Vanadyl nitrate: Difference between revisions
→Mononitratodioxovanadium: redist |
VO<sub>2</sub>NO<sub>3</sub> |
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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%.<ref name="Harris62"/> |
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%.<ref name="Harris62"/> |
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:V<sub>2</sub>O<sub>5</sub> + 3 N<sub>2</sub>O<sub>5</sub> → 2 VO(NO<sub>3</sub>)<sub>3</sub>. |
:V<sub>2</sub>O<sub>5</sub> + 3 N<sub>2</sub>O<sub>5</sub> → 2 VO(NO<sub>3</sub>)<sub>3</sub>. |
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Mononitratodioxovanadium (VO<sub>2</sub>NO<sub>3</sub>) is an intermediate in this synthesis. It is a brick red solid.<ref>{{cite book|last1=Cotton|first1=F. Albert|last2=Wilkinson|first2=Geoffrey|title=Advanced Inorganic Chemistry A Comprehensive Text|year=1966|publisher=John Wiley|page=814|edition=5}}</ref><ref name="Pantonin1960">{{cite journal|last=Pantonin|first=John A.|author2=Albert K. Fischer |author3=Edward A. Heintz |year=1960|title=The preparation of mononitratodioxovanadium(V), VO2NO3|journal=Journal of Inorganic and Nuclear Chemistry|volume=14|issue=1–2|pages=145–147|issn=0022-1902|doi=10.1016/0022-1902(60)80220-5}}</ref> |
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Vanadyl nitrate can also be made from vanadyl trichloride VOCl<sub>3</sub> and dinitrogen pentoxide.<ref name="Schmeisser1955">{{cite journal|last=Schmeisser|first=Martin|year=1955|title=Die Chemie der anorganischen Acylnitrate (ein Problem des Nitrylchlorids) und Acylperchlorate (ein Problem des Dichlorhexoxyds)|journal=Angewandte Chemie|volume=67|issue=17–18|pages=493–501|issn=0044-8249|doi=10.1002/ange.19550671708|language=de}}</ref> |
Vanadyl nitrate can also be made from vanadyl trichloride VOCl<sub>3</sub> and dinitrogen pentoxide.<ref name="Schmeisser1955">{{cite journal|last=Schmeisser|first=Martin|year=1955|title=Die Chemie der anorganischen Acylnitrate (ein Problem des Nitrylchlorids) und Acylperchlorate (ein Problem des Dichlorhexoxyds)|journal=Angewandte Chemie|volume=67|issue=17–18|pages=493–501|issn=0044-8249|doi=10.1002/ange.19550671708|language=de}}</ref> |
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==Properties== |
==Properties== |
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Vanadyl nitrate dissolves in dichloromethane, nitromethane, carbon tetrachloride, hydrocarbons.<ref name="Dove1998"/> It hydrolyzes, releasing [[nitric acid]].<ref name="Harris62">{{cite web|title=AD296097 Experimental Studies of the Reactions of N2O5 with Metal Acid Anhydrides and BF3|last=Harris|first=Arlo D.|author2=John C. Trebellas|date=26 April 1962|publisher=Armed Services Technical Information Agency|access-date=30 September 2014|location=Arlington Hall Station|url=http://www.dtic.mil/get-tr-doc/pdf?AD=AD0296037}}</ref> Nitric acid is formed as a result of the reaction with water.<ref name=Varetti>{{cite journal|last=Brandán|first=S.A.|author2=A. Ben Altabef, E.L. Varetti|year=1995|title=Vibrational and electronic spectra of vanadyl nitrate, VO(NO3)3|journal=Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy|volume=51|issue=4|pages=669–675|issn=1386-1425|doi=10.1016/0584-8539(94)00154-4|bibcode=1995AcSpA..51..669B|last3=Varetti|first3=E. L.}}</ref> |
Vanadyl nitrate dissolves in dichloromethane, nitromethane, carbon tetrachloride, and saturated hydrocarbons.<ref name="Dove1998"/> It hydrolyzes, releasing [[nitric acid]].<ref name="Harris62">{{cite web|title=AD296097 Experimental Studies of the Reactions of N2O5 with Metal Acid Anhydrides and BF3|last=Harris|first=Arlo D.|author2=John C. Trebellas|date=26 April 1962|publisher=Armed Services Technical Information Agency|access-date=30 September 2014|location=Arlington Hall Station|url=http://www.dtic.mil/get-tr-doc/pdf?AD=AD0296037}}</ref> Nitric acid is formed as a result of the reaction with water.<ref name=Varetti>{{cite journal|last=Brandán|first=S.A.|author2=A. Ben Altabef, E.L. Varetti|year=1995|title=Vibrational and electronic spectra of vanadyl nitrate, VO(NO3)3|journal=Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy|volume=51|issue=4|pages=669–675|issn=1386-1425|doi=10.1016/0584-8539(94)00154-4|bibcode=1995AcSpA..51..669B|last3=Varetti|first3=E. L.}}</ref> |
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1-Hexene, or other unsaturated hydrocarbons ignite upon contact with vanadyl nitrate.<ref name="Harris62"/><ref name=fed10>{{cite book|last1=Fedoroff|first1=Basil T|last2=Sheffield|first2=Oliver E |title=Encyclopedia of Explosives and Related Items Vol 10 of 10- U to Z|volume=10|page=V4|url=https://html1-f.scribdassets.com/5n1zz8vvr4sm3p8/images/136-c19277b6e3.jpg}}</ref> |
