Oxides nickel

Nickel oxide, NiO, which adopts the sodium chloride structure (Fig. 1.14), can readily be made slightly oxygen rich, and, because the solid then contains more oxygen than nickel, the crystal must also contain a population of point defects. This situation can formally be considered as a reaction of oxygen gas with stoichiometric NiO, and the simplest assumption is to suppose that the extra oxygen extends the crystal by adding extra oxygen sites. Atoms are added as neutral atoms, and 

The charges balance, in accordance with rule 3 above. Finally, it may be regarded as reasonable to assume that the added oxygen ends up as O2-. In this case each added atom of oxygen must gain two electrons. These will be taken from another source in the crystal, thereby generating two positive holes, h  

The creation of each vacancy is accompanied by the creation of a hole. If the ionic assumption is correct, the solid would therefore be expected to behave as a p-type semiconductor. This is, in fact, the case for NiO. However, if for some analogous case this is not confirmed experimentally, the equation is not valid. 

Chemically, it might be preferable to specify exactly the source of the electrons donated to form O2- ions in NiO. The physical properties of the solid suggest that the two electrons actually come from separate Ni2+ ions, converting each of them to the ion Ni3+. The defect is then a Ni3+ ion located on a Ni2+ site. This defect has an effective positive charge of one unit compared to the Ni2+ ion, so it would be written Ni. Taking this into account, the reaction Eq. (1.4) needs to be 

This reveals that two alternative defect structures can be imagined, one with free holes and one with Ni3+ defects. A further possibility is that the hole may be lightly bound to an Ni2+ ion to give a defect complex that could be written (NiNi + h ). All of these descriptions are valid. The one adopted would be the one most consistent with the measured properties of the solid. 

Nickel(ii) oxide, NiO, possesses electrochromic properties and has been prepared by the CVD of nickel acetylacetate (Ni(acac)2 acac 6) [58, 67, 68]. 

It was deemed necessary, in a study on the evolution of the electrical behavior of this material in the presence of gases, and particularly in the presence of sulfur dioxide, to better analyze and control its chemical sirrface states under different temperatme and oxygen pressirre conditions. 

The samples studied were in pirlverulent form and weighed 1 g. The heating rate was 14°C/min. 

To better grasp and characterize these different species, we adopted a protocol that consisted of controlhng the temperature that corresponds to oxygen admittance on a perfectly degassed sample. It is reasonable to think that the concentration of each adsorbed species, which is related to its adsorption or desorption rate, is a function of temperature and oxygen treatment time. 

From a practical standpoint, the sample that is degassed for one night at 750°C is subjected to 100 Pa pressitre oxygen at the temperature Ta and for a time t. After 

The effects of introducing the gas at the temperature Ta are shown in Figitre 6.22 for foirr different temperature values, with an oxygen expositre time t of one horn and a degassing temperature of 20°C. 

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Within the periodic Hartree-Fock approach it is possible to incorporate many of the variants that we have discussed, such as LFHF or RHF. Density functional theory can also be used. I his makes it possible to compare the results obtained from these variants. Whilst density functional theory is more widely used for solid-state applications, there are certain types of problem that are currently more amenable to the Hartree-Fock method. Of particular ii. Icvance here are systems containing unpaired electrons, two recent examples being the clci tronic and magnetic properties of nickel oxide and alkaline earth oxides doped with alkali metal ions (Li in CaO) [Dovesi et al. 2000]. 

The first process utilizes a bed of nickel catalyst which has been regenerated with hydrogen to reduce the nickel content to metallic form. The finely divided metal then reacts with impurities and retains them in the bed, probably as nickel oxide in the case of oxygen or as physisorbed compounds for other impurities. Periodically, the bed is regenerated at elevated temperature using hydrogen to restore the metallic content. The nickel process can be used and regenerated indefinitely. 

Molten Carbonate Fuel Cell. The electrolyte ia the MCFC is usually a combiaation of alkah (Li, Na, K) carbonates retaiaed ia a ceramic matrix of LiA102 particles. The fuel cell operates at 600 to 700°C where the alkah carbonates form a highly conductive molten salt and carbonate ions provide ionic conduction. At the operating temperatures ia MCFCs, Ni-based materials containing chromium (anode) and nickel oxide (cathode) can function as electrode materials, and noble metals are not required. 

Na.tura.1 Ga.s Reforma.tion. In the United States, most hydrogen is presently produced by natural gas reformation or methane—steam reforming. In this process, methane mixed with steam is typically passed over a nickel oxide catalyst at an elevated temperature. The reforming reaction is... 

An emerging electrochemical appHcation of lithium compounds is in molten carbonate fuel ceUs (qv) for high efficiency, low poUuting electrical power generation. The electrolyte for these fuel ceUs is a potassium carbonate—hthium carbonate eutectic contained within a lithium aluminate matrix. The cathode is a Hthiated metal oxide such as lithium nickel oxide. 

