Titanium tetrachloride
General
Systematic name	Titanium tetrachloride Titanium(IV) chloride
Molecular formula	TiCl4
Molar mass	189.71 g/mol
Appearance	colorless fuming liquid
CAS number	[7550-45-0] [1]
Properties
Density and phase	1.730 g/ml, liquid
Solubility in water	Decomposes
Melting point	-24 °C
Boiling point	136.4 °C
Viscosity	? cP at ? °C
Structure
Molecular shape	Tetrahedral
Dipole moment	zero
Thermodynamic data
Standard enthalpy of formation ΔfH°liquid	-804.16 kJ/mol
Standard molar entropy S°liquid	221.93 J·K−1·mol−1
Safety data
EU classification	Corrosive
R-phrases	R14, R34
S-phrases	S1/S2, S7/S8, S26, S36/S37/S39, S45
NFPA 704	Image File history File links Download high-resolution version (1084x1100, 252 KB) File links The following pages on the English Wikipedia link to this file (pages on other projects are not listed): Titanium tetrachloride ... IUPAC nomenclature is a system of naming chemical compounds and of describing the science of chemistry in general. ... A chemical formula (also called molecular formula) is a concise way of expressing information about the atoms that constitute a particular chemical compound. ... Molar mass is the mass of one mole of a chemical element or chemical compound. ... CAS registry numbers are unique numerical identifiers for chemical compounds, polymers, biological sequences, mixtures and alloys. ... Density (symbol: ρ - Greek: rho) is a measure of mass per volume. ... In the physical sciences, a phase is a set of states of a macroscopic physical system that have relatively uniform chemical composition and physical properties (i. ... It has been suggested that this article or section be merged with Solution. ... This article describes water from a scientific and technical perspective. ... The melting point of a solid is the temperature at which it changes state from solid to liquid. ... The boiling point of a substance is the temperature at which it can change its state from a liquid to a gas throughout the bulk of the liquid at a given pressure. ... The pitch drop experiment at the University of Queensland. ... The poise (P) is the cgs unit of viscosity, 1 P = 1 g·cm-1·s-1 The SI analog is 1 pascal second (Pa·s) = 1 kg·m-1·s-1 = 10 P. It is named after Jean Louis Marie Poiseuille. ... four sp³ orbitals three sp² orbitals In chemistry, hybridisation or hybridization (see also spelling differences) is the concept of mixing atomic orbitals to form new hybrid orbitals suitable for the qualitative description of atomic bonding properties. ... // The Earths magnetic field, which is approximately a dipole. ... The standard enthalpy of formation or standard heat of formation of a compound is the change of enthalpy that accompanies the formation of 1 mole of a substance in its standard state from its constituent elements in their standard states (the most stable form of the element at 1 atmosphere... In chemistry, the standard molar entropy is the entropy content of one mole of substance, under conditions of standard temperature and pressure. ... Council Directive 67/548/EEC of 27 June 1967 on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances (as amended) is the main source of European Union law concerning chemical safety. ... R-phrases are defined in Annex III of European Union Directive 67/548/EEC: Nature of special risks attributed to dangerous substances and preparations. ... S-phrases are defined in Annex IV of European Union Directive 67/548/EEC: Safety advice concerning dangerous substances and preparations. ... NFPA 704 is a standard maintained by the U.S. National Fire Protection Association. ... Image File history File links NFPA_704. ... 0 3 2 W
Supplementary data page
Structure and properties	n, εr, etc.
Thermodynamic data	Phase behaviour Solid, liquid, gas
Spectral data	UV, IR, NMR, MS
Related compounds
Other anions	Titanium(IV) fluoride Titanium(IV) bromide Titanium(IV) iodide
Other cations	Zirconium(IV) chloride Hafnium(IV) chloride
Related compounds	Titanium(II) chloride Titanium(III) chloride
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox disclaimer and references

