Zirconium nitrate

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Zirconium nitrate
Zirconium(IV) nitrate pentahydrate.jpg
Pentahydrate
Names
Other names
zirconium tetranitrate, tetranitratozirconium, zirconium(4+) tetranitrate, zirconium(IV) nitrate
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.033.917 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/4NO3.Zr/c4*2-1(3)4;/q4*-1;+4
    Key: OERNJTNJEZOPIA-UHFFFAOYSA-N
  • [Zr+4].O=[N+]([O-])[O-].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O
Properties
Zr(NO3)4
Molar mass 339.243591 g/mol
Appearancetransparent plates
Melting point 58.5 °C [1]
Boiling point decompose 100 °C
water, ethanol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
oxidiser
Lethal dose or concentration (LD, LC):
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).

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.

Contents

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 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 Å3 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 Å3 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]

Related Research Articles

<span class="mw-page-title-main">Nitric acid</span> Highly corrosive mineral acid

Nitric acid is an inorganic compound with the formula HNO3. It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into oxides of nitrogen. Most commercially available nitric acid has a concentration of 68% in water. When the solution contains more than 86% HNO3, it is referred to as fuming nitric acid. Depending on the amount of nitrogen dioxide present, fuming nitric acid is further characterized as red fuming nitric acid at concentrations above 86%, or white fuming nitric acid at concentrations above 95%.

<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">Copper(II) nitrate</span> Chemical compound

Copper(II) nitrate describes any member of the family of inorganic compounds with the formula Cu(NO3)2(H2O)x. The hydrates are blue solids. Anhydrous copper nitrate forms blue-green crystals and sublimes in a vacuum at 150-200 °C. Common hydrates are the hemipentahydrate and trihydrate.

<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 contain only nitrogen and oxygen. It exists as colourless crystals that sublime slightly above room temperature, yielding a colorless gas.

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

Zinc nitrate is an inorganic chemical compound with the formula Zn(NO3)2. This colorless, crystalline salt is highly deliquescent. It is typically encountered as a hexahydrate Zn(NO3)2·6H2O. It is soluble in both water and alcohol.

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

Cadmium nitrate describes any of the related members of a family of inorganic compounds with the general formula Cd(NO3)2·xH2O. The most commonly encountered form being the tetrahydrate.The anhydrous form is volatile, but the others are colourless crystalline solids that are deliquescent, tending to absorb enough moisture from the air to form an aqueous solution. Like other cadmium compounds, cadmium nitrate is known to be carcinogenic. According to X-ray crystallography, the tetrahydrate features octahedral Cd2+ centers bound to six oxygen ligands.

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">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">Cerium nitrates</span> Chemical compound

Cerium nitrate refers to a family of nitrates of cerium in the +3 or +4 oxidation state. Often these compounds contain water, hydroxide, or hydronium ions in addition to cerium and nitrate. Double nitrates of cerium also exist.

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

Xenon fluoride nitrate, also known as fluoroxenonium nitrate, is the chemical compound with formula FXeONO2.

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

Thorium(IV) nitrate is a chemical compound, a salt of thorium and nitric acid with the formula Th(NO3)4. A white solid in its anhydrous form, it can form tetra- and pentahydrates. As a salt of thorium it is weakly radioactive.

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

Terbium(III) nitrate is an inorganic chemical compound, a salt of terbium and nitric acid, with the formula Tb(NO3)3. The hexahydrate crystallizes as triclinic colorless crystals with the formula [Tb(NO3)3(H2O)4]·2H2O. It can be used to synthesize materials with green emission.

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.

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

Tin(IV) nitrate is a salt of tin with nitric acid. It is a volatile white solid, subliming at 40 °C under a vacuum. Unlike other nitrates, it reacts with water to produce nitrogen dioxide.

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

Dysprosium(III) nitrate is an inorganic compound, a salt of dysprosium and nitric acid with the chemical formula Dy(NO3)3. The compound forms yellowish crystals, dissolves in water, forms a crystalline hydrate.

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

Thulium(III) nitrate is an inorganic compound, a salt of thulium and nitric acid with the chemical formula Tm(NO3)3. The compound forms dark-green crystals, readily soluble in water, also forms crystalline hydrates.

<span class="mw-page-title-main">Transition metal nitrate complex</span> Compound of nitrate ligands

A transition metal nitrate complex is a coordination compound containing one or more nitrate ligands. Such complexes are common starting reagents for the preparation of other compounds.

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

Zirconium selenate is an inorganic compound with the chemical formula Zr(SeO4)2. Its tetrahydrate can be obtained by the reaction of selenic acid and a saturated aqueous solution of zirconium oxychloride octahydrate (or zirconium hydroxide). The tetrahydrate belongs to the orthorhombic crystal system and is isostructural with Zr(SO4)2·4H2O. It loses water when heated and becomes anhydrous at 220-230 °C. It reacts with potassium fluoride to obtain K2Zr(SeO4)2F2·3H2O.

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. 1 2 3 4 5 6 7 8 9 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. 1 2 3 4 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.
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