Titanium tetrachloride
Template:Short description Template:Chembox
Titanium tetrachloride is the inorganic compound with the formula Template:Chem2. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. Template:Chem2 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide (Template:Chem2) and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as "tickle" or "tickle 4", as a phonetic representation of the symbols of its molecular formula (Template:Chem2).[1][2]
Properties and structure
Template:Chem2 is a dense, colourless liquid, although crude samples may be yellow or even red-brown. It is one of the rare transition metal halides that is a liquid at room temperature, [[vanadium tetrachloride|Template:Chem2]] being another example. This property reflects the fact that molecules of Template:Chem2 weakly self-associate. Most metal chlorides are polymers, wherein the chloride atoms bridge between the metals. Its melting point is similar to that of [[Carbon tetrachloride|Template:Chem2]].[3][4]
Template:Chem2 has a "closed" electronic shell, with the same number of electrons as the noble gas argon. The tetrahedral structure for Template:Chem2 is consistent with its description as a d0 metal center (Template:Chem2) surrounded by four identical ligands. This configuration leads to highly symmetrical structures, hence the tetrahedral shape of the molecule. Template:Chem2 adopts similar structures to [[Titanium tetrabromide|Template:Chem2]] and [[Titanium tetraiodide|Template:Chem2]]; the three compounds share many similarities. Template:Chem2 and Template:Chem2 react to give mixed halides Template:Chem2, where x = 0, 1, 2, 3, 4. Magnetic resonance measurements also indicate that halide exchange is also rapid between Template:Chem2 and Template:Chem2.[5]
Template:Chem2 is soluble in toluene and chlorocarbons. Certain arenes form complexes of the type Template:Chem2.[6] Template:Chem2 reacts exothermically with donor solvents such as THF to give hexacoordinated adducts.[7] Bulkier ligands (L) give pentacoordinated adducts Template:Chem2.
Production
Template:Chem2 is produced by the chloride process, which involves the reduction of titanium oxide ores, typically ilmenite (Template:Chem2), with carbon under flowing chlorine at 900 °C. Impurities are removed by distillation.[4]
The coproduction of [[Iron(III) chloride|Template:Chem2]] 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 Template:Chem2, is derived from ilmenite by removal of iron, either using carbon reduction or extraction with sulfuric acid. Crude Template:Chem2 contains a variety of other volatile halides, including vanadyl chloride (Template:Chem2), silicon tetrachloride (Template:Chem2), and tin tetrachloride (Template:Chem2), which must be separated.[4]
Applications
Production of titanium metal
The world's supply of titanium metal, about 250,000 tons per year, is made from Template:Chem2. The conversion involves the reduction of the tetrachloride with magnesium metal. This procedure is known as the Kroll process:[8]
In the Hunter process, liquid sodium is the reducing agent instead of magnesium.[9]
Production of titanium dioxide
Around 90% of the Template:Chem2 production is used to make the pigment titanium dioxide (Template:Chem2). The conversion involves hydrolysis of Template:Chem2, a process that forms hydrogen chloride:[8]
In some cases, Template:Chem2 is oxidised directly with oxygen:
Smoke screens
It has been used to produce smoke screens since it produces a heavy, white smoke that has little tendency to rise. "Tickle" was the standard means of producing on-set smoke effects for motion pictures, before being phased out in the 1980s due to concerns about hydrated HCl's effects on the respiratory system.Script error: No such module "Unsubst".
Chemical reactions
Titanium tetrachloride is a versatile reagent that forms diverse derivatives including those illustrated below.[10]
A characteristic reaction of Template:Chem2 is its easy hydrolysis, signaled by the release of HCl vapors and titanium oxides and oxychlorides. Titanium tetrachloride has been used to create naval smokescreens, as the hydrochloric acid aerosol and titanium dioxide that is formed scatter light very efficiently. This smoke is corrosive, however.[4]
Alcohols react with Template:Chem2 to give alkoxides with the formula Template:Chem2 (R = alkyl, n = 1, 2, 4). As indicated by their formula, these alkoxides can adopt complex structures ranging from monomers to tetramers. Such compounds are useful in materials science as well as organic synthesis. A well known derivative is titanium isopropoxide, which is a monomer. Titanium bis(acetylacetonate)dichloride results from treatment of titanium tetrachloride with excess acetylacetone:[11]
Organic amines react with Template:Chem2 to give complexes containing amido (Template:Chem2-containing) and imido (Template:Chem2-containing) complexes. With ammonia, titanium nitride is formed. An illustrative reaction is the synthesis of tetrakis(dimethylamido)titanium Template:Chem2, a yellow, benzene-soluble liquid:[12] This molecule is tetrahedral, with planar nitrogen centers.[13]
Complexes with simple ligands
Template:Chem2 is a Lewis acid as implicated by its tendency to hydrolyze. With the ether THF, Template:Chem2 reacts to give yellow crystals of Template:Chem2. With chloride salts, Template:Chem2 reacts to form sequentially Template:Chem2, Template:Chem2 (see figure above), and Template:Chem2.[14] The reaction of chloride ions with Template:Chem2 depends on the counterion. Template:Chem2 and Template:Chem2 gives the pentacoordinate complex Template:Chem2, whereas smaller Template:Chem2 gives Template:Chem2. These reactions highlight the influence of electrostatics on the structures of compounds with highly ionic bonding.
Redox
Reduction of Template:Chem2 with aluminium results in one-electron reduction. The trichloride ([[Titanium(III) chloride|Template:Chem2]]) and tetrachloride have contrasting properties: the trichloride is a colored 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 Template:Chem2.
Organometallic chemistry
Script error: No such module "Labelled list hatnote". The organometallic chemistry of titanium typically starts from Template:Chem2. An important reaction involves sodium cyclopentadienyl to give titanocene dichloride, Template:Chem2. 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.[10]
Arenes, such as Template:Chem2 react to give the piano-stool complexes Template:Chem2 (R = H, Template:Chem2; see figure above). This reaction illustrates the high Lewis acidity of the Template:Chem2 entity, which is generated by abstraction of chloride from Template:Chem2 by [[aluminium trichloride|Template:Chem2]].[6]
Reagent in organic synthesis
Template:Chem2 finds occasional use in organic synthesis, capitalizing on its Lewis acidity, its oxophilicity, and the electron-transfer properties of its reduced titanium halides. It is used in the Lewis acid catalysed aldol addition[15] Key to this application is the tendency of Template:Chem2 to activate aldehydes (RCHO) by formation of adducts such as Template:Chem2.[16]
Toxicity and safety considerations
Hazards posed by titanium tetrachloride generally arise from its reaction with water that releases hydrochloric acid, which is severely corrosive itself and whose vapors are also extremely irritating. Template:Chem2 is a strong Lewis acid, which exothermically forms adducts with even weak bases such as THF and water.
References
General reading
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- Template:Greenwood&Earnshaw
External links
- Titanium tetrachloride: Health Hazard Information
- NIST Standard Reference Database
- ChemSub Online: Titanium tetrachloride
Template:Titanium compounds Template:Chlorides
- ↑ [1] Template:Webarchive American Chemistry Council – "Titanium Tetrachloride: Stepping Stone to Amazing Technology"
- ↑ Script error: No such module "citation/CS1". Iowa State University – "Chemistry Material Safety Data Sheets"
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- ↑ Mariappan Periasamy (2002): "New synthetic methods using the TiCl4-NR3 reagent system", Arkivoc, p. 151-166.
- ↑ Script error: No such module "citation/CS1".