Titanium nitrate

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.

Not to be confused with Titanium nitride.
Titanium nitrate
Names
Other names
titanium tetranitrate, tetranitratotitanium
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.222.601
Properties
Ti(NO3)4
Molar mass 295.8866 g/mol
Appearance white volatile solid
Density 2.192[1]
Melting point 58.5 °C (137.3 °F; 331.6 K)
Boiling point decompose
Soluble
Structure[2]
monoclinic
P21/C
a = 7.80, b = 13.57, c = 10.34 Å
α = 90°, β = 125·0°, γ = 90°
896.52 Å3
4
8
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

Preparation

Similarly to its original method,[3][4] Ti(NO3)4 is prepared by the nitration of titanium tetrachloride using dinitrogen pentoxide:[5]

TiCl4 + 4 N2O5 → Ti(NO3)4 + 4 ClNO2

A hydrated titanium nitrate is produced upon dissolution of titanium compounds in nitric acid.[6]

Structure

The complex has D2d symmetry, with four bidentate nitrate ligands. The N-O distances are 1·29 Å and 1·185 Å (noncoordinated).[2]

Physical properties

In the infrared spectrum, it absorbs strongly at 1635 cm−1, assigned to a N-O vibrational mode.[7]

It is soluble in nonpolar solvents silicon tetrachloride and carbon tetrachloride.[8][4]

Reactions

Titanium nitrate is hygroscopic, converting to ill-defined hydrates.[9] The anhydrous material is highly reactive, even toward hydrocarbons.[9] Titanium nitrate also reacts with n-dodecane,[10] p-dichlorobenzene, anisole, biphenyl,[10][11]

It decomposes thermally to titanium dioxide.[12]

References
  1. "Titanium(iv) nitrate (Ti(NO3)4)". Retrieved 27 September 2014.
  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.
  3. 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.
  4. 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.
  5. P. Ehrlich "Titanium Tetranitrate" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1237.
  6. Wiberg, Egon; Wiberg, Nils (2001). Inorganic Chemistry. Academic Press. p. 1331. ISBN 9780123526519. Retrieved 28 September 2014.
  7. C. C. Addison, N. Logan, S. C. Wallwork and C. D. Garner, "Structural Aspects of Coordinated Nitrate Groups" Quart. Rev., Chem. Soc., 1971, volume 25, 289-322. doi:10.1039/qr9712500289.
  8. 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.
  9. 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.
  10. 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.
  11. Schofield, Kenneth (1980). Aromatic Nitration. CUP Archive. pp. 97–98. ISBN 9780521233620. Retrieved 27 September 2014.
  12. 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.

Other reading
  • Partington, J. R.; A. L. Whynes (1949). "660. Reactions of nitrosyl chloride. Part II". Journal of the Chemical Society (Resumed): 3135. doi:10.1039/JR9490003135. ISSN 0368-1769.
  • Dauerman, L.; G.E. Salser (1973). "Mass spectra of covalent inorganic nitrates: copper(II) nitrate and titanium(IV) nitrate". Journal of Inorganic and Nuclear Chemistry. 35 (1): 304–306. doi:10.1016/0022-1902(73)80643-8. ISSN 0022-1902.
Salts and covalent derivatives of the nitrate ion
HNO3 He
LiNO3 Be(NO3)2 B(NO
3)−
4		 RONO2 NO−
3
NH4NO3		 O FNO3 Ne
NaNO3 Mg(NO3)2 Al(NO3)3 Si P S 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 Ge As Se Br Kr
RbNO3 Sr(NO3)2 Y(NO3)3 Zr(NO3)4 Nb Mo Tc Ru(NO3)3 Rh(NO3)3 Pd(NO3)2
Pd(NO3)4		 AgNO3
Ag(NO3)2		 Cd(NO3)2 In Sn Sb(NO3)3 Te I Xe(NO3)2
CsNO3 Ba(NO3)2   Hf Ta W Re Os Ir 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 At Rn
FrNO3 Ra(NO3)2   Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
↓
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 Cf Es Fm Md No Lr
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