Nickel salts

COT is prepared by the polymerization of ethyne at moderate temperature and pressure in the presence of nickel salts. The molecule is non-planar and behaves as a typical cyclic olefin, having no aromatic properties. It may be catalytically hydrogenated to cyclo-octene, but with Zn and dil. sulphuric acid gives 1,3,6-cyclooclairiene. It reacts with maleic anhydride to give an adduct, m.p. 166 C, derived from the isomeric structure bicyclo-4,2,0-octa-2,4,7-triene(I) ... 

Gyclooctatetraene (GOT). Tetramerization of acetylene to cyclooctatetraene [629-20-9], CgHg, although interesting, does not seem to have been used commercially. Nickel salts serve as catalysts. Other catalysts give ben2ene. The mechanism of this cyclotetramerhation has been studied (4). 

The reaction is initiated with nickel carbonyl. The feeds are adjusted to give the bulk of the carbonyl from carbon monoxide. The reaction takes place continuously in an agitated reactor with a Hquid recirculation loop. The reaction is mn at about atmospheric pressure and at about 40°C with an acetylene carbon monoxide mole ratio of 1.1 1 in the presence of 20% excess alcohol. The reactor effluent is washed with nickel chloride brine to remove excess alcohol and nickel salts and the brine—alcohol mixture is stripped to recover alcohol for recycle. The stripped brine is again used as extractant, but with a bleed stream returned to the nickel carbonyl conversion unit. The neutralized cmde monomer is purified by a series of continuous, low pressure distillations. 

In electroless deposition, the substrate, prepared in the same manner as in electroplating (qv), is immersed in a solution containing the desired film components (see Electroless plating). The solutions generally used contain soluble nickel salts, hypophosphite, and organic compounds, and plating occurs by a spontaneous reduction of the metal ions by the hypophosphite at the substrate surface, which is presumed to catalyze the oxidation—reduction reaction. 

Simple nickel salts form ammine and other coordination complexes (see Coordination compounds). The octahedral configuration, in which nickel has a coordination number (CN) of 6, is the most common stmctural form. The square-planar and tetrahedral configurations (11), iu which nickel has a coordination number of 4, are less common. Generally, the latter group tends to be reddish brown. The 5-coordinate square pyramid configuration is also quite common. These materials tend to be darker in color and mostiy green (12). 

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 plays a role in the Reppe polymeriza tion of acetylene where nickel salts act as catalysts to form cyclooctatetraene (62) the reduction of nickel haUdes by sodium cyclopentadienide to form nickelocene [1271 -28-9] (63) the synthesis of cyclododecatrienenickel [39330-67-1] (64) and formation from elemental nickel powder and other reagents of nickel(0) complexes that serve as catalysts for oligomerization and hydrocyanation reactions (65). 

Nickel salts form coordination compounds with many ligands. Dibromobis(tri- -butylphosphine)nickel(Il) [15242-92-9], [( -C4H2)3P]2NiBr2, dicyanoammineaquanickel(11), Ni(NH3)(H20)(CN)2, and bromonitrosobis(triphenylphosphine)nickel(Il) [14586-72-2], are complexes used for syntheses in preparative organonickel chemistry. 

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. 

Other simple nickel salts of organic acids include the oxalate [20543-06-0] oleate [68538-38-5], and stearate [2223-95-2]. The latter two have been used as oil-soluble nickel forms in the dyeing of synthetic polyolefin fibers (see Driers and metallic soaps). Nickel oxalate has been used as a catalyst intermediate (59). 

Eye and Skin Contact. Some nickel salts and aqueous solutions of these salts, eg, the sulfate and chloride, may cause a primary irritant reaction of the eye and skin. The most common effect of dermal exposure to nickel is allergic contact dermatitis. Nickel dermatitis may occur in sensitized individuals following close and prolonged contact with nickel-containing solutions or metallic objects such as jewelry, particularly pierced earrings. It is estimated that 8—15% of the female human population and 0.2—2% of the male human population is nickel-sensitized (125). 

