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Titanium(IV) nitrate

January 01, 1970

Not to be confused with Titanium nitride.

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.

Titanium(IV) nitrate

Names
Other names
titanium tetranitrate, tetranitratotitanium
Identifiers
  • 12372-56-4 N
3D model (JSmol)
  • Interactive image
ChemSpider
  • 8123716 N
ECHA InfoCard 100.222.601
  • 139314
  • DTXSID50924580
  • InChI=1S/4NO3.Ti/c4*2-1(3)4;/q4*-1;+4
    Key: QDZRBIRIPNZRSG-UHFFFAOYSA-N
  • [Ti](O[N+]([O-])=O)(O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O
Properties
Ti(NO3)4
Molar mass 295.8866 g/mol
Appearance white volatile solid
Density 2.192[3]
Melting point 58[4] °C (136 °F; 331 K)
Boiling point decompose
Reacts[5]
Structure[6]
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).

Preparation edit

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 edit

The complex has D2d symmetry, with four bidentate nitrate ligands. The N-O distances are 1·29 Å and 1·185 Å (noncoordinated).[6]

Physical properties edit

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 edit

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]

References edit

  1. ^ 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.
  2. ^ "ICSD 26639 : ICSD Structure : N4 O12 Ti". Cambridge Structural Database: Access Structures. Cambridge Crystallographic Data Centre. Retrieved 2021-05-08.
  3. ^ "Titanium(iv) nitrate (Ti(NO3)4)". Retrieved 27 September 2014.
  4. ^ Chemistry of the Elements (Second Edition). N. N. Greenwood and A. Earnshaw. P966. 21.3.4 Compounds with oxoanions
  5. ^ 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.
  6. ^ a b 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.
  7. ^ 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.
  8. ^ a b 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.
  9. ^ P. Ehrlich "Titanium Tetranitrate" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1237.
  10. ^ Schmeisser, M.; Brandle, K. Acyl nitrates and perchlorates. IV. ClNO3 as starting material for acyl nitrates. Angewandte Chemie, 1957. 69: 781. ISSN: 0044-8249.
  11. ^ Wiberg, Egon; Wiberg, Nils (2001). Inorganic Chemistry. Academic Press. p. 1331. ISBN 9780123526519. Retrieved 28 September 2014.
  12. ^ 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.
  13. ^ 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.
  14. ^ a b 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.
  15. ^ a b 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.
  16. ^ Schofield, Kenneth (1980). Aromatic Nitration. CUP Archive. pp. 97–98. ISBN 9780521233620. Retrieved 27 September 2014.
  17. ^ 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 edit

  • 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.

January 01, 1970
titanium, nitrate, confused, with, titanium, nitride, titanium, nitrate, inorganic, compound, with, formula, colorless, diamagnetic, solid, that, sublimes, readily, unusual, example, volatile, binary, transition, metal, nitrate, defined, species, called, titan. Not to be confused with Titanium nitride 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 Titanium IV nitrate Ball and stick model 1 2 Names Other names titanium tetranitrate tetranitratotitanium Identifiers CAS Number 12372 56 4 N 3D model JSmol Interactive image ChemSpider 8123716 N ECHA InfoCard 100 222 601 PubChem CID 139314 CompTox Dashboard EPA DTXSID50924580 InChI InChI 1S 4NO3 Ti c4 2 1 3 4 q4 1 4Key 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 3 Melting point 58 4 C 136 F 331 K Boiling point decompose Solubility in water Reacts 5 Structure 6 Crystal structure monoclinic Space group P21 C Lattice constant a 7 80 b 13 57 c 10 34 Aa 90 b 125 0 g 90 Lattice volume V 896 52 A3 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 Contents 1 Preparation 2 Structure 3 Physical properties 4 Reactions 5 References 6 Other readingPreparation editSimilarly 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 editThe complex has D2d symmetry with four bidentate nitrate ligands The N O distances are 1 29 A and 1 185 A noncoordinated 6 Physical properties editIn 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 editTitanium 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 References edit 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 a b 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 Uber die Konstitution des N2O4 und N2O3 und die Additionsverbindungen von Nitro und Nitrosokorpern an Zinn und Titantetrachlorid Justus Liebig s Annalen der Chemie in German 452 1 47 67 doi 10 1002 jlac 19274520104 ISSN 0075 4617 a b 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 a b 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 a b 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 Other reading editPartington 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 Retrieved from https en wikipedia org w index php title Titanium IV nitrate amp oldid 1059532065, wikipedia, wiki, book, books, library,

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