Titanium tetrachloride (or titanium(IV) chloride) is the chemical compound with the formla TiCl₄. The refractive index (or index of refraction) of a material is the factor by which the phase velocity of electromagnetic radiation is slowed in that material, relative to its velocity in a vacuum. ... The dielectric constant εr (represented as or K in some cases) is defined as the ratio: where εs is the static permittivity of the material in question, and ε0 is the vacuum permittivity. ... Ultraviolet-Visible Spectroscopy or Ultraviolet-Visible Spectrophotometry (UV/ VIS) involves the spectroscopy of photons (spectrophotometry). ... IR spectrum of a thin film of liquid ethanol. ... Nuclear Magnetic Resonance Spectroscopy most commonly known as NMR Spectroscopy is the name given to the technique which exploits the magnetic properties of nuclei. ... Basic schematic of a mass spectrometer Mass spectrometry (also known as mass spectroscopy (deprecated)[1] or in common speech mass-spec) is an analytical technique used to measure the mass-to-charge ratio of ions. ... An ion is an atom or group of atoms that normally are electrically neutral and achieve their status as an ion by loss (or addition) of an electron(s). ... This article lacks information on the importance of the subject matter. ... Titanium tetrabromide is the chemical compound TiBr4. ... Titanium tetraiodide is TiI4. ... An ion is an atom or group of atoms that normally are electrically neutral and achieve their status as an ion by loss (or addition) of an electron(s). ... Zirconium(IV) chloride, also known as zirconium tetrachloride, is used for the preparation of metallic zirconium by the Kroll process. ... Hafnium(IV) chloride Used for the preparation of metallic hafnium by the Kroll process. ... Titanium(II) chloride is a black solid with the formula TiCl2. ... Titanium(III) chloride, TiCl3, is a red-violet salt that decomposes at 425 °C. Categories: | ... In chemistry, the standard state of a material is its state at 1 bar (100 kilopascals) and 25 degrees Celsius (298. ... General Name, Symbol, Number titanium, Ti, 22 Template:Elementbox s kewlio really eries Group, Period, Block 4, 4, d Appearance silvery metallic Atomic mass 47. ... The chloride ion is formed when the element chlorine picks up one electron to form an anion (negatively-charged ion) Cl−. The salts of hydrochloric acid HCl contain chloride ions and are also called chlorides. ... A chemical compound is a chemical substance consisting of two or more different chemically bonded chemical elements, with a fixed ratio determining the composition. ... A chemical formula (also called molecular formula) is a concise way of expressing information about the atoms that constitute a particular chemical compound. ...

TiCl₄ is an important intermediate in the production of titanium and other titanium compounds. It is an unusual example of a liquid metal halide that is very volatile in air. TiCl₄ is often light-heartedly referred to as "tickle" or "tickle-four" by those that frequently use it. A liquid will usually assume the shape of its container. ... Metal halide lamps are similar to mercury vapor lamps, but instead of just mercury, they also contain all metals in the halide group of the periodic table (Hence the name). ... Volatile is the name of more than one concept: A financial instrument with high volatility is considered volatile in economics. ...

Properties and structure

TiCl₄ is a dense, colourless distillable liquid, although crude samples may be yellow or even red-brown. It is one of the rare transition metal chlorides that is in liquid state at room temperature, VCl₄ being another example. This distinctive property arises from the fact that TiCl₄ is molecular; that is, each TiCl₄ molecule is relatively weakly associated with its neighbors. Most metal chlorides are polymers, where the chloride atoms bridge between the metals. The attraction between the individual TiCl₄ molecules is weak, primarily van der Waals forces, and these weak interactions result in low melting and boiling points, similar to those of CCl₄. Laboratory distillation set-up using, without a fractionating column 1: Heat source 2: Still pot 3: Still head 4: Thermometer/Boiling point temperature 5: Condenser 6: Cooling water in 7: Cooling water out 8: Distillate/receiving flask 9: Vacuum/gas inlet 10: Still receiver 11: Heat control 12: Stirrer speed... Vanadium tetrachloride is the chemical compound with the formula VCl4. ... Polymer is a term used to describe large molecules consisting of repeating structural units, or monomers, connected by covalent chemical bonds. ... The title given to this article is incorrect due to technical limitations. ... The melting point of a solid is the temperature at which it changes state from solid to liquid. ... The boiling point of a substance is the temperature at which it can change its state from a liquid to a gas throughout the bulk of the liquid at a given pressure. ... Carbon tetrachloride, also known by other names (see Table) is the chemical compound CCl4. ...

