Cyanides alumination

A large number of electrolytic treatments of magnesium, anodic or a.c., have been developed, in which adherent white or grey films consisting of fluoride, oxide, hydroxide, aluminate or basic carbonate are deposited from alkaline solutions containing caustic alkali, alkali carbonates, phosphates, pyrophosphates, cyanides, aluminates, oxalates, silicates, borates, etc. Some films are thin, and some are relatively thick. All are more or less absorbent and act as good bases for paint, though none contributes appreciable inhibition. All can, however, absorb chromates with consequent improvement of protective efficiency. 

The major reactions are complicated by a number of minor or secondary reactions, and by impurities in the raw materials. As a result the black ash may contain 1 to 2 per cent, of sodium silicate to If per cent, of sodium aluminate 1 per cent, of sodium ferrous sulphide small proportions of sodium cyanide and thiocyanate derived from the nitrogen of the coal a relatively small amount of ultramarine etc. Proposals to use barium carbonate, etc., in place of limestone in the black-ash process are indicated in connection with the preparation of sodium carbonate from sodium sulphide. 

Tankwater, Bright dip acid (phosphoric), Cyanide rinse bath, Pickle Liquor, Sodium Aluminate Liquor, N.S.S.C. Liquor, Kraft Liquor, Soda Liquor, Sulfite Liquor, Stillage, Corn Syrup, Gelatin, Salt, Soybean Oil, Steepwater, Sugar, Whey, Mercerizing Caustic, Nylon Salt, Rayon Spin Bath, and Sodium Sulfate. 

The chromous salts, derived from the oxide CrO, arc analogous to the salts of divalent vanadium, manganese, and iron. This is seen in the isomorphism of the sulphates of the type R" SOj-THgO. The stability of such salts increases in the order of the atomic number of the metal. The chief basic oxide of chromium is the sesquioxidc CraO, which is closely allied to ferric oxide, and, like the latter, resembles aluminium oxide. The hydroxide, Cr(OH)3, with bases yields chromites analogous to, but less stable than, the aluminates. Chromic sulphate enters into the formation of alums. The chromic salts are very stable, but in the trivaJent condition the metal shows a marked tendency to form complex ions, both anions and cations thus it resembles iron in producing complex cyanides, whilst it also yields compounds similar to the cobaltamines. 

Three tetracyclic systems, triphenylene, benz(c)phenanthrene and chrysene can be derived by angular benzannelation of phenanthrene and hence these hydrocarbons may be synthesized from corresponding phenanthreneacetonitriles. The phenanthrene-1-acetonitrile (81) used for the preparation of the chrysenes (82) was obtained from phenanthrene-l-carbonitrile (72a) in a sequence of conventional steps hydrolysis to the acid (84%) by KOH in triglycol, reduction to the carbinol (82%) by sodium dihydrido-bis(methoxyethoxy)aluminate, conversion by thionyl chloride in benzene to the chloromethyl derivative (98%), and finally reaction of the latter with sodium cyanide in DMSO to (81) (94%). 

Treatment of cyclopropanecarbonyl chloride with excess of lithium tetrakis(trimethyl-silyl)aluminate in the presence of a catalytic amount of copper(I) cyanide gave cyclopropyl-carbonyltrimethylsilane in 89% yield. 

Dialkylaluminum cyanides are prepared by alumination of HCN starting from R3AI or (less preferably) R2AIH (R = Me, Et, Bu-i) ... 

The aqua ions (M = Al, Ga, In, Tl) are acidic (see equation 6.34) and the acidity increases down the group. Solutions of their salts are appreciably hydrolysed and salts of weak acids (e.g. carbonates and cyanides) cannot exist in aqueous solution. Solution NMR spectroscopic studies show that in acidic media, Al(III) is present as octahedral [Al(H20)g], but raising the pH leads to the formation of polymeric species such as hydrated [Al2(OH)2] and [Al7(OH)ig] +. Further increase in pH causes Al(OH)3 to precipitate, and in alkaline solution, the aluminate anions [A1(0H)4] (tetrahedral) and [Al(OH)g] (octahedral) and polymeric species such as [(H0)3Al(p-0)Al(0H)3] are present. The aqueous solution chemistry of Ga(III) resembles that of Al(III), but the later metals are not amphoteric (see Section 12.7). 

Nitriles can be converted into primary amines by lithium tetrahydrido-aluminate or diborane. The products of such reactions, unlike those of catalytic hydrogenation, contain only small amounts of secondary and primary amines, so that these processes are particularly suitable for small batches in the laboratory. Alkali hydridoborates do not effect this reduction. 0.5 mole of lithium tetrahydridoaluminate is necessary for reduction of 1 mole of nitrile, but using an excess of reductant leads to better yields a 1 1 ratio is generally applied. Amundsen and his coworkers28 studied the optimal conditions for this reduction and describe reduction of heptyl cyanide as an example of a generally applicable procedure ... 

The Barin tables are far more complete in coverage than any of the sources described above. All of the natural elements and their compounds are included. In addition to the substance types listed in USBM Bull 677, the Barin tables include a large number of ternary oxides - aluminates, arsenates, borates, chromates, molybdates, nitrates, oxy-halides, phosphates, titanates, tungstates, selenates, vanadates, zirconates, etc. - as well as cyanides, hydroxides, complex silicates and inter-metallic compounds. The only substances not included by Barin, for which tables can be found elsewhere, are the ionized-gas species and a limited number of gas species important only at very high temperatures, which are listed in the JANAF tables. For each table Dr. Barin gives references for each of the major thermochemical values employed (enthalpy of formation and entropy at 298 K, and heat capacity). Like the USBM Bulletins, no attempt is made to discuss the choice between conflicting data sources. 

Potassium nitrate reacts with charcoal to produce potassium carbonate, potassium oxides, and potassium cyanide. More cyanide is formed at high temperature and pressure or in the presence of iron or its compounds. Potassium oxides are formed whenever potassium carbonate is held molten at atmospheric pressure. The rate of reaction is low, and the reaction is an equilibrium reaction which is easily reversed. At atmospheric pressure the molten material produced is predominantly potassium carbonate. The temperature achieved are sufficient to ignite aluminum. Flitter stars can be made with potassium nitrate and aluminum but charcoal is often added to lower the ignition temperature and render the stars more easily ignited. Similarly sulfur, antimony sulfide, or arsenic sulfide is used to start and control the burning of aluminum in flitter stars. Microscopic and microchemical examination of the sparks of such stars show a thin film of potassium oxides and potassium aluminates with some traces of liquid potassium oxide and potassium sulfide films over the mass of molten unreacted aluminum. 

Reaction (2.16) may proceed not only on the upper surface of blocks, but also on the surfaces of pores inside the block. Other reactions [17] of sodium-containing substances with carbon may take place, resulting in the formation of sodium aluminates, aluminium carbide, aluminium nitride, and sodium cyanide in the volume of carbon cathode blocks. 

Ammonium copper fluoride dihydrate Potassium cyanide Chi alumina Calcium aluminate Alpha cadmium iodide... 

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