Nickel carbonates

The carbon is often replaced by a catalyst such as platinized or nickelized carbon or a mixture of carbon, platinum and nickel. 

Nickel tetrafluoroborate [14708-14-6] Ni(BE 2 prepared by dissolving nickel carbonate in tetrafluoroboric acid [16872-11-0] HBE. Nickel... 

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). 

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 Carbonate. Nickel carbonate [3333-67-3], NiCO, is a light-green, rhombic crystalline salt, density 2.6 g/cm, that is very slightly soluble in water. The addition of sodium carbonate to a solution of a nickel salt precipitates an impure basic nickel carbonate. The commercial material is the basic salt 2NiCo2 3Ni(OH)2 4H20 [29863-10-3]. Nickel carbonate is prepared best by the oxidation of nickel powder in ammonia and CO2. Boiling away the ammonia causes precipitation of pure nickel carbonate (32). 

Nickel carbonate is used in the manufacture of catalysts, in the preparation of colored glass (qv), in the manufacture of certain nickel pigments, and as a neutralizing compound in nickel electroplating solutions. It also is used in the preparation of many specialty nickel compounds. 

Nickel Fluoroborate. Fluoroboric acid and nickel carbonate form nickel fluoroborate [14708-14-6] Ni(BF 2 6H20. Upon crystallization, the high purity product is obtained (47). Nickel fluoroborate is used as the electrolyte ia specialty high speed nickel plating. It is available commercially as a concentrated solution. 

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 Phosphate. Tri nickel orthophosphate [14396-43-17, Ni2(P0 2 7H20, exists as apple-green plates which decompose upon heating. It is prepared by the reaction of nickel carbonate and hot dilute phosphoric acid. Nickel phosphate is an additive to control the crystal size of ziac phosphate ia coaversioa coatiags which are appHed to steel prior to its being paiated (see Metal surface treatments). 

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. 

OtherTitanates. Nickel titanate [12035-39-1/, NiTiO, is a canary-yeUow soHd having a density of 73(00). When a mixture of antimony oxide, nickel carbonate, and titanium dioxide is heated at 980°C, nickel antimony titanate [8007-18-9] forms, which is used as a yellow pigment (95). 

In the nickel—carbon and cobalt—carbon systems, the nickel carbide (3 1) [12012-02-1], Ni C, and cobalt carbide (3 1) [12011-59-5] C03C, are isomorphous with Fe C and exist only at low temperatures. The manganese—carbon system contains manganese carbide (3 1) [12121 -90-3] Mn C, isomorphous with Fe C, and manganese carbide (23 6) [12266-65-8] isomorphous with chromium carbide (23 6) [12105-81 -6] These... 

Fig. 2. Diamond.-forming region for the nickel—carbon system (3). To convert GPa to kbar, multiply by 10.

Austenitic stainless steels are the most corrosion-resistant of the three groups. These steels contain 16 to 26 percent chromium and 6 to 22 percent nickel. Carbon is kept low (0.08 percent maximum) to minimize carbide precipitation. These alloys can be work-hardened, but heat treatment will not cause hardening. Tensile strength in the annealed condition is about 585 MPa (85,000 Ibf/in"), but workhardening can increase this to 2,000 MPa (300,000 Ibf/in"). Austenitic stainless steels are tough and ducdile. 

Lithium-nickel oxides form various lithium compounds, lithium hydroxides (LiOH), Li2C03, nickel hydroxide (Ni(OH)2), nickel carbonate (NiC03) and nickel oxide (NiO). Figure 51 shows the discharge characteristics of lithium-nickel oxides synthesized from these compounds. They were heat-treated at 850 °C for 20 h in air. Although the lithium nickel oxides showed a smaller discharge capacity than that of LiCo02, LiOH and Ni(OH)2 were considered to be appropi-ate raw materials. 

