Nickel, chloride

No clear picture of complexing behavior in aqueous nickel chloride solutions has yet been presented. As with cobalt chloride, Libus and Tialowska (OlO) suggest the NiCl complex exists as an outer-sphere ion pair [NifOHa 6 ] 

They presented the following values for the stability constant at 25 C  

In 1980, Lagarde et al. (08) presented the results of their EXAFS (extended x-ray absorption fine structure) study of NiCl2 solutions. Previous studies, including Raman experiments (03, 04, 012), x-ray diffraction (01, 09, Oil), neutron diffraction (07, 013, 014) and inelastic neutron scattering (02) presented conflicting reports of ion pairing behavior. Lagarde et al. were unable to conclude whether there was complex formation or not. 

A more definite picture is presented in the literature for cupric chloride solutions. Lagarde et al. (08) found evidence of Cu-Cl pairing in their EXAFS study, as did Libus (09) in spectrophotometric measurements which resulted in the following stability constants at 25 C  

A uniform view of complexes in a cupric chloride solution is found in the NBS (1) and Russian (2) thermodynamic data tables. Both present data for not only the CuCl complex, but also the aqueous molecule CuClj  

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The 5-nitrosallcylaldehyde reagent is prepared as follows. Add 0-5 g. of 5-nitrosalicylaldehyde (m.p. 124-125°) to 15 ml. of pure triethanolamine and 25 ml. of water shake until dissolved. Then introduce 0-5 g. of crystallised nickel chloride dissolved in a few ml. of water, and dilute to 100 ml. with water. If the triethanolamine contains some ethanolamine (thus causing a precipitate), it may be necessary to add a further 0 - 5 g. of the aldehyde and to filter off the resulting precipitate. The reagent is stable for long periods. 

The carbon disulphide reagent is prepared by adding to a solution of 0-5 g. of crystallised nickel chloride in 100 ml. of water enough carbon disulphide so that after shaking a globule of carbon disulphide is left at the bottom of the bottle. The reagent is stable for long periods in a well-stoppered bottle. If all the carbon disulphide evaporates, more must be added. 

The stoichiometric and the catalytic reactions occur simultaneously, but the catalytic reaction predominates. The process is started with stoichiometric amounts, but afterward, carbon monoxide, acetylene, and excess alcohol give most of the acrylate ester by the catalytic reaction. The nickel chloride is recovered and recycled to the nickel carbonyl synthesis step. The main by-product is ethyl propionate, which is difficult to separate from ethyl acrylate. However, by proper control of the feeds and reaction conditions, it is possible to keep the ethyl propionate content below 1%. Even so, this is significantly higher than the propionate content of the esters from the propylene oxidation route. 

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. 

Nickel [7440-02-0] Ni, recognized as an element as early as 1754 (1), was not isolated until 1820 (2). It was mined from arsenic sulfide mineral deposits (3) and first used in an alloy called German Silver (4). Soon after, nickel was used as an anode in solutions of nickel sulfate [7786-81 A] NiSO, and nickel chloride [7718-54-9] NiCl, to electroplate jewelry. Nickel carbonyl [13463-39-3] Ni(C02)4, was discovered in 1890 (see Carbonyls). This material, distilled as a hquid, decomposes into carbon monoxide and pure nickel powder, a method used in nickel refining (5) (see Nickel and nickel alloys). 

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... 

When nickel hydroxide is oxidized at the nickel electrode in alkaline storage batteries the black trivalent gelatinous nickel hydroxide oxide [12026-04-9], Ni(0H)0, is formed. In nickel battery technology, nickel hydroxide oxide is known as the nickel active mass (see Batteries, secondary cells). Nickel hydroxide nitrate [56171-41-6], Ni(0H)N02, and nickel chloride hydroxide [25965-88-2], NiCl(OH), are frequently mentioned as intermediates for the production of nickel powder in aqueous solution. The binding energies for these compounds have been studied (55). 

The chain-growth catalyst is prepared by dissolving two moles of nickel chloride per mole of bidentate ligand (BDL) (diphenylphosphinobenzoic acid in 1,4-butanediol). The mixture is pressurized with ethylene to 8.8 MPa (87 atm) at 40°C. Boron hydride, probably in the form of sodium borohydride, is added at a molar ratio of two borohydrides per one atom of nickel. The nickel concentration is 0.001—0.005%. The 1,4-butanediol is used to solvent-extract the nickel catalyst after the reaction. 

The vapor-phase conversion of aniline to DPA over a soHd catalyst has been extensively studied (18,22). In general, the catalyst used is pure aluminum oxide or titanium oxide, prepared under special conditions (18). Promoters, such as copper chromite, nickel chloride, phosphoric acid, and ammonium fluoride, have also been recommended. Reaction temperatures are usually from 400 to 500°C. Coke formed on the catalyst is removed occasionally by burning. In this way, conversions of about 35% and yields of 95% have been reported. Carba2ole is frequently a by-product. 

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... 

A battery system closely related to Na—S is the Na—metal chloride cell (70). The cell design is similar to Na—S however, ia additioa to the P-alumiaa electrolyte, the cell also employs a sodium chloroalumiaate [7784-16-9J, NaAlCl, molten salt electrolyte. The positive electrode active material coasists of a transitioa metal chloride such as iroa(Il) chloride [7758-94-3] EeQ.25 or nickel chloride [7791-20-0J, NiQ.25 (71,72) in Heu of molten sulfur. This technology is in a younger state of development than the Na—S. 

The most common plafing bath uses fluoride to complex the fin. A typical solution contains 45 g/L staimous chloride, 300 g/L nickel chloride hexahydrate, and 55 g/L ammonium bifluofide. It is operated at pH 2.0—2.5 usiag ammonium hydroxide temperature is 65—75°C and current about 200 A/m. The bath has excellent throwing power. Air agitation is avoided. The deposit is bright without additives. Anodes are cast nickel, and the fin is replenished by additions of staimous chloride. AHoy anodes of 72% fin have been used to a much lesser extent. Tia-nickel deposits are covered by ASTM (136) and ISO (137) specifications. One other bath based on pyrophosphate has appeared ia the Hterature, but does not seem to be ia commercial use. 

TABLE 2-63 Nickel Chloride (NiCI,) TABLE 2-64 Nickel Nitrate [Ni(N03),l TABLE 2-65 Nickel Sulfate (NiSO ) ... 

Nickel chloride (6H2O) [7791-20-0 (6H2O) 69098-15-3 (xHiO) 7718-54-9 (anhydr)] M 237.7. Crystd from dilute HCl. 

These are initial rates of acetohydroxamic acid formation from acetic acid, catalyzed by nickel chloride. 

Typical plating solutions contain l0-30g/l of nickel chloride or sulfate and l0-50g/l NaH2P02 with suitable pump capacities it is possible to plate up to 10 kg Ni per hour from stich a bath (i.e. 45 m stirface to a thickness of 25 pm). Chemical plating is more expensive than normal electrolytic plating btit is competitive when intricate shapes are being plated and is essential for non-conducting substrates. (Sec also the use of BH.4 in this connection, p. 167.)... 

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