1-Hexene, or other unsaturated hydrocarbons ignite upon contact with vanadyl nitrate.<ref name="Harris62"/><ref name=fed10>{{cite book|last1=Fedoroff|first1=Basil T|last2=Sheffield|first2=Oliver E |title=Encyclopedia of Explosives and Related Items Vol 10 of 10- U to Z|volume=10|page=V4|url=https://html1-f.scribdassets.com/5n1zz8vvr4sm3p8/images/136-c19277b6e3.jpg}}</ref> |
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Revision as of 19:13, 25 August 2021
3Code420596.png)
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| Names | |
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| Other names
trinitratooxovanadium
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| Identifiers | |
3D model (JSmol)
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| ChemSpider | |
PubChem CID
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CompTox Dashboard (EPA)
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| Properties | |
| VO(NO3)3 | |
| Molar mass | 252.953 g/mol |
| Appearance | yellow 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 |
| water | |
| Hazards | |
| Occupational safety and health (OHS/OSH): | |
Main hazards
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oxidant |
| Related compounds | |
Related compounds
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titanium nitrate, vanadyl perchlorate |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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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]
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 achieve 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] It hydrolyzes, releasing nitric acid.[3] Nitric acid is formed as a result of the reaction with water.[9]
1-Hexene, or other unsaturated hydrocarbons ignite upon contact with vanadyl nitrate.[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.[9] 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.[9] 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 compounds
Hexammino-vanadium nitrate
Hexammino-vanadium nitrate V(NH3)6.(NO3)3 was claimed to be formed by reacting hexamino vanadium trichloride with nitric acid.[12] However doubt is cast on the existence of hexammino complexes of vanadium.[13]
Vanadyl (IV) nitrate
Vanadyl (IV) nitrate VO(NO3)2 is made from vanadyl sulfate and barium nitrate, or vanadyl chloride and silver nitrate. It forms a blue solution, but cannot be crystallized, instead forming vanadium pentoxide when evaporated. Another method to make it as green blue needles is via vanadium pentoxide, oxalic acid and dilute nitric acid at 90 °C, but the solid form is not confirmed.[10][14]
References
- ^ a b c d e f 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.
- ^ a b c 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.
- ^ a b c d e 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. Retrieved 30 September 2014.
- ^ Cotton, F. Albert; Wilkinson, Geoffrey (1966). Advanced Inorganic Chemistry A Comprehensive Text (5 ed.). John Wiley. p. 814.
- ^ 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.
- ^ 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. doi:10.1002/ange.19550671708. ISSN 0044-8249.
- ^ 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)
- ^ 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.
- ^ a b c 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.
- ^ a b Fedoroff, Basil T; Sheffield, Oliver E. Encyclopedia of Explosives and Related Items Vol 10 of 10- U to Z. Vol. 10. p. V4.
- ^ 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.
- ^ Meyer, Julius; Robert Backa (1924). "Zur Kenntnis des dreiwertigen Vanadins. I". Zeitschrift für anorganische und allgemeine Chemie. 135 (1): 177–193. doi:10.1002/zaac.19241350113. ISSN 0863-1786.
- ^ Cotton, F. Albert; Wilkinson, Geoffrey (1966). Advanced Inorganic Chemistry A Comprehensive Text (5 ed.). John Wiley. p. 817.
- ^ Honda, Kenichi (May 1964). "The Electrolytic Preparation of Vanadium(II) Developers". Bulletin of the Chemical Society of Japan. 37 (5): 723–730. doi:10.1246/bcsj.37.723. ISSN 1348-0634.
Other reading
- Gmelin, Syst No 48, Teil A & Teil B (Lieferung 1 & 2) (1967); Teil A (Lieferung 1) & Teil A (Lieferung 2) (1968);& Erganzungwerk (Band2)(1971)
- M. Schmeisser, "Chemical Abstracts", (1955), 49, 10873
- L. Bretherick, Ed, "Hazards in the Chemical Laboratory", Royal Society of Chemistry, London, Engl (1979), pg. 1160