Nickel, electrolytic preparation

Fig. 12. Morphology of Raney-nickel-coated cathodes for hydrogen evolution from caustic electrolytes (a) surface of Ni-Zn precursor coatings, (b) surface of Raney-nickel coating prepared by caustic leaching of the Zn content of the precursor, (c) cut through a Raney-nickel coating.

One recent, important development has been (136) the electrolytic preparation from [Ni"(CN)4]2- of [Ni CN H ]-, which has a half-life of 11 minutes in acidic solution at 25°C and serves as a precursor for the incorporation of nickel(III) in other ligand system. The complex is tetragonally elongated from its EPR spectrum and can add other anions axially. The bis aquo species has an absorption... 

Fluorine cannot be prepared directly by chemical methods. It is prepared in the laboratory and on an industrial scale by electrolysis. Two methods are employed (a) using fused potassium hydrogen-fluoride, KHFj, ill a cell heated electrically to 520-570 K or (b) using fused electrolyte, of composition KF HF = 1 2, in a cell at 340-370 K which can be electrically or steam heated. Moissan, who first isolated fluorine in 1886, used a method very similar to (b) and it is this process which is commonly used in the laboratory and on an industrial scale today. There have been many cell designs but the cell is usually made from steel, or a copper-nickel alloy ( Monel metal). Steel or copper cathodes and specially made amorphous carbon anodes (to minimise attack by fluorine) are used. Hydrogen is formed at the cathode and fluorine at the anode, and the hydrogen fluoride content of the fused electrolyte is maintained by passing in... 

Nickel Sulfamate. Nickel sulfamate [13770-89-3] Ni(S02NH2)2 4H2O, commonly is used as an electrolyte ia nickel electroforming systems, where low stress deposits are required. As a crystalline entity for commercial purposes, nickel sulfamate never is isolated from its reaction mixture. It is prepared by the reaction of fine nickel powder or black nickel oxide with sulfamic acid ia hot water solution. Care must be exercised ia its preparation, and the reaction should be completed rapidly because sulfamic acid hydrolyzes readily to form sulfuric acid (57). 

Electrochemistry and Kinetics. The electrochemistry of the nickel—iron battery and the crystal stmctures of the active materials depends on the method of preparation of the material, degree of discharge, the age (Life cycle), concentration of electrolyte, and type and degree of additives, particularly the presence of lithium and cobalt. A simplified equation representing the charge—discharge cycle can be given as ... 

Foreign cations can increasingly lower the yield in the order Fe, Co " < Ca " < Mn < Pb " [22]. This is possibly due to the formation of oxide layers at the anode [42], Alkali and alkaline earth metal ions, alkylammonium ions and also zinc or nickel cations do not effect the Kolbe reaction [40] and are therefore the counterions of choice in preparative applications. Methanol is the best suited solvent for Kolbe electrolysis [7, 43]. Its oxidation is extensively inhibited by the formation of the carboxylate layer. The following electrolytes with methanol as solvent have been used MeOH-sodium carboxylate [44], MeOH—MeONa [45, 46], MeOH—NaOH [47], MeOH—EtsN-pyridine [48]. The yield of the Kolbe dimer decreases in media that contain more than 4% water. 

Preparation. High purity nickel can be produced through electrolytic process or by the carbonyl process. In the latter case carbon monoxide reacts at 50°C with impure Ni (or nickel-copper matte) to give the volatile tetracarbonyl from which the metal (99.9-99.99% purity) is obtained by decomposition at 200-230°C through the reaction ... 

