [3]

V2O5 + 3 N2O5 → 2 VO(NO3)3.

Purification can be achieved by vacuum distillation. [3]

Mononitratodioxovanadium (VO2NO3) is an intermediate in this synthesis. It is a brick red solid. [4] [5]

Vanadyl nitrate can also be made from vanadyl trichloride VOCl3 and dinitrogen pentoxide. [6]

Structure

VO(NO3)3 has a distorted pentagonal bipyramid shape with idealized Cs (mirror) symmetry. The vanadium oxygen bond (157.2 pm) is typical for vanadyl(V). Two nitrate groups in the pentagonal plane are bidentate (V-O distances range from 199 to 206 pm). The third nitrate spans the pentagonal plane (197 pm) to the position trans to oxo (223 pm). [7] [8]

Properties

Vanadyl nitrate dissolves in dichloromethane, nitromethane, carbon tetrachloride, and saturated hydrocarbons. [1] 1-Hexene, or other unsaturated hydrocarbons ignite upon contact with vanadyl nitrate. [3] [9] Upon contact with water, it irreversibly hydrolyzes, releasing nitric acid. [3] [10]

The ultraviolet spectrum of the liquid shows an absorption band peaking at 208 nm with a shoulder at 242 nm. At 55 °C the gaseous vanadyl nitrate has absorption bands also at 486, 582 and 658 nm in the visual light spectrum. [10] in the infrared region, liquid vanadyl nitrate absorbs at 1880, 1633, 1612, 1560, 1306, 1205, 1016, 996, 965, 895, 783, 632, 457, 357, 301, 283, 234, 193, 133, 93 and 59 cm−1. [10] Gaseous vanadyl nitrate has absorption bands at 775, 783, 786, 962.5, 994.4, 997.5, 1000.5, 1006.2, 1012, 1016.3, 1020, 1198, 1211, 1216.3, 1564, 1612, 1629, 1632, 1635, 1648 and 1888 cm−1. [2] Many of these bands are due to stretching in nitrogen–oxygen bonds, but 1016.3 cm−1 is due to the double vanadium–oxygen bond. 786 is due to out of phase wagging in N-O, and 775 is due to deformation in O-N=O in the mirror plane. [2]

Reactions

It is a nitrating agent for aromatic compounds. Reactions proceed at room temperature. Often dichloromethane is used as an inert solvent. [1] Nitrotoluene, methyl benzoate and benzoic acid are nitrated by prolonged exposure over a few days. [1] Benzonitrile does not react. [1] [11]

Vanadyl nitrate form a solid pale yellow adduct with boron trifluoride. [3] An adduct is also formed with acetonitrile. [1]


Related Research Articles

<span class="mw-page-title-main">Nitrogen</span> Chemical element, symbol N and atomic number 7

Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at seventh in total abundance in the Milky Way and the Solar System. At standard temperature and pressure, two atoms of the element bond to form N2, a colorless and odorless diatomic gas. N2 forms about 78% of Earth's atmosphere, making it the most abundant uncombined element. Nitrogen occurs in all organisms, primarily in amino acids (and thus proteins), in the nucleic acids (DNA and RNA) and in the energy transfer molecule adenosine triphosphate. The human body contains about 3% nitrogen by mass, the fourth most abundant element in the body after oxygen, carbon, and hydrogen. The nitrogen cycle describes the movement of the element from the air, into the biosphere and organic compounds, then back into the atmosphere.

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

The nitronium ion, [NO2]+, is a cation. It is an onium ion because its nitrogen atom has +1 charge, similar to ammonium ion [NH4]+. It is created by the removal of an electron from the paramagnetic nitrogen dioxide molecule NO2, or the protonation of nitric acid HNO3.

<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">Dinitrogen tetroxide</span> Chemical compound

Dinitrogen tetroxide, commonly referred to as nitrogen tetroxide (NTO), and occasionally (usually among ex-USSR/Russia rocket engineers) as amyl, is the chemical compound N2O4. It is a useful reagent in chemical synthesis. It forms an equilibrium mixture with nitrogen dioxide. Its molar mass is 92.011 g/mol.

Sulfur trioxide (alternative spelling sulphur trioxide, also known as nisso sulfan) is the chemical compound with the formula SO3. It has been described as "unquestionably the most important economically" sulfur oxide. It is prepared on an industrial scale as a precursor to sulfuric acid.

<span class="mw-page-title-main">Dinitrogen pentoxide</span> Chemical compound

Dinitrogen pentoxide is the chemical compound with the formula N2O5, also known as nitrogen pentoxide or nitric anhydride. It is one of the binary nitrogen oxides, a family of compounds that only contain nitrogen and oxygen. It exists as colourless crystals that melt at 41 °C. Its boiling point is 47 °C, and sublimes slightly above room temperature, yielding a colorless gas.

<span class="mw-page-title-main">Vanadium(V) oxide</span> Chemical compound

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">Arsenic pentoxide</span> Chemical compound

Arsenic pentoxide is the inorganic compound with the formula As2O5. This glassy, white, deliquescent solid is relatively unstable, consistent with the rarity of the As(V) oxidation state. More common, and far more important commercially, is arsenic(III) oxide (As2O3). All inorganic arsenic compounds are highly toxic and thus find only limited commercial applications.

