Chlorides of silicon

Knowing the orbitals carbon uses for bonding, use the periodic table to predict the formula of the chloride of silicon. What orbitals does silicon use for bonding ... 

Only sulfide chlorides of silicon have thus far been described (e.g., 143). Among these, a nonvolatile compound, Si2S3Cl2, was mentioned (351), but no details were given. Areas of vitrification have heen found in the systems Si-S-Br (185), Si-S-I (185), Si-Se-Br (185), and Si-... 

The fluid material remaining in the distilling flask consists of higher homologous chlorides of silicon which may be collected as follows ... 

In order to prevent the decomposition of the higher chlorides of silicon, it is very important that only a small part of the reaction tube should be heated at a time. When the chlorine is first passed through the reaction tube, the temperature of the heating coil is about 250°C. when the reaction is well started, it is lowered to about 150°C. The best rate of flow of chlorine is less than two bubbles per second. Under these conditions, in about 12 or 14 days, all the calcium-silicon will be used up, and about 700 ml. of liquid silicon chlorides will be collected. 

Under ordinary conditions, the chlorides of silicon are colorless liquids, with the exception of Si6Cli4, which is a white solid. They all hydrolyze with great ease, fuming with the moisture of the air. When heated, the vapors of the higher chlorides inflame in air. 

Martin, G. Researches on Silicon Compounds. Part VI. Preparation of Silicon Tetrachloride, Disilicon Hexachloride, and the Higher Chlorides of Silicon by the Action of Chlorine on 50 per cent. Ferrosilicon, Together with a Discussion on Their Mode of Formation. J. chem. Soc. [London] 105, 2836 (1914). 

The higher chlorides of silicon also may be prepared by an electric-discharge method,27 by the action of SiCl4 on silicon,28 and by substitution of chlorine for iodine in hexaiododisilane.29... 

These higher chlorides of silicon hydrolyze in the same way as does the tetrachloride, and they likewise undergo similar reactions with Grignard reagents and with sodium alkyls or aryls.30 Under some conditions, however, the silicon-silicon bond is cleaved by sodium.31 The silicon-silicon chains are destroyed by the action of aqueous alkalies, liberating hydrogen at the rate of one molecule of H2 per silicon-silicon bond, just as are the higher silanes. 

The chlorides of silicon, iron, and aluminum are easily prepared from the elements. Consider the following reactions and boiling points of products (at 1 atm) ... 

Higher chlorides, Si2Cle to Si6Cl,4 (highly branched - some cyclic) are formed from SiCU plus Si or a silicide or by amine catalysed disproportionations of Si2Cl,5, etc. Partial hydrolysis gives oxide chlorides, e.g. CUSiOSiCla. SiCU is used for preparation of silicones. 

Compare and contrast the chemistry of silicon, germanium, tin and lead by referring to the properties and bond types of their oxides and chlorides. 

Silcones are important products of silicon. They may be prepared by hydrolyzing a silicon organic chloride, such as dimethyl silicon chloride. Hydrolysis and condensation of various substituted chlorosilanes can be used to produce a very great number of polymeric products, or silicones, ranging from liquids to hard, glasslike solids with many useful properties. 

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. 

Ninety-six percent of the EDC produced in the United States is converted to vinyl chloride for the production of poly(vinyl chloride) (PVC) (1) (see Vinyl polymers). Chloroform and carbon tetrachloride are used as chemical intermediates in the manufacture of chlorofluorocarbons (CECs). Methjiene chloride, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene have wide and varied use as solvents. Methyl chloride is used almost exclusively for the manufacture of silicone. Vinylidene chloride is chiefly used to produce poly (vinylidene chloride) copolymers used in household food wraps (see Vinylidene chloride and poly(vinylidene chloride). Chloroben2enes are important chemical intermediates with end use appHcations including disinfectants, thermoplastics, and room deodorants. 

The molecular absoi ption spectra, registered at a lower temperature (e.g. 700 °C for iodide or chloride of potassium or sodium), enable one to find the absorbance ratio for any pair of wavelengths in the measurement range. These ratios can be used as a correction factor for analytical signal in atomic absoi ption analysis (at atomization temperatures above 2000 °C). The proposed method was tested by determination of beforehand known silicon and iron content in potassium chloride and sodium iodide respectively. The results ai e subject to random error only. 

