Nickel retention

Nickel retention in the body of mammals is low. The half-time residence of soluble forms of nickel is several days, with little evidence for tissue accumulation except in the lung (USEPA 1980, 1986). Radionickel-63 (63Ni) injected into rats and rabbits cleared rapidly most (75%) of the injected dose was excreted within 24 to 72 h (USEPA 1980). Nickel clears at different rates from various tissues. In mammals, clearance was fastest from serum, followed by kidney, muscle, stomach, and uterus relatively slow clearance was evident in skin, brain, and especially lung (Kasprzak 1987). The half-time persistence in human lung for insoluble forms of nickel is 330 days (Sevin 1980). 

Both regio- and stereospecificiiy may be influenced by the catalyst and by alkali. Raney nickel opens ce>2,3-diphenylbul-2-ene epoxide with retention of configuration to give cr3 f/iro-2,3-diphenylbutan-2-ol, whereas palladium-on-carbon gives the inverted threo isomer. If a small amount of alkali is added to nickel-catalyzed reductions, nickel too gives the threo isomer (d5). 

Aziridines, like oxiranes, undergo hydrogenolysis easily with or without inversion of configuration, depending on the catalyst, reaction parameters, and various additives 65aJ08). For example, hydrogenolysis of 2-methyl-2-phenylaziridine in ethanol occurs mainly with inversion over palladium but with retention over platinum, Raney nickel, or Raney cobalt. Benzene solvent or alkali favor retention over palladium as well. 

Hydrogenolysis of cxo-2-phenyl-9-oxabicyclo[3.3, l]nonan-2-ol proceeds exclusively with retention over Raney nickel and with inversion over palladium. No reduction with palladium occurred at all until a drop of perchloric acid was added (36). 

Articles of complex shape may be impossible to electroplate satisfactorily, and electroless nickel (see Section 12.5) may be useful in providing a relatively uniform protective coating. Even so, the considerations of access of cleaning and process solutions, and retention/draining of all process solutions, still apply. 

Halide exchange, sometimes call the Finkelstein reaction, is an equilibrium process, but it is often possible to shift the equilibrium." The reaction is most often applied to the preparation of iodides and fluorides. Iodides can be prepared from chlorides or bromides by taking advantage of the fact that sodium iodide, but not the bromide or chloride, is soluble in acetone. When an alkyl chloride or bromide is treated with a solution of sodium iodide in acetone, the equilibrium is shifted by the precipitation of sodium chloride or bromide. Since the mechanism is Sn2, the reaction is much more successful for primary halides than for secondary or tertiary halides sodium iodide in acetone can be used as a test for primary bromides or chlorides. Tertiary chlorides can be converted to iodides by treatment with excess Nal in CS2, with ZnCl2 as catalyst. " Vinylic bromides give vinylic iodides with retention of configuration when treated with KI and a nickel bromide-zinc catalyst," or with KI and Cul in hot HMPA." ... 

Nickel carbonyl has been shown to have a very high retention— 98.7%—both in the pure hquid and as 10% solution in n-heptane. It was argued that this represents the results following essentially complete isotopic exchange. Since the exchange of CO with Ni(CO)4 is known to occur quite rapidly by a dissociation mechanism, reformation of nickel carbonyl following the nuclear reaction would proceed rapidly by the reaction... 

Initially the nickel-chromium plating process is designed to minimize the liquid loading to the waste treatment system. Counterflow rinsing, spray rinsing, and stagnant rinse recovery methods are employed in order to minimize the amount of wastes to be treated and allow as much treatment or retention time in the waste treatment system as is possible. 

The olefinic C=C double bond is easy to reduce, under mild conditions, with most of the hydrogenation catalysts, with noble metals, with different forms of nickel as heterogeneous catalysts, with Rh, Pt, Co complexes and with Ziegler catalysts as homogeneous catalysts. In the hydrogenation of dienes and polyenes the selectivity is the most important issue, i.e. how can one double bond be saturated with retention of the other(s). When high selectivity is required, homogeneous catalysts are used. Nevertheless, as known, their separation from the reaction mixture is a difficult task. 

Halides The nickel-catalyzed cathodic addition of (Z)- or ( )-alkenylhahdes to electron-deficient olefins in the presence of a sacrificial iron rod anode proceeds with complete retention of... 

Despite the excess of alkyne used, the transfer of only one vinylic group was observed. A more general approach of this method involves the reaction of (Z,Z)- and (f ,fi)-divinylic tellurides with alkynes under nickel catalysis, to give (Z)- and ( )-enynes with complete retention of configuration."... 

In contrast to phenolic hydroxyl, benzylic hydroxyl is replaced by hydrogen very easily. In catalytic hydrogenation of aromatic aldehydes, ketones, acids and esters it is sometimes difficult to prevent the easy hydrogenolysis of the benzylic alcohols which result from the reduction of the above functions. A catalyst suitable for preventing hydrogenolysis of benzylic hydroxyl is platinized charcoal [28], Other catalysts, especially palladium on charcoal [619], palladium hydride [619], nickel [43], Raney nickel [619] and copper chromite [620], promote hydrogenolysis. In the case of chiral alcohols such as 2-phenyl-2-butanol hydrogenolysis took place with inversion over platinum and palladium, and with retention over Raney nickel (optical purities 59-66%) [619]. 

Hydrocarbon adsorption experiments show significant differences between the nickel contaminated zeolitic and non-zeolitic particles at metals levels comparable to those of the catalytic experiments. Neither hexane nor 1-hexene showed any interaction with nickel on the low surface area, non-zeolitic particles (the unpromoted material of Table I) at temperatures up to 425 C. Additionally, no interaction between hexene and the nickel on the zeolitic particles was observed over the temperature range studied. However, the nickel on the zeolitic component did cause significant retention of hexane at temperatures as low as 200 C with generation of what appeared to be higher molecular weight products. No cracking products were observed. With the uncontaminated zeolitic particles, hexane retention only occurred at temperatures above 300°C. Thus, the lower temperature retention for the contaminated particles appears to be due to the presence of nickel. 

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