<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">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".

The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.

<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.

<span class="mw-page-title-main">Nitrate radical</span> Chemical compound

Trioxidonitrogen(•) or nitrate radical is an oxide of nitrogen with formula NO
3
, consisting of three oxygen atoms covalently bound to a nitrogen atom. This highly unstable blue compound has not been isolated in pure form, but can be generated and observed as a short-lived component of gas, liquid, or solid systems.

<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.

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

Cobalt(III) nitrate is an inorganic compound with the chemical formula Co(NO3)3. It is a green, diamagnetic solid that sublimes at ambient temperature.

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

Tetranitratoaluminate is an anion of aluminium and nitrate groups with formula [Al(NO3)4] that can form salts called tetranitratoaluminates. It is unusual in being a nitrate complex of a light element.

<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">Vanadyl perchlorate</span> Chemical compound

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.

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.

References

  1. 1 2 3 4 5 6 Dove, Michael F. A.; Berthold Manz; John Montgomery; Gerald Pattenden; Simon A. Wood (1998). "Vanadium(V) Oxytrinitrate, VO(NO3)3. A Powerful Reagent for the Nitration of Aromatic Compounds at Room Temperature under Non-Acidic Conditions". Journal of the Chemical Society, Perkin Transactions 1 (10): 1589–1590. doi:10.1039/A801771I. ISSN   0300-922X.
  2. 1 2 3 Brandán, Silvia A.; C. Socolsky; Aida Ben Altabef (2009). "DFT Calculations of the Molecular Force Field of Vanadyl Nitrate, VO(NO3)3". Zeitschrift für anorganische und allgemeine Chemie. 635 (3): 582–592. doi:10.1002/zaac.200801244. ISSN   0044-2313.
  3. 1 2 3 4 5 Harris, Arlo D.; John C. Trebellas (26 April 1962). "AD296097 Experimental Studies of the Reactions of N2O5 with Metal Acid Anhydrides and BF3". Arlington Hall Station: Armed Services Technical Information Agency. Archived from the original on September 24, 2015. Retrieved 30 September 2014.
  4. Cotton, F. Albert; Wilkinson, Geoffrey (1966). Advanced Inorganic Chemistry A Comprehensive Text (5 ed.). John Wiley. p. 814.
  5. Pantonin, John A.; Albert K. Fischer; Edward A. Heintz (1960). "The preparation of mononitratodioxovanadium(V), VO2NO3". Journal of Inorganic and Nuclear Chemistry. 14 (1–2): 145–147. doi:10.1016/0022-1902(60)80220-5. ISSN   0022-1902.
  6. Schmeisser, Martin (1955). "Die Chemie der anorganischen Acylnitrate (ein Problem des Nitrylchlorids) und Acylperchlorate (ein Problem des Dichlorhexoxyds)". Angewandte Chemie (in German). 67 (17–18): 493–501. Bibcode:1955AngCh..67..493S. doi:10.1002/ange.19550671708. ISSN   0044-8249.
  7. Smart, Bruce A.; Heather E. Robertson; David W. H. Rankin; Eric G. Hope; Colin J. Marsden (1999). "What is the coordination number of vanadium in vanadyl nitrate, VO(NO3)3? A Study of its Molecular Structure in the Gas Phase by Electron Diffraction and ab initio calculations". Journal of the Chemical Society, Dalton Transactions (3): 473–478. doi:10.1039/A806710D. ISSN   0300-9246. (free download)
  8. Davidson, G. (2000-01-01). Spectroscopic Properties of Inorganic and Organometallic Compounds. Royal Society of Chemistry. pp. 516–517. ISBN   9780854044269 . Retrieved 30 September 2014.
  9. Fedoroff, Basil T; Sheffield, Oliver E. Encyclopedia of Explosives and Related Items Vol 10 of 10- U to Z. Vol. 10. p. V4.
  10. 1 2 3 Brandán, S.A.; A. Ben Altabef, E.L. Varetti; Varetti, E. L. (1995). "Vibrational and electronic spectra of vanadyl nitrate, VO(NO3)3". Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 51 (4): 669–675. Bibcode:1995AcSpA..51..669B. doi:10.1016/0584-8539(94)00154-4. ISSN   1386-1425.
  11. Aitken, R. Alan; Alajarin, Mateo; Allen, D. W.; Mikael Begtrup; Daniel Bellus; J. Berna-Canovas; H. Boeckemeier; Stefan Bräse; I.R. Butler; Jose Chiara; Henri-J. Cristau; I. Gorrell; D. Keck; Terence Kee; Carmen Lopez-Leonardo; T. Muller; Patrick J. Murphy; Patrick O'Leary; Beate Priewisch; L.K. Rasmussen; Karola Rück-Braun; Bjoern Schlummer; Andreas Schmidt; Paul James Stevenson; J.C. Tebby; David Virieux (2014-05-14). Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 31b: Arene-X (X=N, P). Georg Thieme Verlag. p. 1215. ISBN   9783131720719 . Retrieved 29 September 2014.

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