Zirconium nitrate

Last updated
Zirconium nitrate
Zirconium(IV) nitrate pentahydrate.jpg
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  °C
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) [1]
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 [2] and is class 5.1, meaning oxidising substance. [3]

Formation

The anhydrous salt can be made from zirconium tetrachloride reacting with dinitrogen pentoxide. [4]

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. [4]

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. [4]

Zirconium is highly resistant to nitric acid even in the presence of other impurities and high temperatures. [5] 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. [6]

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). [4] The pentanitrato complex Zr(NO3)−5 has all the nitrate groups bidentate, and has a bicapped square antiprism shape. [4]

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. [4]

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. [4]

(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. [4]

A mixed nitronium, nitrosonium pentanitratozirconate crystallizing in the tetragonal system also exists. [4]

Use

Zirconium nitrate is manufactured by a number of chemical suppliers. It is used as a source of zirconium for other salts, [6] as an analytical standard, [6] or as a preservative. [6] Zirconium nitrate [7] and nitronium pentanitratozirconate can be used as chemical vapour deposition precursors as they are volatile, and decompose above 100 °C to form zirconia. [8] 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. [9]

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. [10]

Zirconium nitrate can be used as a Lewis acid catalyst in the formation of N-substituted pyrroles. [11]

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. [12]

Related Research Articles

Nitric acid is the inorganic compound with the formula HNO3. It is a highly corrosive mineral acid. The compound is colorless, but older samples tend to be yellow cast 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%.

Zirconium Chemical element, symbol Zr and atomic number 40

Zirconium is a chemical element with the symbol Zr and atomic number 40. The name zirconium is taken from the name of the mineral zircon. The word is related to Persian zargun, the most important source of zirconium. It is a lustrous, grey-white, strong transition metal that closely resembles hafnium and, to a lesser extent, titanium. Zirconium is mainly used as a refractory and opacifier, although small amounts are used as an alloying agent for its strong resistance to corrosion. Zirconium forms a variety of inorganic and organometallic compounds such as zirconium dioxide and zirconocene dichloride, respectively. Five isotopes occur naturally, four of which are stable. Zirconium compounds have no known biological role.

Group 4 element Group of chemical elements

Group 4 is the second group of transition metals in the periodic table. It contains the four elements titanium (Ti), zirconium (Zr), hafnium (Hf), and rutherfordium (Rf). The group is also called the titanium group or titanium family after its lightest member.

Dinitrogen pentoxide 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.

Hafnium tetrachloride Chemical compound

Hafnium(IV) chloride is the inorganic compound with the formula HfCl4. This colourless solid is the precursor to most hafnium organometallic compounds. It has a variety of highly specialized applications, mainly in materials science and as a catalyst.

Zirconium carbide Chemical compound

Zirconium carbide (ZrC) is an extremely hard refractory ceramic material, commercially used in tool bits for cutting tools. It is usually processed by sintering.

Indium(III) sulfate (In2(SO4)3) is a sulfate salt of the metal indium. It is a sesquisulfate, meaning that the sulfate group occurs 11/2 times as much as the metal. It may be formed by the reaction of indium, its oxide, or its carbonate with sulfuric acid. An excess of strong acid is required, otherwise insoluble basic salts are formed. As a solid indium sulfate can be anhydrous, or take the form of a pentahydrate with five water molecules or a nonahydrate with nine molecules of water. Indium sulfate is used in the production of indium or indium containing substances. Indium sulfate also can be found in basic salts, acidic salts or double salts including indium alum.

Cadmium nitrate Chemical compound

Cadmium nitrate describes any of the related members of a family of inorganic compounds with the general formula , 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.

Palladium(II) nitrate Chemical compound

Palladium(II) nitrate is the inorganic compound with the formula Pd(NO3)2.(H2O)x where x = 0 or 2. The anhydrous and dihydrate are deliquescent solids. According to X-ray crystallography, both compounds feature square planar Pd(II) with unidentate nitrate ligands. The anhydrous compound, which is a coordination polymer, is yellow.

Zirconium(IV) sulfate Chemical compound

Zirconium(IV) sulfate is the name for a family of inorganic salts with the formula Zr(SO4)2(H2O)n where n = 0, 4, 5, 7. These species are related by the degree of hydration. They are white or colourless solids that are soluble in water.

Tetranitratoaluminate 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.

Cerium nitrates 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.

Titanium(IV) nitrate 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.

Zirconium perchlorate is a molecular substance containing zirconium and perchlorate groups with formula Zr(ClO4)4. Zr(ClO4)4 is a volatile crystalline product. It can be formed by reacting zirconium tetrachloride with dry perchloric acid at liquid nitrogen temperatures. Zr(ClO4)4 sublimes slowly in a vacuum at 70°C showing that the molecule is covalently bound rather than being ionic. The reaction also forms some zirconyl perchlorate (or zirconium oxyperchlorate) ZrO(ClO4)2 as even apparently pure perchloric acid is in equilibrium with dichlorine heptoxide, hydronium ions and perchlorate ions. This side product can be minimised by adding more dichlorine heptoxide or doing the reaction as cold as possible.

