Liquid titanium tetrachloride

The ease of oxidation of magnesium is important in the commercial manufacture of titanium metal. Titanium, when quite pure, shows great promise as a structural metal, but the economics of production have thus far inhibited its use. One of the processes currently used, the Kroll process, involves the reduction of liquid titanium tetrachloride with molten metallic magnesium ... 

The chlorination of titanium mixture is exothermal, the temperature in the furnace spontaneously rises therefore, the chlorinator is fashioned with special elements for heat withdrawal. They are water-cooled graphite blocks with steel pipes inside. Excess heat can also be withdrawn by spraying the melt with some of the obtained liquid titanium tetrachloride the heat in this case is spent on heating, evaporating and overheating TiCl4 to the temperature of the outlet vapour and gas mixture. 

The liquid titanium tetrachloride is corrosive to skin and membranes of the eye. This may be due to liberation of hydrochloric acid on hydrolysis. 

General Toxicology. Liquid titanium tetrachloride causes skin irritation and bums (Sanotskii, 1960 Lawson, 1961), and plashes of titanium tetrachloride cause comeal injury (Sanotskii, 1960). 

Titanium(IV) chloride (10%). To 90 ml of 6m hydrochloric acid add 10 ml liquid titanium tetrachloride, TiCl4, and mix. 

Titanium tetrachloride TiCU Colourless to light yellow fuming corrosive liquid Vapour is irritating Reacts vigorously with water, liberating heat and corrosive HCI gas Reacts more strongly with hot water Use water spray to keep exposed containers cool in fire... 

This is a clear liquid that vaporizes and, on contact with damp air, combines with w ater to produce a dense acid mist. Titanium tetrachloride can be painted on to surfaces, such as fume cupboard sills, from which it will evaporate over a period of several seconds showing the airflow patterns close to the surface. (Airflow patterns close to a surface could also be visualized by fastening short filaments of wool or cotton to the surface). Titanium tetrachloride can also be used, when soaked onto a cotton swab, in a similar way to a smoke tube. It is a simple and inexpensive method but the production of smoke, which is toxic and corrosive, is uncontrollable. 

Another chloride reduction process, originally developed by Hunter for titanium tetrachloride and known by his name, uses sodium as the reductant. In this process liquid sodium and titanium tetrachloride are simultaneously metered into a steel retort under an argon atmosphere. The highly exothermic reduction reaction... 

In the production of titanium, the chlorination of rutile generates approximately 0.12 tons of waste for every ton of titanium tetrachloride produced. If ilmenite is directly chlorinated, the amount of waste is 1.5 tons for every ton of titanium tetrachloride. Large amounts of ferric chloride are produced along with volatile chlorides and oxychlorides (e.g., aluminum trichloride, silicon tetrachloride, carbon oxychloride, tin tetrachloride, vanadium tetrachloride, vanadium oxychloride) these can be removed by selective distillation. In flu-idized-bed chlorination, the build-up of liquid calcium chloride and magnesium chloride in the fluid bed interferes with the process of fluidization and hence these must be removed. 

The only solid acidic catalyst which has given high polymers at an appreciable rate at low temperatures, and which has been studied in some detail, is that described by Wichterle [41, 42]. This was prepared as follows A 10 per cent solution in hexane of aluminium tri-(s- or t-butoxide) was saturated with boron fluoride at room temperature, and excess boron fluoride was removed from the precipitate by pumping off about half the hexane. Two moles of boron fluoride were absorbed per atom of aluminium, and butene oligomers equivalent to two-thirds of the alkoxy groups were found in the solution the resulting solid had hardly any catalytic activity. When titanium tetrachloride was added to the suspension in hexane, an extremely active catalyst was formed but the supernatant liquid phase had no catalytic activity. The DP of the polymers formed by the catalyst prepared from the s-butoxide was much lower than that of polymers formed with a catalyst prepared from the r-butoxidc. 

Presently there are two main processes for manufacturing this important white pigment. The main one involves reaction of rutile ore (about 95% Ti02) with chlorine to give titanium tetrachloride. For this reason we have chosen to group this key chemical under chlorine and sodium chloride. The titanium tetrachloride is a liquid and can be purified by distillation, bp 136°C. It is then oxidized to pure titanium dioxide and the chlorine is regenerated. Approximately 94% of all titanium dioxide is made by this process. 

