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">Nitronium ion</span> Polyatomic 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">Nitrogen dioxide</span> Chemical compound with formula NO₂

Nitrogen dioxide is a chemical compound with the formula NO2. One of several nitrogen oxides, nitrogen dioxide is a reddish-brown gas. It is a paramagnetic, bent molecule with C2v point group symmetry. Industrially, NO2 is an intermediate in the synthesis of nitric acid, millions of tons of which are produced each year, primarily for the production of fertilizers.

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

Dinitrogen pentoxide is the chemical compound with the formula N2O5. It is one of the binary nitrogen oxides, a family of compounds that only contain nitrogen and oxygen. It exists as colourless crystals that sublime slightly above room temperature, yielding a colorless gas.

<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">Scandium nitrate</span> Chemical compound

Scandium(III) nitrate, Sc(NO3)3, is an ionic compound. It is an oxidizer, as all nitrates are. The salt is applied in optical coatings, catalysts, electronic ceramics and the laser industry.

<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.

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 common 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">Nickel(II) nitrate</span> Chemical compound

Nickel nitrate is the inorganic compound Ni(NO3)2 or any hydrate thereof. In the hexahydrate, the nitrate anions are not bonded to nickel. Other hydrates have also been reported: Ni(NO3)2.9H2O, Ni(NO3)2.4H2O, and Ni(NO3)2.2H2O.

<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

Nitrogen trioxide 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">Dinitrogen trioxide</span> Chemical compound

Dinitrogen trioxide is the inorganic compound with the formula N2O3. It is a nitrogen oxide. It forms upon mixing equal parts of nitric oxide and nitrogen dioxide and cooling the mixture below −21 °C (−6 °F):

<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">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; it ignites organic solvents on contact and explodes at temperatures above 80 °C.

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.

Barbara J. Finlayson-Pitts is a Canadian-American atmospheric chemist. She is a professor in the chemistry department at the University of California, Irvine and is the Director of AirUCI Institute. Finlayson-Pitts and James N. Pitts, Jr. are the authors of Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications (1999). She has been a member of the National Academy of Sciences since 2006 and is the laureate for the 2017 Garvan–Olin Medal. In 2016 she co-chaired the National Academy of Science report "The Future of Atmospheric Chemistry Research"

Indium(III) nitrate is a nitrate salt of indium which forms various hydrates. Only the pentahydrate has been crystallographically verified. Other hydrates are also reported in literature, such as the trihydrate.

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

Nitratoauric acid, hydrogen tetranitratoaurate, or simply called gold(III) nitrate is a crystalline gold compound that forms the trihydrate, HAu(NO3)4·3H2O or more correctly H5O2Au(NO3)4·H2O. This compound is an intermediate in the process of extracting gold. In older literature it is also known as aurinitric acid.

Rhenium trioxynitrate, also known as rhenium(VII) trioxide nitrate, is a chemical compound with the formula ReO3NO3. It is a white solid that readily hydrolyzes in moist air.

References

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  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. hdl: 11336/53374 . 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.[ permanent dead link ]
  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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