Zirconium nitrate

Zirconium nitrate is a volatile anhydrous transition metal nitrate salt of zirconium with formula Zr(NO₃)₄. It has alternate names of zirconium tetranitrate, or zirconium(IV) nitrate.

Zirconium nitrate

Pentahydrate
Names
Other names zirconium tetranitrate, tetranitratozirconium, zirconium(4+) tetranitrate, zirconium(IV) nitrate
Identifiers
CAS Number	13746-89-9 Y
3D model (JSmol)	Interactive image
ChemSpider	24459 N
ECHA InfoCard	100.033.917
PubChem CID	26251
UNII	L68X591SNQ Y
CompTox Dashboard (EPA)	DTXSID9049821
InChI InChI=1S/4NO3.Zr/c4*2-1(3)4;/q4*-1;+4 Key: OERNJTNJEZOPIA-UHFFFAOYSA-N
SMILES [Zr+4].O=[N+]([O-])[O-].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O
Properties
Chemical formula	Zr(NO3)4
Molar mass	339.243591 g/mol
Appearance	transparent plates
Melting point	58.5 °C[1]
Boiling point	decompose 100 °C
Solubility in water	water, ethanol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards	oxidiser
Lethal dose or concentration (LD, LC):
LCLo (lowest published)	500 mg/m3 (rat, 30 min)[2]
Related compounds
Related compounds	Zirconyl nitrate, hafnium nitrate, titanium nitrate, zirconium perchlorate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

It has a UN number of UN 2728^[3] and is class 5.1, meaning oxidising substance.^[4]

Formation

The anhydrous salt can be made from zirconium tetrachloride reacting with dinitrogen pentoxide.^[5]

ZrCl₄ + 4 N₂O₅ → Zr(NO₃)₄ + 4ClNO₂

The product can be purified by sublimation in a vacuum. A contaminating substance in this is nitronium pentanitratozirconate. (NO₂)Zr(NO₃)₅.^[5]

Zirconium nitrate pentahydrate Zr(NO₃)₄·5H₂O can be formed by dissolving zirconium dioxide in nitric acid and then evaporating the solution until it is dry. However it is easier to crystallise zirconyl nitrate trihydrate ZrO(NO₃)₂·3H₂O from such a solution.^[5]

Zirconium is highly resistant to nitric acid even in the presence of other impurities and high temperatures.^[6] So zirconium nitrate is not made by dissolving zirconium metal in nitric acid.

Properties

Zirconium nitrate pentahydrate dissolves easily in water and alcohol. It is acidic in aqueous solution, and a base such as ammonium hydroxide will cause zirconium hydroxide to precipitate. The pentahydrate crystals have a refractive index of 1.6.^[7]

Related substances

Related substances are zirconium nitrate complexes. Zr(NO₃)₃(H₂O)+3 has a tricapped trigonal prismatic structure, with the nitrates connected by two oxygen atoms each (bidentate).^[5] The pentanitrato complex Zr(NO₃)−5 has all the nitrate groups bidentate, and has a bicapped square antiprism shape.^[5]

NO₂[Zr(NO₃)₃·3H₂O]₂(NO₃)₃ crystallizes in the hexagonal system, space group P3c1, with unit cell dimensions a = 10.292 Å, b = 10.292 Å, c = 14.84 Å, volume 1632.2 ų with 2 formulae per unit cell, density = 2.181.^[5]

CsZr(NO₃)₅ crystallizes in the monoclinic system, space group P2₁/n, with unit cell dimensions a = 7.497 Å, b = 11.567 Å, c = 14.411 Å, β=96.01°, volume 1242.8 ų with 4 formulae per cell, density = 2.855.^[5]

(NH₄)Zr(NO₃)₅·HNO₃ crystallizes in the orthorhombic system, space group Pna2₁ with unit cell dimensions a=14.852 Å, b = 7.222 Å, c = 13.177 Å, volume 1413.6 Å³ with 4 formulae per cell, density = 2.267.^[5]

A mixed nitronium, nitrosonium pentanitratozirconate crystallizing in the tetragonal system also exists.^[5]