The matte can be treated in different ways, depending on the copper content and on the desired product. In some cases, the copper content of the Bessemer matte is low enough to allow the material to be cast directly into sulfide anodes for electrolytic refining. Usually it is necessary first to separate the nickel and copper sulfides. The copper—nickel matte is cooled slowly for ca 4 d to faciUtate grain growth of mineral crystals of copper sulfide, nickel—sulfide, and a nickel—copper alloy. This matte is pulverized, the nickel and copper sulfides isolated by flotation, and the alloy extracted magnetically and refined electrolyticaHy. The nickel sulfide is cast into anodes for electrolysis or, more commonly, is roasted to nickel oxide and further reduced to metal for refining by electrolysis or by the carbonyl method. Alternatively, the nickel sulfide may be roasted to provide a nickel oxide sinter that is suitable for direct use by the steel industry. 

Pyrometa.llurgica.1 Processes. Nickel oxide ores are processed by pyrometaHurgical or hydrometaHurgical methods. In the former, oxide ores are smelted with a sulfiding material, eg, gypsum, to produce an iron—nickel matte that can be treated similarly to the matte obtained from sulfide ores. The iron—nickel matte may be processed in a converter to eliminate iron. The nickel matte then can be cast into anodes and refined electrolyticaHy. 

HydrometaHurgical Processes. The hydrometaHurgical treatments of oxide ores involve leaching with ammonia or with sulfuric acid. In the ammoniacal leaching process, the nickel oxide component of the ore first is reduced selectively. Then the ore is leached with ammonia which removes the nickel into solution, from which it is precipitated as nickel carbonate by heating. A nickel oxide product used in making steel is produced by roasting the carbonate. 

Ma.nufa.cture. Several nickel oxides are manufactured commercially. A sintered form of green nickel oxide is made by smelting a purified nickel matte at 1000°C (30) a powder form is made by the desulfurization of nickel matte. Black nickel oxide is made by the calcination of nickel carbonate at 600°C (31). The carbonate results from an extraction process whereby pure nickel metal powder is oxidized with air in the presence of ammonia (qv) and carbon dioxide (qv) to hexaamminenickel(TT) carbonate [67806-76-2], [Ni(NH3)3]C03 (32). Nickel oxides also ate made by the calcination of nickel carbonate or nickel nitrate that were made from a pure form of nickel. A high purity, green nickel oxide is made by firing a mixture of nickel powder and water in air (25). 

Uses. The sinter oxide form is used as charge nickel in the manufacture of alloy steels and stainless steels (see Steel). The oxide furnishes oxygen to the melt for decarburization and slagging. In 1993, >100, 000 metric tons of nickel contained in sinter oxide was shipped to the world s steel industry. Nickel oxide sinter is charged as a granular material to an electric furnace with steel scrap and ferrochrome the mixture is melted and blown with air to remove carbon as CO2. The melt is slagged, pouted into a ladle, the composition is adjusted, and the melt is cast into appropriate shapes. A modification of the use of sinter oxide is its injection directiy into the molten metal (33). 

Properties. Nickel sulfate hexahydrate [10101 -97-0], NiSo 6H20 is a monoclinic emerald-green crystalline salt that dissolves easily in water and in ethanol. When heated, it loses water and above 800°C decomposes into nickel oxide and SO3. Its density is 2.03 g/cm. ... 

Nickel sulfate also is made by the reaction of black nickel oxide and hot dilute sulfuric acid, or of dilute sulfuric acid and nickel carbonate. The reaction of nickel oxide and sulfuric acid has been studied and a reaction induction temperature of 49°C deterrnined (39). High purity nickel sulfate is made from the reaction of nickel carbonyl, sulfur dioxide, and oxygen in the gas phase at 100°C (40). Another method for the continuous manufacture of nickel sulfate is the gas-phase reaction of nickel carbonyl and nitric acid, recovering the soHd product in sulfuric acid, and continuously removing the soHd nickel sulfate from the acid mixture (41). In this last method, nickel carbonyl and sulfuric acid are fed into a closed-loop reactor. Nickel sulfate and carbon monoxide are produced the CO is thus recycled to form nickel carbonyl. 

Nickel chloride hexahydrate [7791-20-0] is formed by the reaction of nickel powder or nickel oxide with a hot mixture of water and HCl. Nickel duoride [13940-83-5], 4H2O, is prepared by the reaction of hydroduoric acid on nickel carbonate. Nickel bromide [18721 -96-5], NiBr2 6H20, is made... 

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). 

Nickel Arsenate. Nickel arsenate [7784-48-7] Ni2(As0 2 8H20, is a yellowish green powder, density 4.98 g/cm. It is highly iasoluble ia water but is soluble ia acids, and decomposes on heating to form As20 and nickel oxide. Nickel arsenate is formed by the reaction of a water solution of arsenic anhydride and nickel carbonate. Nickel arsenate is a selective hydrogenation catalyst for iaedible fats and oils (59). 

Nickel Salts and Chelates. Nickel salts of simple organic acids can be prepared by reaction of the organic acid and nickel carbonate of nickel hydroxide reaction of the acid and a water solution of a simple nickel salt and, in some cases, reaction of the acid and fine nickel powder or black nickel oxide. 

Nickel acetate tetrahydrate [6018-89-9] Ni(C2H202) 4H2O, is a green powder which has an acetic acid odor, density 1.74 g/cm. When heated, it loses its water of crystallization and then decomposes to form nickel oxide. Nickel acetate is used as a catalyst intermediate, as an intermediate in the formation of other nickel compounds, as a dye mordant, as a sealer for anodized aluminum, and in nickel electroplating (59). 

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