Reduction with Metallic Elements

In 1964, Skell and Goldstein reduced SiCljMej at 280°C with Na/K vapor to give SiMej  

However, as reasoned by Atwell and Weyenberg, silylenes are not likely to be involved in the reactions of dichlorodiorganosilanes and metals in various aprotic solvents.  

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The complexing action of cyanide is also important in the metallurgy of silver and gold. Both gold and silver in the elemental state will dissolve in a solution of cyanide if air is present to effect an oxidation both metals form complexes of the type M(CN)7, from which the metals themselves may be recovered by reduction with metallic zinc. 

The two-stage reaction of SiO with Mg was not observed in the reduction with other elemental metals, although the final products were mostly analogous. The alkali metals Li, Na, K, and Rb did react with SiO, although the products (possibly silicides) could not be identified with certainty due to their extreme sensitivity. In the reaction mixtures of solid SiO with strontium or titanium, SrSi, SrSi2 and TisSia were identified by XRD. Reaction with aluminum did not result in the formation of a silicide but of elemental silicon instead. It should be noted that elemental silicon forms silicides with Mg, Ca, Sr, Ti and the alkali metals, for example, but not with Al. 

C, b.p. 907"C, d 713. Transition element occurring as zinc blende, sphalerite (Zn,Fe)S calamine or smithsonite (ZnCO j), willemite (Zo2Si04), franklinite (ZnFe204). Extracted by roasting to ZnO and reduction with carbon. The metal is bluish-white (deformed hep) fairly hard and brittle. Burns... 

Reduction of metal oxides with hydrogen is of interest in the metals refining industry (94,95) (see Metallurgy). Hydrogen is also used to reduce sulfites to sulfides in one step in the removal of SO2 pollutants (see Airpollution) (96). Hydrogen reacts directiy with SO2 under catalytic conditions to produce elemental sulfur and H2S (97—98). Under certain conditions, hydrogen reacts with nitric oxide, an atmospheric poUutant and contributor to photochemical smog, to produce N2 ... 

Two methods are used to measure pH electrometric and chemical indicator (1 7). The most common is electrometric and uses the commercial pH meter with a glass electrode. This procedure is based on the measurement of the difference between the pH of an unknown or test solution and that of a standard solution. The instmment measures the emf developed between the glass electrode and a reference electrode of constant potential. The difference in emf when the electrodes are removed from the standard solution and placed in the test solution is converted to a difference in pH. Electrodes based on metal—metal oxides, eg, antimony—antimony oxide (see Antimony AND ANTIMONY ALLOYS Antimony COMPOUNDS), have also found use as pH sensors (8), especially for industrial appHcations where superior mechanical stabiUty is needed (see Sensors). However, because of the presence of the metallic element, these electrodes suffer from interferences by oxidation—reduction systems in the test solution. 

Selenium and precious metals can be removed selectively from the chlorination Hquor by reduction with sulfur dioxide. However, conditions of acidity, temperature, and a rate of reduction must be carefliUy controlled to avoid the formation of selenium monochloride, which reacts with elemental selenium already generated to form a tar-like substance. This tar gradually hardens to form an intractable mass which must be chipped from the reactor. Under proper conditions of precipitation, a selenium/precious metals product substantially free of other impurities can be obtained. Selenium can be recovered in a pure state by vacuum distillation, leaving behind a precious metals residue. 

Sihca is reduced to siUcon at 1300—1400°C by hydrogen, carbon, and a variety of metallic elements. Gaseous siUcon monoxide is also formed. At pressures of >40 MPa (400 atm), in the presence of aluminum and aluminum haUdes, siUca can be converted to silane in high yields by reaction with hydrogen (15). SiUcon itself is not hydrogenated under these conditions. The formation of siUcon by reduction of siUca with carbon is important in the technical preparation of the element and its alloys and in the preparation of siUcon carbide in the electric furnace. Reduction with lithium and sodium occurs at 200—250°C, with the formation of metal oxide and siUcate. At 800—900°C, siUca is reduced by calcium, magnesium, and aluminum. Other metals reported to reduce siUca to the element include manganese, iron, niobium, uranium, lanthanum, cerium, and neodymium (16). 