TiCl₄ is tetrahedral, which is consistent with its description as Ti⁴⁺ surrounded by four Cl^- ligands. Ti⁴⁺ has a "closed" electronic shell, with the same number of electrons as the inert gas argon. This configuration leads to highly symmetrical structures, hence the tetrahedral shape of the molecule. A tetrahedron (plural: tetrahedra) is a polyhedron composed of four triangular faces, three of which meet at each vertex. ... An inert gas is any gas that is not reactive under normal circumstances. ... General Name, Symbol, Number argon, Ar, 18 Chemical series noble gases Group, Period, Block 18, 3, p Appearance colorless Atomic mass 39. ... Sphere symmetry group o. ...

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.^[1] Bulkier ligands (L) give pentacoordinated derivatives TiCl₄L. Toluene, also known as methylbenzene or phenylmethane is a clear, water-insoluble liquid with the typical smell of paint thinners, reminiscent of the sweet smell of the related compound benzene. ... It has been suggested that this article or section be merged into Chlorinated_hydrocarbon. ... The polarity of an object is, in general, its physical alignment of atoms. ... Arene or Ar means several things: Another term for aromatic hydrocarbon In Greek mythology, Arene was the wife of Aphareus and mother of Idas and Lynceus. ... Exothermic means to release energy in the form of heat. ... A solvent is a fluid phase (liquid, gas, or plasma) that dissolves a solid, liquid, or gaseous solute, resulting in a solution. ... Tetrahydrofuran, also known as THF, hydrofuran, oxolane, oxacyclopentane, or furanidine, is a heterocyclic organic compound. ... Wikipedia does not yet have an article with this exact name. ... In chemistry, a ligand is an atom, ion, or molecule (see also: functional group) that generally donates one or more of its electrons through a coordinate covalent bond to, or shares its electrons through a covalent bond with, one or more central atoms or ions (these ligands act as a...

The main problem with handling TiCl₄, aside from its tendency to release corrosive hydrogen chloride, is the formation of titanium oxides and oxychlorides that cement stoppers and syringes. R-phrases , S-phrases , , , , Flash point non-flammable Supplementary data page Structure and properties n, εr, etc. ... Titanium dioxide, also known as titanium(IV) oxide or titania, is the naturally occurring oxide of titanium, chemical formula TiO2. ... The term stopper may refer to one of the following Stopper, a type of a knot at the end of the rope Stopper, a plug or a bung. ... A syringe consists of a plunger fitted to a tube, called the barrel, which has a small opening on one end. ...

Production

TiCl₄ is produced by the Kroll process, which involves the reduction of titanium oxide ores, typically ilmenite or rutile, with carbon under flowing chlorine at 900 °C. Impurities are removed by distillation to afford pure TiCl₄. The Kroll process is a pyrometallurgical industrial process used produce metallic titanium and was invented in 1940 by William J. Kroll, at the Albany Research center in Oregon. ... Semi-accurate illustration of a redox reaction Redox reactions include all chemical processes in which atoms have their oxidation number (oxidation state) changed. ... Ilmenite (FeTiO3) is a weakly magnetic iron-black or steel-gray mineral found in metamorphic and plutonic igneous rocks. ... Rutile in trellis texture characteristic of secondary rutile. ... General Name, Symbol, Number carbon, C, 6 Chemical series nonmetals Group, Period, Block 14, 2, p Appearance black (graphite) colorless (diamond) Atomic mass 12. ... General Name, Symbol, Number chlorine, Cl, 17 Chemical series halogens Group, Period, Block 17, 3, p Appearance yellowish green Atomic mass 35. ... Laboratory distillation set-up using, without a fractionating column 1: Heat source 2: Still pot 3: Still head 4: Thermometer/Boiling point temperature 5: Condenser 6: Cooling water in 7: Cooling water out 8: Distillate/receiving flask 9: Vacuum/gas inlet 10: Still receiver 11: Heat control 12: Stirrer speed...

