Titanium reductions

It is not possible to obtain titanium metal by the usual method of reduction of the dioxide with carbon, because a very stable carbide is formed. Moreover the metal is reactive towards nitrogen and oxygen at elevated temperatures, and hydrogen at 900 °C only reduces Ti02 as far as Ti3Os. Reduction of the dioxide with most reducing metals, e.g. Na, Al, Ca or Mg, seldom seems to yield a pure product the most common contaminants, and in some cases the principal products, are lower oxides of titanium. Reduction of the tetrachloride is, therefore, the basis of the preferred methods. 

Use Tetraethyl and tetramethyl lead, titanium reduction, sodium peroxide, sodium hydride, polymerization catalyst for synthetic rubber, lab reagent, coolant in nuclear reactors, electric power cable (encased in polyethylene), nonglare lighting for highways, radioactive forms in tracer studies and medicine, heat transfer agent in solar-powered electric generators. 

The coordination chemistry of this oxidation state is virtually confined to that of titanium. Reduction of zirconium and hafnium from the quadrivalent to the tervalent state is not easy and cannot be attempted in water which is itself reduced by Zr and A few adducts of the trihalides of these two elements with N- or P- donor ligands have been prepared. ZrBrj treated with liquid ammonia yields a hexaammine stable to room temperature... 

The synthesis of these nonatetraenoates Schemes 1.8 and 1.9) [21] utilizes low-valent titanium reductive elimination, a methodology which was also used in the stereospecific synthesis of ali-trans retinoic acid [21]. Because of the high stereospecificity, purification of intermediates prior to the final step was not necessary. 

Buchwald and his colleagues have made extensive use of the titanium reductive ring closure in an indolization as summarized in Scheme 8, equations 1 and 2 [76]. A small selection of indoles prepared using these methodologies is shown. 

Proprietary lost wax ceramic shell systems have been developed by the several fotmdries engaged in titanivim casting manufacture. Of necessity, these shell systems must be relatively inert to molten titanium and cannot be made with the conventional foimdiy ceramics used in the ferrous and nonferrous industries. Usually, the face coats are made with special re actoiy oxides and appropriate binders. After the initial face coat ceramic is applied to the wax pattern, more traditional refractoiy systems are used to add shell strength om repeated backup ceramic coatings. Regardless of face coat composition, some metal/mold reaction inevitably occurs from titanium reduction... 

Loncle, C., Salmi, C., Letourneux, Y, and Brunei, J.M. (2007) Synthesis of new 7-aminosterol squalamine analogues with high antimicrobial activities through a stereoselective titanium reductive amination reaction. Tetrahedron, 63,12968-12974. 

Madey and co-workers followed the reduction of titanium with XPS during the deposition of metal overlayers on TiOi [87]. This shows the reduction of surface TiOj molecules on adsorption of reactive metals. Film growth is readily monitored by the disappearance of the XPS signal from the underlying surface [88, 89]. This approach can be applied to polymer surfaces [90] and to determine the thickness of polymer layers on metals [91]. Because it is often used for chemical analysis, the method is sometimes referred to as electron spectroscopy for chemical analysis (ESCA). Since x-rays are very penetrating, a grazing incidence angle is often used to emphasize the contribution from the surface atoms. 

The extraction of titanium is still relatively costly first the dioxide Ti02 is converted to the tetrachloride TiCl4 by heating with carbon in a stream of chlorine the tetrachloride is a volatile liquid which can be rendered pure by fractional distillation. The next stage is costly the reduction of the tetrachloride to the metal, with magnesium. must be carried out in a molybdenum-coated iron crucible in an atmospheric of argon at about 1100 K ... 

The colour sequence already described, for the reduction of van-adium(V) to vanadium(II) by zinc and acid, gives a very characteristic test for vanadium. Addition of a few drops of hydrogen peroxide to a vanadate V) gives a red colour (formation of a peroxo-complex) (cf. titanium, which gives an orange-yellow colour). 

Reductive coupling of carbonyl compounds to yield olefins is achieved with titanium (0), which is freshly prepared by reduction of titanium(III) salts with LiAIH4 or with potassium. The removal of two carbonyl oxygen atoms is driven by T1O2 formation- Yields are often excellent even with sensitive or highly hindered olefins. (J.E. McMurry, 1974, 1976A,B). 

Fluoridation of UO2 peUets Catalyst regeneration Hydrogen reduction of ores Titanium dioxide... 

Very reactive metals, eg, titanium or 2irconium, which in the Hquid state react with all the refractory materials available to contain them, also require reduction to soHd metal. Titanium is produced by metallothermic reduction of its chloride using Hquid magnesium at 750°C (KroU process). 

Fig. 4. Flow sheet for the processing of titanium ore by chlorination followed by reduction with magnesium.