In the reaction of Ni(CNBu )4 and methyl iodide oligomerization of the isocyanide was observed the only isolable nickel complex was (I), shown below. This product is believed to arise through sequential insertions of three isocyanides into a nickel-carbon bond. Upon further treatment with additional isocyanide at a temperature greater than 60° C one obtains a polymer (RNC) presumably through multiple isocyanide insertion reactions. The addition of benzoyl chloride to Ni(CNBu )4 gave two isolable compounds Ni(CNBu )3(COPh)Cl (74%) and (II) (8.2%). This latter reaction, and the isolation of (II) in particular, suggests that the proposed mechanism for polymerization of isocyanides is reasonable. 

Mixing of the electrode products causes hydrolytic precipitation of the nickel and, after separation of the nickel hydroxide, the filtrate was returned to the cells. The sequence of the electrolytic purification steps is outlined in Figure 6.28. Nickel hydroxide slurry is first added to the anolyte for the purpose of raising the pH to 3.7 (2 H+ + Ni(OH) = Ni2+ + 2 H20), and iron(II) is oxidized by introducing chlorine. This causes hydrolytic precipitation of the iron(III) and corrects the nickel ion deficiency by the low anodic current efficiency. The iron(III) hydroxide is removed by filteration. The clarified solution is then treated with nickel carbonate and further chlorine to oxidize the cobalt(II) and allow its separation as cobalt(I II) hydroxide. 

X-Ray studies confirm that platinum crystallites exist on carbon supports at least down to a metal content of about 0.03% (2). On the other hand, it has been claimed that nickel crystallites do not exist in nickel/carbon catalysts (50). This requires verification, but it does draw attention to the fact that carbon is not inert toward many metals which can form carbides or intercalation compounds with graphite. In general, it is only with the noble group VIII metals that one can feel reasonably confident that a substantial amount of the metal will be retained on the carbon surface in its elemental form. Judging from Moss s (35) electron micrographs of a reduced 5% platinum charcoal catalyst, the platinum crystallites appear to be at least as finely dispersed on charcoal as on silica or alumina, or possibly more so, but both platinum and palladium (51) supported on carbon appear to be very sensitive to sintering. 

Derbishire, F. and Trimm, D., Kinetics of deposition of pyrolytic carbon on nickel, Carbon, 13, 189, 1975. 

Decomposition of either nickel hydroxide or nickel carbonate yields NiO, the only oxide of nickel of any importance. However, two oxides of copper are known, Cu20 and CuO. Of these, Cu20 is the more stable, and it is the product when CuO is heated to very high temperature. 

The behavior of 3 toward ether or amines on the one hand and toward phosphines, carbon monoxide, and COD on the other (Scheme 2), can be qualitatively explained on the basis of the HSAB concept4 (58). The decomposition of 3 by ethers or amines is then seen as the displacement of the halide anion as a weak hard base from its acid-base complex (3). On the other hand, CO, PR3, and olefins are soft bases and do not decompose (3) instead, complexation to the nickel atom occurs. The behavior of complexes 3 and 4 toward different kinds of electron donors explains in part why they are highly active as catalysts for the oligomerization of olefins in contrast to the dimeric ir-allylnickel halides (1) which show low catalytic activity. One of the functions of the Lewis acid is to remove charge from the nickel, thereby increasing the affinity of the nickel atom for soft donors such as CO, PR3, etc., and for substrate olefin molecules. A second possibility, an increase in reactivity of the nickel-carbon and nickel-hydrogen bonds toward complexed olefins, has as yet found no direct experimental support. 

Reactions leading to the formation of the catalytically active nickel hydride species from organonickel precursors (Section III) can be regarded as model reactions for olefin oligomerization reactions. The reactions described by Eq. (8) and Scheme 3 (Section III) show that RNiX compounds (R = methyl orallyl, X = halide or acetylacetonate) activated by Lewis acids add to double bonds under mild reaction conditions (-40° or 0°C). It follows further from these reactions that under conditions leading to olefin dimerization a rapid nickel hydride /3-hydrogen elimination reaction occurs. The fact that products resulting from olefin insertion into the nickel-carbon bond are only observed when /3-hydride... 

---