2 FeTiO₃ + 7 Cl₂ + 6 C → 2 TiCl₄ + 2 FeCl₃ + 6 CO Ilmenite (FeTiO3) is a weakly magnetic iron-black or steel-gray mineral found in metamorphic and plutonic igneous rocks. ... General Name, Symbol, Number chlorine, Cl, 17 Chemical series halogens Group, Period, Block 17, 3, p Appearance yellowish green Atomic mass 35. ... General Name, Symbol, Number carbon, C, 6 Chemical series nonmetals Group, Period, Block 14, 2, p Appearance black (graphite) colorless (diamond) Atomic mass 12. ... Iron(III) chloride, generically called ferric chloride, is an iron-based salt of chemical formula FeCl3. ... Carbon monoxide,with the chemical formula CO, is a colourless, odourless and tasteless gas. ...

TiCl₄ is inexpensive, thus it is typically purchased for laboratory operations.

Applications

Production of titanium metal

TiO₂ + 2Cl₂ + C → TiCl₄ + 2 CO

Reduction of TiCl₄ using magnesium metal produces titanium metal; this is in fact the final step of the Kroll process. Titanium dioxide, also known as titanium(IV) oxide or titania, is the naturally occurring oxide of titanium, chemical formula TiO2. ... General Name, Symbol, Number chlorine, Cl, 17 Chemical series halogens Group, Period, Block 17, 3, p Appearance yellowish green Atomic mass 35. ... General Name, Symbol, Number magnesium, Mg, 12 Chemical series alkaline earth metals Group, Period, Block 2, 3, s Appearance silvery white Atomic mass 24. ...

2Mg + TiCl₄ → 2 MgCl₂(l) + Ti

General Name, Symbol, Number magnesium, Mg, 12 Chemical series alkaline earth metals Group, Period, Block 2, 3, s Appearance silvery white Atomic mass 24. ... Magnesium chloride is composed of magnesium and chlorine and is a typical ionic halide, being highly polar and soluble in water. ...

Production of titanium dioxide

Around 90% of the TiCl₄ production is used to make pigment; titanium(IV) oxide (TiO₂). Key is the reaction of TiCl₄ with water to form hydrochloric acid: TiCl₄ + 2 H₂O → TiO₂ + 4 HCl Titanium dioxide, also known as titanium(IV) oxide or titania, is the naturally occurring oxide of titanium, chemical formula TiO2. ... The chemical compound hydrochloric acid is the aqueous (water-based) solution of hydrogen chloride (HCl) gas. ... This article describes water from a scientific and technical perspective. ...

Smoke-screens

In the past titanium tetrachloride has also been used to create naval smokescreens. When sprayed into the air, TiCl₄ rapidly reacts with atmospheric moisture: A U.S. Army Humvee laying a smoke screen A smoke-screen is a release of smoke in order to mask the movement or location of military units such as infantry, tanks or ships. ...

TiCl₄ + 2 H₂O → TiO₂ + 4 HCl

The hydrogen chloride immediately absorbs more water to form tiny droplets of hydrochloric acid, which (depending on humidity) may absorb still more water, to produce large droplets that efficiently scatter light. In addition, the intensely white titanium dioxide is also an efficient light scatterer. Due to the corrosiveness of this smoke, however, TiCl₄ is no longer used. This article describes water from a scientific and technical perspective. ... The chemical compound hydrochloric acid is the aqueous (water-based) solution of hydrogen chloride (HCl) gas. ...

