SUBJECTS cobalt

Metals can be precipitated from the Hquid or gas phase. For example, nickel ammonium carbonate gives nickel powder when subjected to hydrogen in an autoclave. Copper, cobalt, molybdenum, and titanium powders can also be formed by precipitation. 

The second principal advantage is that CYANEX 272 is the only one of the three above-mentioned compounds that extracts cobalt in preference to calcium (52). This property can minimise or eliminate the solvent losses that are associated with calcium extraction and the subsequent precipitation of gypsum cmds in the scmbbing or stripping circuits. This is illustrated in Eigure 1 where calcium extraction is shown as a function of pH for the three subject reagents. 

Pressure-acid leaching was used to extract cobalt from Blackbird mine ores before its closing in 1974. The result was a very fine cobalt powder which was subjected to a seeding process to produce cobalt granules. Leaching methods are also used in the refinement of lateritic ores. 

Metals in the platinum family are recognized for their ability to promote combustion at lowtemperatures. Other catalysts include various oxides of copper, chromium, vanadium, nickel, and cobalt. These catalysts are subject to poisoning, particularly from halogens, halogen and sulfur compounds, zinc, arsenic, lead, mercury, and particulates. It is therefore important that catalyst surfaces be clean and active to ensure optimum performance. 

In a typical process adiponitrile is formed by the interaction of adipic acid and gaseous ammonia in the presence of a boron phosphate catalyst at 305-350°C. The adiponitrile is purified and then subjected to continuous hydrogenation at 130°C and 4000 Ibf/in (28 MPa) pressure in the presence of excess ammonia and a cobalt catalyst. By-products such as hexamethyleneimine are formed but the quantity produced is minimized by the use of excess ammonia. Pure hexamethylenediamine (boiling point 90-92°C at 14mmHg pressure, melting point 39°C) is obtained by distillation, Hexamethylenediamine is also prepared commercially from butadience. The butadiene feedstock is of relatively low cost but it does use substantial quantities of hydrogen cyanide. The process developed by Du Pont may be given schematically as ... 

A number of ferrites have been subjected to shock modification and studied with x-ray diffraction as well as static magnetization and Mossbauer spectroscopy [87V01], Studies were carried out on cobalt, nickel, and copper ferrites as well as magnetite (iron ferrite). 

Perfluoroalkyl or -aryl halides undergo oxidative addition with metal vapors to form nonsolvated fluonnated organometallic halides and this topic has been die subject of a review [289] Pentafluorophenyl halides react with Rieke nickel, cobalt, and iron to give bispentafluorophenylmetal compounds, which can be isolated in good yields as liquid complexes [290] Rieke nickel can also be used to promote the reaction of pentafluorophenyl halides with acid halides [297] (equation 193)... 

The production of cobalt is usually subsidiary to that of copper or nickel and the methods employed differ widely, depending on which of these it is associated with. In general the ore is subjected to appropriate roasting treatment so as to remove gangue material as a slag and produce a speiss of mixed metal and oxides. In the case of arsenical ores, AS2O6 is condensed and provides a valuable byproduct. In the case of copper ores, the primary process... 

Chiral salen chromium and cobalt complexes have been shown by Jacobsen et al. to catalyze an enantioselective cycloaddition reaction of carbonyl compounds with dienes [22]. The cycloaddition reaction of different aldehydes 1 containing aromatic, aliphatic, and conjugated substituents with Danishefsky s diene 2a catalyzed by the chiral salen-chromium(III) complexes 14a,b proceeds in up to 98% yield and with moderate to high ee (Scheme 4.14). It was found that the presence of oven-dried powdered 4 A molecular sieves led to increased yield and enantioselectivity. The lowest ee (62% ee, catalyst 14b) was obtained for hexanal and the highest (93% ee, catalyst 14a) was obtained for cyclohexyl aldehyde. The mechanism of the cycloaddition reaction was investigated in terms of a traditional cycloaddition, or formation of the cycloaddition product via a Mukaiyama aldol-reaction path. In the presence of the chiral salen-chromium(III) catalyst system NMR spectroscopy of the crude reaction mixture of the reaction of benzaldehyde with Danishefsky s diene revealed the exclusive presence of the cycloaddition-pathway product. The Mukaiyama aldol condensation product was prepared independently and subjected to the conditions of the chiral salen-chromium(III)-catalyzed reactions. No detectable cycloaddition product could be observed. These results point towards a [2-i-4]-cydoaddition mechanism. 

The reaction is a sensitive one, but is subject to a number of interferences. The solution must be free from large amounts of lead, thallium (I), copper, tin, arsenic, antimony, gold, silver, platinum, and palladium, and from elements in sufficient quantity to colour the solution, e.g. nickel. Metals giving insoluble iodides must be absent, or present in amounts not yielding a precipitate. Substances which liberate iodine from potassium iodide interfere, for example iron(III) the latter should be reduced with sulphurous acid and the excess of gas boiled off, or by a 30 per cent solution of hypophosphorous acid. Chloride ion reduces the intensity of the bismuth colour. Separation of bismuth from copper can be effected by extraction of the bismuth as dithizonate by treatment in ammoniacal potassium cyanide solution with a 0.1 per cent solution of dithizone in chloroform if lead is present, shaking of the chloroform solution of lead and bismuth dithizonates with a buffer solution of pH 3.4 results in the lead alone passing into the aqueous phase. The bismuth complex is soluble in a pentan-l-ol-ethyl acetate mixture, and this fact can be utilised for the determination in the presence of coloured ions, such as nickel, cobalt, chromium, and uranium. 

For the preparation of standard cobalt solutions, use analytical grade cobalt(II) chloride or spectroscopically pure cobalt dissolved in hydrochloric acid subject solutions containing 0, 5, 10, 25, 50, 100, 150, and 200 jug of Co to the whole procedure. 

Partenheimer showed (ref. 15) that when toluene was subjected to dioxygen in acetic acid no reaction occurred, even at 205 °C and 27 bar. He also showed that when a solution of cobalt(II) acetate in acetic acid at 113 °C was treated with dioxygen ca. 1 % of the cobalt was converted to the trivalent state. In the presence of a substituted toluene two reactions are possible formation of a benzyl radical via one-electron oxidation of the substrate or decarboxylation of the acetate ligand (Fig. 9). Unfortunately, at the temperatures required for a reasonable rate of ArCH3 oxidation (> 130 °C) competing decarboxylation predominates. As noted earlier, two methods have been devised to circumvent this undesirable... 

A number of cobalt carbonyl derivatives have been subjected to y-irradiation and subsequent EPR spectroscopic investigation. 

Ammoniacal leaching is typically applied to oxidic nickel-bearing materials that have been subjected to a reductive roast, which converts the cobalt and nickel present to their metallic form (or as ferro-alloys) and most of the iron to Fe11.106,107... 

Despite H/D kinetic isotope studies, application of modern techniques such as atomic force microscopy (AFM), electrochemical mass spectrometry (EMS) [60], and electrochemical quartz microbalance (EQCM), the mechanism of electroless nickel and cobalt, whatever reducing agent is involved, continues to be the subject of much discussion and varying opinions. 

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