Aluminum. All primary aluminum as of 1995 is produced by molten salt electrolysis, which requires a feed of high purity alumina to the reduction cell. The Bayer process is a chemical purification of the bauxite ore by selective leaching of aluminum according to equation 35. Other oxide constituents of the ore, namely siUca, iron oxide, and titanium oxide remain in the residue, known as red mud. No solution purification is required and pure aluminum hydroxide is obtained by precipitation after reversing reaction 35 through a change in temperature or hydroxide concentration the precipitate is calcined to yield pure alumina. 

Other Metals. AH the sodium metal produced comes from electrolysis of sodium chloride melts in Downs ceUs. The ceU consists of a cylindrical steel cathode separated from the graphite anode by a perforated steel diaphragm. Lithium is also produced by electrolysis of the chloride in a process similar to that used for sodium. The other alkaH and alkaHne-earth metals can be electrowon from molten chlorides, but thermochemical reduction is preferred commercially. The rare earths can also be electrowon but only the mixture known as mischmetal is prepared in tonnage quantity by electrochemical means. In addition, beryIHum and boron are produced by electrolysis on a commercial scale in the order of a few hundred t/yr. Processes have been developed for electrowinning titanium, tantalum, and niobium from molten salts. These metals, however, are obtained as a powdery deposit which is not easily separated from the electrolyte so that further purification is required. 

Naphthaleneamine. 1-Naphthylamine or a-naphth5iamine/7i5 -i2- can be made from 1-nitronaphthalene by reduction with iron—dilute HCl, or by catalytic hydrogenation it is purified by distillation and the content of 2-naphthylamine can be reduced as low as 8—10 ppm. Electroreduction of 1-nitronaphthalene to 1-naphthylamine using titania—titanium composite electrode has been described (43). Photoinduced reduction of 1-nitronaphthalene on semiconductor (eg, anatase) particles produces 1-naphthylamine in 77% yield (44). 1-Naphthylamine/7J4-J2-. can also be prepared by treating 1-naphthol with NH in the presence of a catalyst at elevated temperature. The sanitary working conditions are improved by gas-phase reaction at... 

Analytical and Test Methods. o-Nitrotoluene can be analyzed for purity and isomer content by infrared spectroscopy with an accuracy of about 1%. -Nitrotoluene content can be estimated by the decomposition of the isomeric toluene diazonium chlorides because the ortho and meta isomers decompose more readily than the para isomer. A colorimetric method for determining the content of the various isomers is based on the color which forms when the mononitrotoluenes are dissolved in sulfuric acid (45). From the absorption of the sulfuric acid solution at 436 and 305 nm, the ortho and para isomer content can be deterrnined, and the meta isomer can be obtained by difference. However, this and other colorimetric methods are subject to possible interferences from other aromatic nitro compounds. A titrimetric method, based on the reduction of the nitro group with titanium(III) sulfate or chloride, can be used to determine mononitrotoluenes (32). Chromatographic methods, eg, gas chromatography or high pressure Hquid chromatography, are well suited for the deterrnination of mononitrotoluenes as well as its individual isomers. Freezing points are used commonly as indicators of purity of the various isomers. 

Titanium slag and synthetic mtile are also used as raw materials in the production of titanium whites. Titanium slag results from a metaHurgical process during which iron (qv) is removed from ilmenite by reduction with coke in an electric arc furnace at 1200—1600°C. Under these conditions, iron oxide is reduced to metal, melts, and separates from the formed titanium slag. Titanium slag contains 70—75% Ti02 and only 5—8% iron. 

The cake produced by the digestion is extracted with cold water and possibly with some diluted acids from the subsequent processes. During the cake dissolution it is necessary to maintain the temperature close to 65°C, the temperature of iron sulfate maximum solubiUty. To prevent the reoxidation of the Fe " ions during processing, a small amount of Ti " is prepared in the system by the Ti reduction. The titanium extract, a solution of titanium oxo-sulfate, iron sulfate, and sulfuric acid, is filtered off. Coagulation agents are usually added to the extract to faciUtate the separation of insoluble sludge. 

Both the Toth and Alcoa processes provide aluminum chloride for subsequent reduction to aluminum. Pilot-plant tests of these processes have shown difficulties exist in producing aluminum chloride of the purity needed. In the Toth process for the production of aluminum chloride, kaolin [1332-58-7] clay is used as the source of alumina (5). The clay is mixed with sulfur and carbon, and the mixture is ground together, pelletized, and calcined at 700°C. The calcined mixture is chlorinated at 800°C and gaseous aluminum chloride is evolved. The clay used contains considerable amounts of silica, titania, and iron oxides, which chlorinate and must be separated. Silicon tetrachloride and titanium tetrachloride are separated by distillation. Resublimation of aluminum chloride is requited to reduce contamination from iron chloride. 

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