Thorium(IV) nitrate Chemical compound

Thorium(IV) nitrate is a chemical compound 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.

Terbium(III) nitrate 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.

Plutonium(IV) nitrate Chemical compound

Plutonium (IV) nitrate is an inorganic compound, a salt of plutonium and nitric acid with the chemical formula Pu(NO3)4. The compound dissolves in water and forms crystalline hydrates as dark green crystals.

Dysprosium(III) nitrate 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.

Holmium(III) nitrate Chemical compound

Holmium (III) nitrate is an inorganic compound, a salt of holmium and nitric acid with the chemical formula Ho(NO3)3. The compound forms yellowish crystals, dissolves in water, also forms crystalline hydrates.

Transition metal nitrate complex 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.

References

  1. ↑ "Zirconium compounds (as Zr)". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  2. ↑ "App A". The Code of Federal Regulations of the United States of America. U.S. Government Printing Office. 1988. p. 254.
  3. ↑ Recommendations on the Transport of Dangerous Goods: Model Regulations. United Nations Publications. 2009. p. 430. ISBN   9789211391367.
  4. 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.
  5. ↑ Wah Chang (10 September 2003). "Zirconium in Nitric Acid Applications" (PDF). Retrieved 13 October 2014.
  6. 1 2 3 4 Patnaik, Pradyot (2003). Handbook of inorganic chemicals. McGraw-Hill. p.  1000. ISBN   0070494398.
  7. ↑ 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.
  8. ↑ 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.
  9. ↑ Houssa, Michel (2003-12-01). High k Gate Dielectrics. CRC Press. pp. 73, 76–77. ISBN   9781420034141 . Retrieved 17 October 2014.
  10. ↑ Cox, R. P.; G. H. Beyer (23 December 1955). "Separation of Hafnium from Zirconium using Tributyl Phosphate" . Retrieved 13 October 2014.
  11. ↑ 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. doi:10.1039/C2RA20294H. ISSN   2046-2069. registration required
  12. ↑ Schofield, Kenneth (1980). Aromatic Nitration. CUP Archive. p. 97. ISBN   9780521233620 . Retrieved 17 October 2014.
Salts and covalent derivatives of the nitrate ion
HNO3 He
LiNO3 Be(NO3)2 B(NO
3)−
4 		RONO2 NO−
3
NH4NO3 		HOONO2 FNO3 Ne
NaNO3 Mg(NO3)2 Al(NO3)3 SiPS ClONO2 Ar
KNO3 Ca(NO3)2 Sc(NO3)3 Ti(NO3)4 VO(NO3)3 Cr(NO3)3 Mn(NO3)2 Fe(NO3)2
Fe(NO3)3 		Co(NO3)2
Co(NO3)3 		Ni(NO3)2 CuNO3
Cu(NO3)2 		Zn(NO3)2 Ga(NO3)3 GeAsSe BrNO3 Kr
RbNO3 Sr(NO3)2 Y(NO3)3 Zr(NO3)4 NbMoTc Ru(NO3)3 Rh(NO3)3 Pd(NO3)2
Pd(NO3)4 		AgNO3
Ag(NO3)2 		Cd(NO3)2 In(NO3)3 Sn(NO3)4 Sb(NO3)3 Te INO3 Xe(NO3)2
CsNO3 Ba(NO3)2   Hf(NO3)4 TaWReOsIr Pt(NO3)2
Pt(NO3)4 		Au(NO3)3 Hg2(NO3)2
Hg(NO3)2 		TlNO3
Tl(NO3)3 		Pb(NO3)2 Bi(NO3)3
BiO(NO3) 		Po(NO3)4 AtRn
FrNO3 Ra(NO3)2  RfDbSgBhHsMtDsRgCnNhFlMcLvTsOg
↓
La(NO3)3 Ce(NO3)3
Ce(NO3)4 		Pr(NO3)3 Nd(NO3)3 Pm(NO3)3 Sm(NO3)3 Eu(NO3)3 Gd(NO3)3 Tb(NO3)3 Dy(NO3)3 Ho(NO3)3 Er(NO3)3 Tm(NO3)3 Yb(NO3)3 Lu(NO3)3
Ac(NO3)3 Th(NO3)4 PaO2(NO3)3 UO2(NO3)2 Np(NO3)4 Pu(NO3)4 Am(NO3)3 Cm(NO3)3 Bk(NO3)3 CfEsFmMdNoLr
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