Titanium(IV) nitrate

Titanium(IV) nitrate
	; Ball-and-stick model
Names
	Other names titanium tetranitrate, tetranitratotitanium
Identifiers
CAS Number	12372-56-4 ;
3D model (JSmol)	Interactive image ;
ChemSpider	8123716 ;
ECHA InfoCard	100.222.601
PubChem CID	139314 ;
CompTox Dashboard (EPA)	DTXSID50924580 ;
	InChI InChI=1S/4NO3.Ti/c42-1(3)4;/q4-1;+4 Key: QDZRBIRIPNZRSG-UHFFFAOYSA-N;
	SMILES [Ti](O[N+]([O-])=O)(O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O;
Properties
Chemical formula	Ti(NO3)4
Molar mass	295.8866 g/mol
Appearance	white volatile solid
Density	2.192
Melting point	58 °C (136 °F; 331 K)
Boiling point	decompose
Solubility in water	Reacts
Structure
Crystal structure	monoclinic
Space group	P21/C
Lattice constant	a = 7.80, b = 13.57, c = 10.34 Å α = 90°, β = 125·0°, γ = 90°
Lattice volume (V)	896.52 Å3
Formula units (Z)	4
Coordination geometry	8
Molecular shape	flattened tetrahedral
Related compounds
Related compounds	hafnium nitrate, zirconium nitrate, titanium phosphate, titanium perchlorate
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
	Infobox references

Last updated December 10, 2021

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.

Preparation

Similarly to its original method,^[7]^[8] Ti(NO₃)₄ is prepared by the nitration of titanium tetrachloride using dinitrogen pentoxide ^[9] or chlorine nitrate:^[10]

TiCl₄ + 4 N₂O₅ → Ti(NO₃)₄ + 4 ClNO₂

Hydrated titanium nitrate, the nitrate salt of the aquo complex [Ti(H₂O)₆]³⁺, is produced upon dissolution of titanium compounds in nitric acid.^[11]

Structure

The complex has D_2d symmetry, with four bidentate nitrate ligands. The N-O distances are 1·29 Å and 1·185 Å (noncoordinated).^[6]

Physical properties

In the infrared spectrum, it absorbs strongly at 1635 cm⁻¹, assigned to a N-O vibrational mode.^[12]

It is soluble in nonpolar solvents silicon tetrachloride and carbon tetrachloride.^[13]^[8]

Reactions

Titanium nitrate is hygroscopic, converting to ill-defined hydrates.^[14] The anhydrous material is highly reactive, even toward hydrocarbons.^[14] Titanium nitrate also reacts with n-dodecane,^[15] p-dichlorobenzene, anisole, biphenyl,^[15]^[16]

It decomposes thermally to titanium dioxide.^[17]

Related Research Articles

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 is blue-green crystals and sublimes in a vacuum at 150-200 °C. Common hydrates are the hemipentahydrate and trihydrate.

Titanium tetrachloride Inorganic chemical compound

Titanium tetrachloride is the inorganic compound with the formula TiCl₄. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl₄ is a volatile liquid. Upon contact with humid air, it forms spectacular opaque clouds of titanium dioxide (TiO₂) and hydrated hydrogen chloride. It is sometimes referred to as "tickle" or "tickle 4" due to the phonetic resemblance of its molecular formula (TiCl₄) to the word.

Tin(IV) chloride, also known as tin tetrachloride or stannic chloride, is an inorganic compound with the formula SnCl₄. It is a colorless hygroscopic liquid, which fumes on contact with air. It is used as a precursor to other tin compounds. It was first discovered by Andreas Libavius (1550–1616) and was known as spiritus fumans libavii.

Titanium(III) chloride is the inorganic compound with the formula TiCl₃. At least four distinct species have this formula; additionally hydrated derivatives are known. TiCl₃ is one of the most common halides of titanium and is an important catalyst for the manufacture of polyolefins.

Titanium tetraiodide is an inorganic compound with the formula TiI₄. It is a black volatile solid, first reported by Rudolph Weber in 1863. It is an intermediate in the van Arkel–de Boer process for the purification of titanium.

Titanium tetrabromide is the chemical compound with the formula TiBr₄. It is the most volatile transition metal bromide. The properties of TiBr₄ are an average of TiCl₄ and TiI₄. Some key properties of these four-coordinated Ti(IV) species are their high Lewis acidity and their high solubility in nonpolar organic solvents. TiBr₄ is diamagnetic, reflecting the d⁰ configuration of the metal centre.

Thorium(IV) chloride describes a family of inorganic compounds with the formula ThCl₄(H₂O)_n. Both the anhydrous and tetrahydrate (n = 4) forms are known. They are hygroscopic, water-soluble white solids.

Titanium tetrafluoride Chemical compound

Titanium(IV) fluoride is the inorganic compound with the formula TiF₄. It is a white hygroscopic solid. In contrast to the other tetrahalides of titanium, it adopts a polymeric structure. In common with the other tetrahalides, TiF₄ is a strong Lewis acid.

Titanium disilicide (TiSi₂) is an inorganic chemical compound of titanium and silicon.

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.

Titanium ethoxide is a chemical compound with the formula Ti₄(OCH₂CH₃)₁₆. It is a colorless liquid that is soluble in organic solvents but hydrolyzes readily. It is sold commercially as a colorless solution. Alkoxides of titanium(IV) and zirconium(IV) are used in organic synthesis and materials science. They adopt more complex structures than suggested by their empirical formulas.