Chemical reactions

Organometallic and inorganic chemistry

TiCl₄ adopts similar structures to TiBr₄ and TiI₄; the three compounds share many similarities. TiCl₄ and TiBr₄ react to give mixed halides TiCl_4-xBr_x, where x = 0, 1, 2, 3, 4. Magnetic resonance measurements also indicate that halide exchange is also rapid between TiCl₄ and VCl₄.^[2] Titanium tetrabromide is the chemical compound TiBr4. ... Titanium tetraiodide is TiI4. ...

TiCl₄ is a superb and versatile Lewis acid, as indicated by its tendency to hydrolyze, which implicates the intermediacy of TiCl₄(H₂O). With THF, TiCl₄ forms yellow crystals of TiCl₄(THF)₂. With Cl^- donors, TiCl₄ reacts to form sequentially [Ti₂Cl₉]^-, [Ti₂Cl₁₀]^2-, and [TiCl₆]^2-.^[3] Interestingly, the reaction of chloride ions with TiCl₄ depends on the counterion. NBu₄Cl reacts with TiCl₄ to give the pentacoordinate complex NBu₄TiCl₅, whereas smaller NEt₄ reacts to give (NEt₄)₂Ti₂Cl₁₀. These reactions highlight the influence of electrostatic forces on the structures of compounds with highly ionic bonding. In chemistry, a Lewis acid can accept a pair of electrons and form a coordinate covalent bond, after the American chemist Gilbert Lewis. ...

Much of the extensive organometallic chemistry of titanium starts from TiCl₄. Its most important reaction is with sodium cyclopentadienyl to give titanocene dichloride, TiCl₂(C₅H₅)₂. This compound is used in organic synthesis (Tebbe's reagent). Arenes, such as C₆(CH₃)₆ reacts to give [Ti(C₆(CH₃)₆)Cl₃]⁺, which is a piano-stool complex.^[4] This reaction illustrates the extraordinary Lewis acidity of the TiCl₃⁺ entity, which is derived from TiCl₄ using the even stronger chloride-abstracting agent AlCl₃. It has been suggested that Organometallic compounds be merged into this article or section. ... Cyclopentadiene, with molecular formula C5H6, is a clear, colorless, liquid organic chemical, with an odor reminiscent of turpentine or camphor. ... The Tebbe reagent is (C5H5)2TiCH2ClAl(CH3)2. ... Space-filling model of ferrocene, the archetypal sandwich compound A sandwich compound in organometallic chemistry is any chemical compound containing a metal atom sandwiched between two arene units. ...

TiCl₄ reacts with four equivalents LiNMe₂ to give Ti(NMe₂)₄, a yellow, benzene-soluble liquid.^[5] This molecule is tetrahedral, with planar nitrogen centers.^[6]

Reagent in organic synthesis

It is widely used in organic synthesis as a Lewis acid,^[7] for example in the Mukaiyama aldol condensation. Key to this application is the tendency of TiCl₄ to interact with aldehydes, RCHO, to give adducts such (RCHO)TiCl₄OC(H)R. It is also used in the McMurry reaction in conjunction with Zn, LiAlH₄, or another reducing agent in order to join two carbonyls in making a carbon-carbon double bond. Organic synthesis is the construction of organic molecules via chemical processes. ... In chemistry, a Lewis acid can accept a pair of electrons and form a coordinate covalent bond, after the American chemist Gilbert Lewis. ... Wikipedia does not yet have an article with this exact name. ... The McMurry reaction of benzophenone The McMurry reaction is an organic reaction in which two ketone or aldehyde groups are coupled to an alkene in the presence of a titanium chloride compound such as titanium(III) trichloride and a reducing agent . ...

Olefin polymerisation

This compound and many of its derivatives are important precursors to Ziegler-Natta catalysts. A Ziegler-Natta catalyst is a reagent used in the production of unbranched, stereoregular vinyl polymers. ...