Other Specialty Chemicals. In fuel-ceU technology, nickel oxide cathodes have been demonstrated for the conversion of synthesis gas and the generation of electricity (199) (see Fuel cells). Nickel salts have been proposed as additions to water-flood tertiary cmde-oil recovery systems (see Petroleum, ENHANCED oil recovery). The salt forms nickel sulfide, which is an oxidation catalyst for H2S, and provides corrosion protection for downweU equipment. Sulfur-containing nickel complexes have been used to limit the oxidative deterioration of solvent-refined mineral oils (200). 

Nickel salts and soaps have been used in electrosensitive copy paper for image development. Nickel bis-(3,5 di-Z fZ-butylsaHcylate) [68569-24-4] has been studied in pressure-sensitive color developer sheets (201). It has also been used for color stabili2ation of color copy paper (see Electroplating). 

A principal commercial appHcation of the hypophosphites is ia the electroless plating (qv) process. Nickel salts are chemically reduced by hypophosphites to form a smooth adherent nickel plating to protect the iateriors of large vessels and tank cars. The coating, which can be hardened by heat treatment, usually contains 8—10 wt % phosphoms and is highly impervious. 

Diacetone-L-sorbose (DAS) is oxidized at elevated temperatures in dilute sodium hydroxide in the presence of a catalyst (nickel chloride for bleach or palladium on carbon for air) or by electrolytic methods. After completion of the reaction, the mixture is worked up by acidification to 2,3 4,6-bis-0-isoptopyhdene-2-oxo-L-gulonic acid (2,3 4,6-diacetone-2-keto-L-gulonic acid) (DAG), which is isolated through filtration, washing, and drying. With sodium hypochlorite/nickel chloride, the reported DAG yields ate >90% (65). The oxidation with air has been reported, and a practical process was developed with palladium—carbon or platinum—carbon as catalyst (66,67). The electrolytic oxidation with nickel salts as the catalyst has also... 

The reaction is carried out in the Hquid phase at 373—463 K and 3 MPa (30 atm) of carbon monoxide pressure using nickel salt catalyst, or at 313 K and 0.1 MPa (1 atm) using nickel carbonyl as both the catalyst and the source of carbon monoxide. Either acryHc acid or methyl acrylate may be produced directly, depending on whether water or methanol is used as solvent (41). New technology for acryHc acid production uses direct propjdene oxidation rather than acetylene carbonylation because of the high cost of acetjdene. This new process has completely replaced the old in the United States (see... 

Dehalogenation of monochlorotoluenes can be readily effected with hydrogen and noble metal catalysts (34). Conversion of -chlorotoluene to Ncyanotoluene is accompHshed by reaction with tetraethyl ammonium cyanide and zero-valent Group (VIII) metal complexes, such as those of nickel or palladium (35). The reaction proceeds by initial oxidative addition of the aryl haHde to the zerovalent metal complex, followed by attack of cyanide ion on the metal and reductive elimination of the aryl cyanide. Methylstyrene is prepared from -chlorotoluene by a vinylation reaction using ethylene as the reagent and a catalyst derived from zinc, a triarylphosphine, and a nickel salt (36). 

Titanate Pigments. When a nickel salt and antimony oxide are calcined with mtile titanium dioxide at just below 1000°C, some of the added metals diffuse into the titanium dioxide crystal lattice and a yellow color results. In a similar manner, a buff may be produced with chromium and antimony a green, with cobalt and nickel and a blue, with cobalt and aluminum. These pigments are relatively weak but have extreme heat resistance and outdoor weatherabihty, eg, the yellow is used where a light cadmium could not be considered. They are compatible with most resins. 