Metal halides are compounds between metals and halogens. Some, such as sodium chloride are ionic, while others are covalently bonded. A few metal halides are discrete molecules, such as uranium hexafluoride, but most adopt polymeric structures, such as palladium chloride.

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.

Titanium perchlorate is a molecular compound of titanium and perchlorate groups with formula Ti(ClO₄)₄. Anhydrous titanium perchlorate decomposes explosively at 130°C and melts at 85°C with a slight decomposition. It can sublime in a vacuum as low as 70°C, and can form vapour at up to 120°. Titanium perchlorate is quite volatile. It has density 2.35. It decomposes to TiO₂, ClO₂ and dioxygen O₂ Also TiO(ClO₄)₂ is formed during decomposition.

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.

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.

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.

Difluorophosphate or difluorodioxophosphate or phosphorodifluoridate is an anion with formula PO^₂F⁻
₂. It has a single negative charge and resembles perchlorate (ClO⁻
₄) and monofluorosulfonate (SO₃F⁻) in shape and compounds. These ions are isoelectronic, along with tetrafluoroaluminate, phosphate, orthosilicate, and sulfate. It forms a series of compounds. The ion is toxic to mammals as it causes blockage to iodine uptake in the thyroid. However it is degraded in the body over several hours.

Transition metal chloride complex Coordination complex

In chemistry, a transition metal chloride complex is a coordination complex that consists of a transition metal coordinated to one or more chloride ligand. The class of complexes is extensive.

Neptunium(IV) nitrate is an inorganic compound, a salt of neptunium and nitric acid with the chemical formula Np(NO₃)₄. The compound forms gray crystals, dissolves in water, and forms crystal hydrates.

References

↑ Garner, C. D.; Wallwork, S. C. (1966). "The crystal structures of anhydrous nitrates and their complexes. Part III. Titanium(IV) nitrate". J. Chem. Soc. A : 1496–1500. doi:10.1039/J19660001496.
↑ "ICSD 26639 : ICSD Structure : N₄ O₁₂ Ti". Cambridge Structural Database: Access Structures. Cambridge Crystallographic Data Centre . Retrieved 2021-05-08.
↑ "Titanium(iv) nitrate (Ti(NO3)4)" . Retrieved 27 September 2014.
↑ Chemistry of the Elements (Second Edition). N. N. Greenwood and A. Earnshaw. P₉₆₆. 21.3.4 Compounds with oxoanions
↑ Nathaniel Howell Furman; R. J. Mundy; G. H. Morrison (1955). The Distribution of Uranyl Nitrate from Aqueous Solutions to Diethyl Ether. the University of Michigan: U.S. Atomic Energy Commission. Technical Information Service. p. 51.
1 2 Garner, C. David; Ian H. Hillier; Martyn F. Guest (1975). "Ab initio self-consistent field molecular-orbital calculation of the ground state of tetranitratotitanium(IV); comments on the reactivity of anhydrous metal nitrates". Journal of the Chemical Society, Dalton Transactions (19): 1934. doi:10.1039/DT9750001934. ISSN 0300-9246.
↑ Reihlen, Hans; Andreas Hake (1927). "Über die Konstitution des N2O4 und N2O3 und die Additionsverbindungen von Nitro- und Nitrosokörpern an Zinn- und Titantetrachlorid". Justus Liebig's Annalen der Chemie (in German). 452 (1): 47–67. doi:10.1002/jlac.19274520104. ISSN 0075-4617.
1 2 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.
↑ P. Ehrlich "Titanium Tetranitrate" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1237.
↑ Schmeisser, M.; Brandle, K. Acyl nitrates and perchlorates. IV. ClNO3 as starting material for acyl nitrates. Angewandte Chemie, 1957. 69: 781. ISSN: 0044-8249.
↑ Wiberg, Egon; Wiberg, Nils (2001). Inorganic Chemistry. Academic Press. p. 1331. ISBN 9780123526519 . Retrieved 28 September 2014.
↑ Addison, C. C.; Logan, N.; Wallwork, S. C.; Garner, C. D. (1971). "Structural Aspects of Co-ordinated Nitrate Groups". Quarterly Reviews, Chemical Society. 25 (2): 289. doi:10.1039/qr9712500289.
↑ Amos, D.W.; G.W. Flewett (1974). "Raman spectra of titanium (IV) and tin (IV) nitrates". Spectrochimica Acta Part A: Molecular Spectroscopy. 30 (2): 453–461. Bibcode:1974AcSpA..30..453A. doi:10.1016/0584-8539(74)80085-1. ISSN 0584-8539.
1 2 Amos, D.W.; D.A. Baines, G.W. Flewett (1973). "Nitration by titanium (IV) nitrate". Tetrahedron Letters. 14 (34): 3191–3194. doi:10.1016/S0040-4039(00)79808-X. ISSN 0040-4039.
1 2 Coombes, Robert G.; Leslie W. Russell (1974). "Nitration of aromatic compounds by tetranitratotitanium(IV) in carbon tetrachloride solution". Journal of the Chemical Society, Perkin Transactions 2 (7): 830. doi:10.1039/P29740000830. ISSN 0300-9580.
↑ Schofield, Kenneth (1980). Aromatic Nitration. CUP Archive. pp. 97–98. ISBN 9780521233620 . Retrieved 27 September 2014.
↑ Allendorf, Mark Donald (1999-01-01). "Titanium Oxide CVD from Titanium (IV) Nitrate ...". Proceedings of the Symposium on Fundamental Gas-Phase and Surface Chemistry of Vapor-Phase Materials Synthesis. The Electrochemical Society. pp. 395–397. ISBN 9781566772174 . Retrieved 27 September 2014.