Unlike boron fluoride, titanium tetrachloride does not catalyze the liquid phase polymerization of isobutylene under anhydrous conditions (Plesch et al., 83). The addition of titanium tetrachloride to a solution of the olefin in hexane at —80° failed to cause any reaction. Instantaneous polymerization occurred when moist air was added. Oxygen, nitrogen, carbon dioxide, and hydrogen chloride had no promoting effect. Ammonia and sulfur dioxide combined with the catalyst if these were added in small quantity only, subsequent addition of moist air permitted the polymerization to occur. Ethyl alcohol and ethyl ether, on the other hand, prevented the polymerization even on subsequent addition of moist air. They may be regarded as true poisons. 

The addition of boron fluoride to a nonreacting mixture of isobutylene and titanium tetrachloride at -80° resulted in a rapid polymerization of isobutylene. In other words, as has already been mentioned, the liquid phase polymerization of isobutylene with boron fluoride catalyst apparently does not require the presence of water. 

The action of water in the titanium tetrachloride catalyzed polymerization is paradoxical, since water at —60 to —80° was present only in the solid phase its solubility in hexane at these temperatures is in the order of 10-10 moles per liter (Plesch et al., 83). It was found to be essential that the water be present as an extremely fine dispersion such as might result from the rapid bubbling of moist air through the liquid at the low temperature. Addition of liquid water which formed lumps of ice in the reaction mixture did not initiate polymerization. It may be concluded that a fine dispersion is necessary in order that reaction with titanium tetrachloride can occur and a chain reaction is initiated ... 

Type 2 2-kg Target Indicator consisted of a Bakelite cylinder with round nose and tail provided with fins. The filling consisted of liquid FM (Titanium Tetrachloride). This smoke mixture was scattered when the bomb was released from a plane, hit the target and broke (pp 113-14, Fig 86)... 

Titanium Tetrachloride — Fire Hazards Flash Point (deg. F) Not flammable Flammable Limits in Air (%>) Not flammable Fire Extinguishing Agents Dry powder or carbon dioxide on adjacent fires Fire Extinguishing Agents Not To Be Used Do not use water if it can directly contact this chemical Special Hazards of Combustion Products Not pertinent Behavior in Fire If containers leak, a very dense white fume can form and obscure operations Ignition Temperature (deg. F) Not flammable Electrical Hazard Not pertinent Burning Rate Not flammable. Chemical Reactivity Reactivity with Water Reacts with moisture in air forming a dense white fume. Reaction with liquid... 

Titanium tetrachloride reacts with trimethylsilanol in the presence of ammonia (equation 17). This complex is a colourless liquid, and the method can be used to produce complexes of... 

FIGURE 5.48 Titanium tetrachloride, TiCl4, is a liquid that reacts with water to form titanium dioxide, Ti02. When squirted out of appropriate containers, it can be used for producing smoke screens or, as here, for skywriting. 

The chloride process (Fig. 2) involves the reaction of rutile (an ore containing approximately 95% by weight titanium dioxide, Ti02) with chlorine to give titanium tetrachloride (T1C14), a liquid that can be purified by... 

Titanium tetrachloride can also be purified from impurities by the continuous technique. The installation for continuous purification consists of several vertical pipe coolers. Liquid products of the reaction are sent into the first cooler, which is located a little higher than the rest, where the mixture is cooled at agitation to -3 - -5°C. After that, the mixture is abruptly cooled to -20 - -23.5 °C the solution deposits crystals of Si2Cl6 and VOCI3. The deposited crystals remain in the primary cooler, and the solution self-flows into the secondary coolers, where it is gradually cooled from -23 to -27 °C titanium tetrachloride deposits as white sediment. It is collected in the secondary coolers and washed with water. The TiCl4 thus purified is 99.92% pure. 

Titanium tetrachloride is a colourless transparent liquid (the boiling point is 136 °C) it is easily decomposed with water forming hydrogen chloride and titanium dioxide. It joins the moisture in air to form white suffocating fumes, which are drops of hydrochloric acid. 

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