Electrochemically generated nickei(lll) oxide, deposited onto a nickel plate, is generally useful for the oxidation of alcohols in aqueous alkali [49]. The immersion of nickel in aqueous alkali results in the formation of a surface layer of nickel(ll) oxide which undergoes reversible electrochemical oxidation to form nickel(lll) oxide with a current maximum in cyclic voltammetry at 1.13 V vj. see, observed before the evolution of oxygen occurs [50]. This electrochemical step is fast and oxidation at a prepared oxide film, of an alcohol in solution, is governed by the rate of the chemical reaction between nickel oxide and the substrate [51]. When the film thickness is increased to about 0.1 pm, the oxidation rate of organic species increases to a rate that is fairly indifferent to further increases in the film thickness. This is probably due to an initial increase in the surface area of the electrode [52], In laboratory scale experiments, the nickel oxide electrode layer is prepared by prior electrolysis of nickel sulphate at a nickel anode [53]. It is used in an undivided cell with a stainless steel cathode and an alkaline electrolyte. 

Nickel hydroxide in high purity is prepared by an electrolytic process using metalhc nickel as the anode and nickel nitrate solution as the electrolyte. Nickel hydroxide is electrodeposited at an inert cathode. 

Nickel sulfamate is used as an electrolyte in nickel electroplating systems. Preparation... 

Pure nickel electrodeposits with macropores were prepared from electrolytic solutions of 0.2 mol dm NiCl2 and NH4CI with concentrations varying between 0.25 and 4 mol dm [64]. The effects of the electrodeposition current density and the NH4CI concentration on the surface morphology were determined. Surface area, faradaic efficiency, and fractal dimension... 

Numerous methods for the synthesis of salicyl alcohol exist. These involve the reduction of salicylaldehyde or of salicylic acid and its derivatives. The alcohol can be prepared in almost theoretical yield by the reduction of salicylaldehyde with sodium amalgam, sodium borohydride, or lithium aluminum hydride by catalytic hydrogenation over platinum black or Raney nickel or by hydrogenation over platinum and ferrous chloride in alcohol. The electrolytic reduction of salicylaldehyde in sodium bicarbonate solution at a mercury cathode with carbon dioxide passed into the mixture also yields saligenin. It is formed by the electrolytic reduction at lead electrodes of salicylic acids in aqueous alcoholic solution or sodium salicylate in the presence of boric acid and sodium sulfate. Salicylamide in aqueous alcohol solution acidified with acetic acid is reduced to salicyl alcohol by sodium amalgam in 63% yield. Salicyl alcohol forms along with -hydroxybenzyl alcohol by the action of formaldehyde on phenol in the presence of sodium hydroxide or calcium oxide. High yields of salicyl alcohol from phenol and formaldehyde in the presence of a molar equivalent of ether additives have been reported (60). Phenyl metaborate prepared from phenol and boric acid yields salicyl alcohol after treatment with formaldehyde and hydrolysis (61). 

The impregnation of porous nickel discs with CoPc was difficult because of the limited solubility of the chelate in the usual solvents. CoPc cathodes with carbon as substrate were therefore prepared for use in H2/O2 fuel cells. A mixture of 72 mg CoPc and 48 mg acetylene black, with PTFE as binder, was pressed into a nickel mesh of area 5 cm2. Electrodes of this type were tested in an H2/O2 fuel cell with 35% KOH electrolyte in an asbestos matrix at 80° C. Figure 5 compares the current/voltage characteristics of CoPc cathodes (14 mg/cm2) with those of other catalysts, including platinum (9 mg/cm2), silver (40 mg/cm2), and pure acetylene black (20 mg/cm2). An hydrogen electrode (9 mg Pt/cm2) was used as the anode in all tests. To facilitate comparison of the activity of different cathodes, the pure ohmic internal resistance of the cells (of the order of 0.02 ohm) was eliminated. 

Another example has been found in the author s laboratory. In the course of studies on the synthesis of metal-olefin complexes by means of cathodic reduction in dry organic mediums, a variety of linear oligomers were prepared on the nickel atom formed at the platinum cathode in electrolytic solution (32). The solution contained tetracispyridine nickel perchlorate or nickel dichloride and butadiene in ethanol or dimethoxye-thane, using tetrabutylammonium perchlorate as an electrolyte. 

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