Preparation of Uranium Metal. Uranium is a highly electropositive element, and extremely difficult to reduce. As such, elemental uranium caimot be prepared by reduction with hydrogen. Instead, uranium metal must be prepared using a number of rather forcing conditions. Uranium metal can be prepared by reduction of uranium oxides (UO2 [1344-59-8] or UO [1344-58-7] with strongly electropositive elements (Ca, Mg, Na), reduction of uranium halides (UCl [10025-93-1], UCl [10026-10-5] UF [10049-14-6] with electropositive metals (Li, Na, Mg, Ca, Ba), electro deposition from molten... 

Yttrium and lanthanum are both obtained from lanthanide minerals and the method of extraction depends on the particular mineral involved. Digestions with hydrochloric acid, sulfuric acid, or caustic soda are all used to extract the mixture of metal salts. Prior to the Second World War the separation of these mixtures was effected by fractional crystallizations, sometimes numbered in their thousands. However, during the period 1940-45 the main interest in separating these elements was in order to purify and characterize them more fully. The realization that they are also major constituents of the products of nuclear fission effected a dramatic sharpening of interest in the USA. As a result, ion-exchange techniques were developed and, together with selective complexation and solvent extraction, these have now completely supplanted the older methods of separation (p. 1228). In cases where the free metals are required, reduction of the trifluorides with metallic calcium can be used. 

Dilute binary alloys of nickel with elements such as aluminium, beryllium and manganese which form more stable sulphides than does nickel, are more resistant to attack by sulphur than nickel itself. Pfeiffer measured the rate of attack in sulphur vapour (13 Pa) at 620°C. Values around 0- 15gm s were reported for Ni and Ni-0-5Fe, compared with about 0-07-0-1 gm s for dilute alloys with 0-05% Be, 0-5% Al or 1-5% Mn. In such alloys a parabolic rate law is obeyed the rate-determining factor is most probably the diffusion of nickel ions, which is impeded by the formation of very thin surface layers of the more stable sulphides of the solute elements. Iron additions have little effect on the resistance to attack of nickel as both metals have similar affinities for sulphur. Alloying with other elements, of which silver is an example, produced decreased resistance to sulphur attack. In the case of dilute chromium additions Mrowec reported that at low levels (<2%) rates of attack were increased, whereas at a level of 4% a reduction in the parabolic rate constant was observed. The increased rates were attributed to Wagner doping effects, while the reduction was believed to result from the... 

Rhodium was discovered in 1803 by the eminent Norfolk scientist W.H. Wollaston he dissolved platinum metal concentrates in aqua regia and found that on removing platinum and palladium he was left with a red solution. From this he obtained the salt Na3RhCl6, which yielded the metal on reduction with hydrogen. The rose-red colour (Greek rhodon) of many rhodium salts gave the element its name. 

Pure elemental silicon is a hard, dark gray solid with a metallic luster and with a crystalline structure the same as that of the diamond form of carbon. For this reason, silicon shows many chemical and physical similarities. There is also a brown, powdery form of silicon having a microcrystalline form. The element is prepared commercially by reducing the oxide by reacting it with carbon (as coke) in electric furnaces. On a small scale, silicon has been obtained from the oxide by reduction with aluminum meted. 

Zinc is a bluish-white, lustrous metal which tarnishes in air. It is present in the earth s crust as sulfide (sphalerite), carbonate, or silicate ores, to the extent of only 78 ppm, making it the 23rd most abundant element.2 The metal is obtained from its ores by roasting and subsequent reduction with coke or by electrolysis. Approximately 8.36 million metric tons of zinc were produced worldwide in 2002 of this amount, two-thirds were from ores, while one-third was obtained from recycled zinc.3 The ease of mining and refining of the ore and the subsequent low price of the metal (ca. 1.2 kg-1 in 1998)3 have made zinc the third most popular non-ferrous metal (after aluminum and copper). 

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