Tungsten and Chlorine

The binary compounds WCle, WCI5, WCI4, and WCI2 and the ternary oxychlorides WOCI4, WO2CI2, WOCI3, and WOCI2 exist. 

PR By direct chlorination of tungsten in a flowing system at 600 °C. On cooling between 168 °C and 170 °C a violent, explosion-like expansion of the solid occurs due to an a2-ai transition. 

By reaction of compounds like S2CI2, PCI5, HCl, COCI2, or CCI4 with tungsten or tungsten trioxide. 

It is very soluble in CS2, alcohol, CCI3, CCI4, ether, benzene, acetone, and ammonia. Decomposition with water starts above 60 °C. Gaseous WCU will be stepwise reduced by hydrogen to lower chlorides and finally to W. 

It is commercially available and is used as starting material for the chemical vapor deposition of tungsten (see Sections 5.6.3. and 5.7.5) and for the preparation of metathesis catalysts which form double and triple bonds with carbon (see Chapter 10). 

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The composition of this alloy (54% nickel, 15% molybdenum, 15% chromium, 5% tungsten and 5% iron) is less susceptible to intergranular corrosion at welds. The presence of chromium in this alloy gives it better resistance to oxidizing conditions than the nickel/molybdenum alloy, particularly for durability in wet chlorine and concentrated hypochlorite solutions, and has many applications in chlorination processes. In cases in which hydrochloric and sulfuric acid solutions contain oxidizing agents such as ferric and cupric ions, it is better to use the nickel/molybdenum/ chromium alloy than the nickel/molybdenum alloy. 

Chromium, 122 ppm of the earth s crustal rocks, is comparable in abundance with vanadium (136 ppm) and chlorine (126 ppm), but molybdenum and tungsten (both 1.2 ppm) are much rarer (cf. Ho 1.4 ppm, Tb 1.2 ppm), and the concentration in their ores is low. The only ore of chromium of any commercial importance is chromite, FeCr204, which is produced principally in southern Africa (where 96% of the known reserves are located), the former Soviet Union and the Philippines. Other less plentiful sources are crocoite, PbCr04, and chrome ochre, Cr203, while the gemstones emerald and ruby owe their colours to traces of chromium (pp. 107, 242). 

Antimony, arsenic, selenium, tellurium, iridium, iron, molybdenum, osmium, potassium, rhodium, tungsten (and when primed with charcoal,) aluminium, copper, lead, magnesium, silver, tin, zinc. Interaction of lithium or calcium with chlorine tri- or penta-fluorides is hypergolic and particularly energetic. 

The action of carbon tetrachloride or a mixture of chlorine with a hydrocarbon or carbon monoxide on the oxide.—H. N. Warren 9 obtained aluminium chloride by heating the oxide to redness with a mixture of petroleum vapour and hydrogen chloride or chlorine, naphthalene chloride or carbon tetrachloride was also used. The bromide was prepared in a similar manner. E. Demarpay used the vapour of carbon tetrachloride, the chlorides of chromium, titanium, niobium, tantalum, zirconium, cobalt, nickel, tungsten, and molybdenum H. Quantin, a mixture of carbon monoxide and chlorine and W. Heap and E. Newbery, carbonyl chloride. 

Tungsten(VI) fluoride (WF6) and molybdenum(VI) fluoride (MoF6) are available commercially, and can be made by reaction of the metals with fluorine.4 In the case of uranium(VI) fluoride (UF6), a preparation that is claimed5 to be feasible in the laboratory uses uranium metal and chlorine trifluoride uranium(VI) fluoride is prepared6 commercially by the fluorination of uranium(IV) fluoride, itself prepared from an oxide and hydrogen fluoride. 

Phillips and Timms [599] described a less general method. They converted germanium and silicon in alloys into hydrides and further into chlorides by contact with gold trichloride. They performed GC on a column packed with 13% of silicone 702 on Celite with the use of a gas-density balance for detection. Juvet and Fischer [600] developed a special reactor coupled directly to the chromatographic column, in which they fluorinated metals in alloys, carbides, oxides, sulphides and salts. In these samples, they determined quantitatively uranium, sulphur, selenium, technetium, tungsten, molybdenum, rhenium, silicon, boron, osmium, vanadium, iridium and platinum as fluorides. They performed the analysis on a PTFE column packed with 15% of Kel-F oil No. 10 on Chromosorb T. Prior to analysis the column was conditioned with fluorine and chlorine trifluoride in order to remove moisture and reactive organic compounds. The thermal conductivity detector was equipped with nickel-coated filaments resistant to corrosion with metal fluorides. Fig. 5.34 illustrates the analysis of tungsten, rhenium and osmium fluorides by this method. 

The hexachlorides of tungsten and uranium have a deformed hexagonal close-packing of chlorine atoms with metal atoms filling only one sixth of the octahedral holes. 

Tungsten (W) and chlorine (Cl) form a series of compounds with the following compositions ... 

Because of practical problems such as the sensitivity of WC16 to moisture and air, Shroff169b proposed in situ generation of WC16 by the reaction between the metal and chlorine at about 900°C in a separate chamber. The tungsten chloride is then transported to the deposition chamber where reduction with hydrogen leads to tungsten deposition. 

The discovery of elements over and above the nine known to the ancients and the four studied by medieval alchemists has been mentioned in Chapter 4. The gaseous elements, nitrogen, hydrogen, oxygen, and chlorine, had all been discovered in the eighteenth century. So had the metals, cobalt, platinum, nickel, manganese, tungsten, molybdenum, uranium, titanium, and chromium. 

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