Fluidized bed reactors do not have to perform poorly, but special conditions must be maintained for good performance. A basic process for silicone manufacturing, which is not practiced much anymore, is the reaction of silicon metal with methyl chloride to form dimethyl dichlorosilane ... 

The trichlorosilane may be obtained by reacting hydrogen chloride with silicon in yields of 70% and thus is obtainable at moderate cost. As the olefins are also low-cost materials this method provides a relatively cheap route to the intermediates. It is, of course, not possible to produce chloromethylsilanes by this method. 

This method depends on the reaction of an organic chloride with silicon tetrachloride in the presence of sodium, lithium or potassium. 

Electronic Grade Silicon (EGS). As the first step in the production of electronic grade silicon (EGS), an impure grade of silicon is pulverized and reacted with anhydrous hydrochloric acid, to yield primarily tricholorosilane, HSiClg. This reaction is carried out in afluidizedbed at approximately 300°C in the presence of a catalyst. At the same time, the impurities in the starter impure silicon reactto form their respective chlorides. These chlorides are liquid at room temperature with the exception of vanadium dichloride and iron dichloride, which are soluble in HSiCl3 at the low concentration prevailing. Purification is accomplished by fractional distillation. 

DMSO or other sulfoxides react with trimethylchlorosilanes (TCS) 14 or trimefhylsilyl bromide 16, via 789, to give the Sila-Pummerer product 1275. Rearrangement of 789 and further reaction with TCS 14 affords, with elimination of HMDSO 7 and via 1276 and 1277, methanesulfenyl chloride 1278, which is also accessible by chlorination of dimethyldisulfide, by treatment of DMSO with Me2SiCl2 48, with formation of silicon oil 56, or by reaction of DMSO with oxalyl chloride, whereupon CO and CO2 is evolved (cf also Section 8.2.2). On heating equimolar amounts of primary or secondary alcohols with DMSO and TCS 14 in benzene, formaldehyde acetals are formed in 76-96% yield [67]. Thus reaction of -butanol with DMSO and TCS 14 gives, via intermediate 1275 and the mixed acetal 1279, formaldehyde di-n-butyl acetal 1280 in 81% yield and methyl mercaptan (Scheme 8.26). Most importantly, use of DMSO-Dg furnishes acetals in which the 0,0 -methylene group is deuter-ated. Benzyl alcohol, however, affords, under these reaction conditions, 93% diben-zyl ether 1817 and no acetal [67]. 

In addition to its uses for electronic devices, silicon is a major component of silicone polymers. The silicone backbone consists of alternating silicon and oxygen atoms. The synthesis of these polymers begins with an organic chloride such as methyl chloride and an alloy of silicon and copper ... 

V. B. Kvashenkin. Plugging solution for cementing low pressure oil and gas wells—contains plugging Portland cement, waste of silicon production as the lightening additive and calcium chloride as mineral salt, and water. Patent SU 1832149-A, 1993. 

Titanium tetrachloride is produced on an industrial scale by the chlorination of titanium dioxide-carbon mixtures in reactors lined with silica. During the reactor operation, the lining comes into contact not only with chlorine but also with titanium tetrachloride. There appears to be no attack on silica by either of these as the lining remains intact. However, the use of such a reactor for chlorinating beryllium oxide by the carbon-chlorine reduction chlorination procedure is not possible because the silica lining is attacked in this case. This corrosion of silica can be traced to the attack of beryllium chloride on silica. The interaction of beryllium chloride with silica results in the formation of silicon tetrachloride in accordance with the reaction... 

In the case of silicon, the tendency for catenation allows halides having the formula Si2X6 to be prepared. The chloride can be prepared by the reaction... 

Linear phosphonitrilic chlorides (LPNCs), silicone fluids and, 22 573 Linear photodiode arrays, 19 153 Linear polyesters, 14 116 Linear polyethylene fibers, 20 398 Linear polyimides, synthesis of, 20 273 Linear polymers, 20 391 25 455 high molecular weight, 23 733 zero-shear viscosity of, 19 839 Linear poly(thioarylene)s, 23 705 Linear PPS, 23 704. See also... 

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