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Titanium tetrachloride
IUPAC name[hide] Titanium tetrachloride Systematic name[hide] Tetrachlorotitanium Other names[hide] Titanium(IV) chloride Identifiers 7550-45-0 24193 22615 231-441-9 1838 Titanium+tetrachloride XR1925000 Image 1 SMILES
CAS number PubChem ChemSpider EC number UN number MeSH RTECS number Jmol-3D images
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InChI [show]
Molecular formula Molar mass Appearance Odor Density Melting point Boiling point Solubility in water Solubility Vapor pressure Refractive index (nD) Viscosity Coordination geometry Molecular shape Dipole moment Std enthalpy of formation fHo298 Standard molar entropy So298 MSDS EU Index EU classification
C
Properties TiCl
4
189.679 g/mol Colourless liquid penetrating acid odor 1.726 g/cm3 -24.1 C, 249 K, -11 F 136.4 C, 410 K, 278 F Reacts soluble in ethanol, HCl 1.3 kPa (20 C) 1.61 (10.5 C) 827 Pa s Structure Tetragonal Tetrahedral 0D Thermochemistry 763 kJmol1[1] 355 Jmol1K1[1] Hazards MSDS 022-001-00-5
R-phrases S-phrases
NFPA 704
0 3 2
W
Related compounds Titanium(II) chloride Titanium(III) chloride
Hafnium(IV) chloride Related compounds Titanium(IV) bromide Titanium(IV) fluoride Titanium(IV) iodide Zirconium(IV) chloride (verify) (what is: / ?) Except where noted otherwise, data are given for materials in their standard state (at 25 C, 100 kPa) Infobox references
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 an unusual example of a metal halide that is highly volatile. Upon contact with humid air, it forms spectacular opaque clouds of titanium dioxide (TiO2) and hydrogen chloride (HCl). It is sometimes referred to as "tickle".[2] [3]
Contents
1 Properties and structure 2 Production 3 Applications o 3.1 Production of titanium metal o 3.2 Production of titanium dioxide o 3.3 Smoke screens 4 Chemical reactions o 4.1 Hydrolysis and related reactions o 4.2 Complexes with simple ligands o 4.3 Redox o 4.4 Organometallic chemistry o 4.5 Reagent in organic synthesis 5 Toxicity and safety considerations 6 References 7 General reading 8 External links
Ti4+ has a "closed" electronic shell, with the same number of electrons as the inert gas argon. The tetrahedral structure for TiCl4 is consistent with its description as a d0 metal center (Ti4+) surrounded by four identical ligands. This configuration leads to highly symmetrical structures, hence the tetrahedral shape of the molecule. TiCl4 adopts similar structures to TiBr4 and TiI4; the three compounds share many similarities. TiCl4 and TiBr4 react to give mixed halides TiCl4 -xBrx, where x = 0, 1, 2, 3, 4. Magnetic resonance measurements also indicate that halide exchange is also rapid between TiCl4 and VCl4.[4] TiCl4 is soluble in toluene and chlorocarbons, as are other non-polar species. Evidence exists that certain arenes form complexes of the type [(C6R6)TiCl3]+. TiCl4 reacts exothermically with donor solvents such as THF to give hexacoordinated adducts.[5] Bulkier ligands (L) give pentacoordinated adducts TiCl4L.
Production
TiCl4 is produced by the chloride process, which involves the reduction of titanium oxide ores, typically ilmenite (FeTiO3) with carbon under flowing chlorine at 900 C. Impurities are removed by distillation. 2 FeTiO3 + 7 Cl2 + 6 C 2 TiCl4 + 2 FeCl3 + 6 CO The coproduction of FeCl3 is undesirable, which has motivated the development of alternative technologies. Instead of directly using ilmenite, "rutile slag" is used. This material, an impure form of TiO2, is derived from ilmenite by removal of iron, either using carbon reduction or extraction with sulfuric acid. Crude TiCl4 contains a variety of other volatile halides, including vanadyl chloride (VOCl3), silicon tetrachloride (SiCl4), and tin tetrachloride (SnCl4), which must be separated.
Applications
Production of titanium metal
The world's supply of titanium metal, about 4M tons per year, is made from TiCl4. The conversion takes place by the reduction of the chloride with magnesium metal, and yields titanium metal and magnesium chloride. This procedure is the final step of the Kroll process: 2 Mg + TiCl4 2 MgCl2 + Ti Liquid sodium has also been used instead of magnesium as the reducing agent.
TiCl4 + 2 H2O TiO2 + 4 HCl In some cases, TiCl4 is oxidised directly with oxygen: TiCl4 + O2 TiO2 + 2 Cl2
Smoke screens
It has been used to produce smoke screens since it produces a heavy, white smoke that has little tendency to rise.[7]
Chemical reactions
Titanium tetrachloride is a versatile reagent that forms diverse derivatives including those illustrated below.
Redox
Reduction of TiCl4 with aluminium results in one-electron reduction. The trichloride (TiCl3) and tetrachloride have contrasting properties: the trichloride is a solid, being a coordination polymer, and is paramagnetic. When the reduction is conducted in THF solution, the Ti(III) product converts to the light-blue adduct TiCl3(thf)3.
Organometallic chemistry
Main article: Organotitanium compound The organometallic chemistry of titanium typically starts from TiCl4. An important reaction involves sodium cyclopentadienyl to give titanocene dichloride, TiCl2(C5H5)2. This compound and many of its derivatives are precursors to Ziegler-Natta catalysts. Tebbe's reagent, useful in organic chemistry, is an aluminium-containing derivative of titanocene that arises from the reaction of titanocene dichloride with trimethylaluminium. It is used for the "olefination" reactions. Arenes, such as C6(CH3)6 react to give the piano-stool complexes [Ti(C6R6)Cl3]+ (R = H, CH3; see figure above).[11] This reaction illustrates the high Lewis acidity of the TiCl3+ entity, which is generated by abstraction of chloride from TiCl4 by AlCl3.
Hazards posed by titanium tetrachloride generally arise from the release of hydrogen chloride (HCl). TiCl4 is a strong Lewis acid, exothermically forming adducts with even weak bases such as THF and explosively with water, releasing HCl.