Titanium reductant

Typically, oc,0-unsaturated esters, a,0-unsaturated aldehydes and a,0-unsaturated nitriles are poor acceptors for the Lewis acid catalyzed silylallylation procedure, but they are excellent acceptors for the complementary fluoride ion mediated allylation procedure (cf. Volume 4, Chapter 1.2, Section 1.2.2.1.7). Other suitable acceptors include 1,4-quinones,70 a,0-unsaturated acyl cyanides (162),718 silyl ot,0-enoates (163)71b and nitroalkenes (Scheme 26) 72 reduction (titanium(III) trichloride) of the intermediate nitronates arising from nitroalkene allylation affords y,8-enones (166). 

Reduction. Titanium(IV) is reduced to Ti by Nang, Mg, Zn, Zn g, A1 in acid, and Sn. With the Jones reductor (Znng), large amounts of the element may be determined volumetrically. The Ti is mixed with Fe sulfate, excluding air, and the Fe " produced is titrated with Mn04. ... 

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. 

Reduction. Just as aromatic amine oxides are resistant to the foregoing decomposition reactions, they are more resistant than ahphatic amine oxides to reduction. Ahphatic amine oxides are readily reduced to tertiary amines by sulfurous acid at room temperature in contrast, few aromatic amine oxides can be reduced under these conditions. The ahphatic amine oxides can also be reduced by catalytic hydrogenation (27), with 2inc in acid, or with staimous chloride (28). For the aromatic amine oxides, catalytic hydrogenation with Raney nickel is a fairly general means of deoxygenation (29). Iron in acetic acid (30), phosphoms trichloride (31), and titanium trichloride (32) are also widely used systems for deoxygenation of aromatic amine oxides. 

Direct ammonolysis involving dehydratioa catalysts is geaerahy ma at higher temperatures (300—500°C) and at about the same pressure as reductive ammonolysis. Many catalysts are active, including aluminas, siUca, titanium dioxide [13463-67-7], and aluminum phosphate [7784-30-7] (41—43). Yields are acceptable (>80%), and coking and nitrile formation are negligible. However, Htfle control is possible over the composition of the mixture of primary and secondary amines that can be obtained. 

High purity 50% ferrosihcon containing <0.1% Al and C is used for production of stainless steel and corded wire for tires, where residual aluminum can cause harm fill alumina-type inclusions. These are also useflil in continuous cast heats, where control of aluminum is necessary. High purity grades of 50 and 75% ferrosihcon containing low levels of aluminum, calcium, and titanium are used for sihcon additions to grain-oriented electrical steels, where low residual aluminum content contributes to the attainment of desired electrical properties, eg, significant reduction of eddy currents. 

Vanadium—Silicon. Vanadium—shicon ahoy is made by the reduction of vanadium oxides with shicon in an electric furnace. Apphcation is essentiahy the same as that of the titanium ahoys. Vanadium ahoys sometimes offer the most economical way of introducing vanadium into molten steel. 

The manufacture of refractory metals such as titanium, zirconium, and hafnium by sodium reduction of their haHdes is a growing appHcation, except for titanium, which is produced principally via magnesium reduction (109—114). Typical overall haHde reactions are... 

Sodium nitrite has been synthesized by a number of chemical reactions involving the reduction of sodium nitrate [7631-99-4] NaNO. These include exposure to heat, light, and ionizing radiation (2), addition of lead metal to fused sodium nitrate at 400—450°C (2), reaction of the nitrate in the presence of sodium ferrate and nitric oxide at - 400° C (2), contacting molten sodium nitrate with hydrogen (7), and electrolytic reduction of sodium nitrate in a cell having a cation-exchange membrane, rhodium-plated titanium anode, and lead cathode (8). 

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