Reduction

Reduction of TiCl₄ yields TiCl₃. E.g. reduction of TiCl₄ with aluminium in THF results in the light-blue THF-adduct TiCl₃(THF)₃. Titanium(III) chloride, TiCl3, is a red-violet salt that decomposes at 425 °C. Categories: | ... Tetrahydrofuran, also known as THF, hydrofuran, oxolane, oxacyclopentane, or furanidine, is a heterocyclic organic compound. ...

Toxicity and safety considerations

Given the tendency of TiCl₄ to hydrolyze, the hazards generally arise from the effect of hydrogen chloride. TiCl₄ is a strong Lewis acid, exothermically forming adducts with even weak bases such as THF and explosively with water, again releasing HCl. R-phrases , S-phrases , , , , Flash point non-flammable Supplementary data page Structure and properties n, εr, etc. ... In chemistry, a Lewis acid can accept a pair of electrons and form a coordinate covalent bond, after the American chemist Gilbert Lewis. ... Tetrahydrofuran, also known as THF, hydrofuran, oxolane, oxacyclopentane, or furanidine, is a heterocyclic organic compound. ...

References

1. ^ L. E. Manzer (1982). "Tetrahydrofuran Complexes of Selected Early Transition Metals". Inorganic Synthesis 21: 135-40.
2. ^ S. P. Webb, M. S. Gordon (1999). "Intermolecular Self-Interactions of the Titanium Tetrahalides TiX4 (X = F, Cl, Br)". Journal of the American Chemical Society 121: 2552-2560. DOI:S0002-7863(98)03339-3 0.1021/ja983339i S0002-7863(98)03339-3.
3. ^ C. S. Creaser , J. A. Creighton (1975). "Pentachloro- and Pentabromotitanate(IV) ions". Journal of the Chemical Society, Dalton Transactions: 1402-1405. DOI:10.1039/DT9750001402.
4. ^ F. Calderazzo, I. Ferri, G. Pampaloni, S. Troyanov (1996). "η⁶-Arene Derivatives of Titanium(IV), Zirconium(IV) and Hafnium(IV)". Journal of Organometallic Chemistry 518: 189-196. DOI:10.1016/0022-328X(96)06194-3.
5. ^ D. C. Bradey, M. Thomas (1960). "Some Dialkylamino-derivatives of Titanium and Zirconium". Journal of the Chemical Society: 3857-3861. DOI:10.1039/JR9600003857.
6. ^ M. E. Davie, T. Foerster, S. Parsons, C. Pulham, D. W. H. Rankin, B. A. Smart (2006). "The Crystal Structure of Tetrakis(dimethylamino)titanium(IV)". Polyhedron 25: 923-929. DOI:10.1016/j.poly.2005.10.019.
7. ^ L.-L. Gundersen, F. Rise, K. Undheim (2004). “Titanium(IV) chloride”, Encyclopedia of Reagents for Organic Synthesis, L. Paquette, J. Wiley & Sons.

A digital object identifier (or DOI) is a permanent identifier (permalink) given to a World Wide Web file or other Internet document so that if its Internet address changes, users will be redirected to its new address. ... A digital object identifier (or DOI) is a permanent identifier (permalink) given to a World Wide Web file or other Internet document so that if its Internet address changes, users will be redirected to its new address. ... A digital object identifier (or DOI) is a permanent identifier (permalink) given to a World Wide Web file or other Internet document so that if its Internet address changes, users will be redirected to its new address. ... A digital object identifier (or DOI) is a permanent identifier (permalink) given to a World Wide Web file or other Internet document so that if its Internet address changes, users will be redirected to its new address. ... A digital object identifier (or DOI) is a permanent identifier (permalink) given to a World Wide Web file or other Internet document so that if its Internet address changes, users will be redirected to its new address. ...

General reading

• Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
• Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.). Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4.

External links

• International Chemical Safety Card 1230
• European Chemicals Bureau
• NIST Standard Reference Database
• Sumitomo Titanium Corporation information sheet

• Link page to external chemical sources.