Use

Zirconium nitrate is manufactured by a number of chemical suppliers. It is used as a source of zirconium for other salts,^[7] as an analytical standard,^[7] or as a preservative.^[7] Zirconium nitrate^[8] and nitronium pentanitratozirconate can be used as chemical vapour deposition precursors as they are volatile, and decompose above 100 °C to form zirconia.^[9] At 95 °C, zirconium nitrate sublimes with a pressure of 0.2 mm of Hg and can be deposited as zirconium dioxide on silicon at 285 °C. It has the advantage in that it is a single source, meaning it does not have to be mixed with other materials like oxygen, and decomposes at a relatively low temperature, and does not contaminate the surface with other elements such as hydrogen or fluorine.^[10]

Zirconium free from hafnium is required for nuclear reactor construction. One way to achieve this is via a mixed aqueous solution of hafnium nitrate and zirconium nitrate, which can be separated by partitioning the zirconium into tributylphosphate dissolved in kerosene.^[11]

Zirconium nitrate can be used as a Lewis acid catalyst in the formation of N-substituted pyrroles.^[12]

Anhydrous zirconium nitrate can nitrate some organic aromatic compounds in an unusual way. Quinoline is nitrated to 3-nitroquinoline and 7-nitroquinoline. Pyridine is nitrated to 3-nitropyridine and 4-nitropyridine.^[13]

References

1. Brauer, Georg (1975). Handbuch der präparativen anorganischen Chemie (in German). Stuttgart: Enke. p. 1380. ISBN 3-432-87813-3.
2. "Zirconium compounds (as Zr)". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
3. "App A". The Code of Federal Regulations of the United States of America. U.S. Government Printing Office. 1988. p. 254.
4. Recommendations on the Transport of Dangerous Goods: Model Regulations. United Nations Publications. 2009. p. 430. ISBN 9789211391367.
5. Morozov, I. V.; A. A. Fedorova; D. V. Palamarchuk; S. I. Troyanov (2005). "Synthesis and crystal structures of zirconium(IV) nitrate complexes (NO2)[Zr(NO3)3(H2O)3]2(NO3) 3, Cs[Zr(NO3)5], and (NH4)[Zr(NO3)5](HNO3)". Russian Chemical Bulletin. 54 (1): 93–98. doi:10.1007/s11172-005-0222-7. ISSN 1066-5285. S2CID 97703681.
6. Wah Chang (10 September 2003). "Zirconium in Nitric Acid Applications" (PDF). Retrieved 13 October 2014.
7. Patnaik, Pradyot (2003). Handbook of inorganic chemicals. McGraw-Hill. p. 1000. ISBN 0070494398.
8. Fundamental Gas-phase and Surface Chemistry of Vapor-phase Deposition II and Process Control, Diagnostics and Modeling in Semiconductor Manufacturing IV: Proceedings of the International Symposium. The Electrochemical Society. 2001. p. 144. ISBN 9781566773195.
9. Nienow, Amanda M.; Jeffrey T. Roberts (2006). "Chemical Vapor Deposition of Zirconium Oxide on Aerosolized Silicon Nanoparticles". Chemistry of Materials. 18 (23): 5571–5577. doi:10.1021/cm060883e. ISSN 0897-4756.
10. Houssa, Michel (2003-12-01). High k Gate Dielectrics. CRC Press. pp. 73, 76–77. ISBN 9781420034141. Retrieved 17 October 2014.
11. Cox, R. P.; G. H. Beyer (23 December 1955). "Separation of Hafnium from Zirconium using Tributyl Phosphate". Retrieved 13 October 2014.
12. Hasaninejad, Alireza; Mohsen Shekouhy; Mohammad Reza Mohammadizadeh; Abdolkarim Zare (2012). "Zirconium nitrate: a reusable water tolerant Lewis acid catalyst for the synthesis of N-substituted pyrroles in aqueous media". RSC Advances. 2 (15): 6174. Bibcode:2012RSCAd...2.6174H. doi:10.1039/C2RA20294H. ISSN 2046-2069. registration required
13. Schofield, Kenneth (1980). Aromatic Nitration. CUP Archive. p. 97. ISBN 9780521233620. Retrieved 17 October 2014.