Specifications, Analysis, and Toxicity. Dicyandiamide is identified quaHtatively by paper chromatography and quantitatively by ultraviolet spectrometry of the chromatogram. More commonly, total nitrogen analysis is used as a purity control or the dicyandiamide is converted by hydrolysis to guanylurea, which is determined gravimetrically as the nickel salt (50). Methods based on the precipitation of silver dicyandiamide picrate are sometimes used (51). Dicyandiamide can also be titrated with tetrabutylammonium hydroxide ia pyridine solution. Table 4 gives a typical analysis of a commercial sample. Dicyandiamide is essentially nontoxic. It may, however, cause dermatitis. 

In the past, juglone had been used to dye wool and cotton a yellowish brown. Although it no longer has any commercial value as a dye, it is a fungicide and as such finds use in the treatment of skin diseases. Its toxic properties have been made use of in catching fish. Juglone has been used to detect very small amounts of nickel salts since it gives a deep violet color with such salts. 

Nickel. Nickel plating continues to be very important. Many plating baths have been formulated, but most of the nickel plating is done in either Watts baths or sulfamate baths. Watts baths contain sulfate and chloride nickel salts along with boric acid, and were first proposed in 1916 (111). Nickel was first plated from sulfamate in 1938 (112) and patented in 1943 (108). The process was brought to market in 1950 (113). Typical bath compositions and conditions are shown in Table 14. 

Nickel salts are commercially available as Hquid concentrates. 

Nickel sulfamate is more soluble than the sulfate salt, and baths can be operated using higher nickel concentrations and higher currents. Sulfamate baths have been found to have superior microthrowing power, the abiUty to deposit in small cracks or crevices. Using one nickel salt, only a hydrometer and pH paper are needed to control the bath. A small amount of chloride salt was added as a proprietary. Highly purified nickel sulfamate concentrates are commercially available that can be used to make up new plating baths without further purification. 

Bright Nickel. Nickel as electroplated from pure nickel salts is a dull grey, satin—like deposit that has to be buffed to obtain a bright finish. 

ARBUZOV MICHAELIS Phosphonale Synihesis Ni catalyzed phosphonate synthesis from phosphites and aryl halides Reaction of alkyl halides with phosphites proceeds without nickel salts... 

In a permeation experiment, an HERO module with a membrane area of 200 m is used to remove a nickel salt from an electroplating wastewater. TTie feed to the module has a flowrate of 5 x IQ— m /s, a nickel-salt composition of 4,(X)0 ppm and an osmotic pressure of 2.5 atm. The average pressure difference across the membrane is 28 atm. The permeate is collected at atmospheric pressure. The results of the experiment indicate that the water recovery is 80% while the solute rejection is 95%. Evaluate the transport parameters Ay and (D2u/KS). 

Jfickeloxydul, n. nickelous oxide, nickel(II) oxide, NiO. -hydrat, n, nickelous hydroxide, nickel (II) hydroxide, -salz, n. nickelous salt, nickel(II) salt, -verbindung,/. nickelous compound, nickel(II) compound. Nickelpapier, n. nickel foil, nickelplattiert, a. nickel-plated. 

In certain concentrated acidic solutions, e.g. H2SO4, nickel, whilst not truly passive, may exhibit pseudo-passivity owing to crystallisation of a layer of nickel salt (in cone. H2SO4 probably /3-NiS04-6H20) on the surface". ... 

Commercial processes Commercial electroless nickel plating stems from an accidental discovery by Brenner and Riddell made in 1944 during the electroplating of a tube, with sodium hypophosphite added to the solution to reduce anodic oxidation of other bath constituents. This led to a process available under licence from the National Bureau of Standards in the USA. Their solutions contain a nickel salt, sodium hypophosphite, a buffer and sometimes accelerators, inhibitors to limit random deposition and brighteners. The solutions are used as acid baths (pH 4-6) or, less commonly, as alkaline baths (pH 8-10). Some compositions and operating conditions are given in Table 13.17 . 

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