Determination of Nickel II

I. Narin, M. Soylak, Enrichment and determinations of nickel (II), cadmium(II), copper(II), cobalt(II), and lead(II) ions in natural waters, table salts, tea and urine samples as pyrrolydine dithiocarbamate chelates by membrane filtration-flame atomic absorption spectrometry combination, Anal. Chim. Acta, 493 (2003), 205-212. 

F. Albertus, A. Cladera, E. Becerra, V. Cerda, A robust multi-syringe system for process flow analysis. Part 3. Time based injection applied to the spectrophotometric determination of nickel(II) and iron speciation, Analyst 126 (2001) 903. 

Structure determination of nickel(II)-containing ARD has revealed a mononuclear nickel(II) center ligated by four protein ligands His-96, His-98, Glu-102, and His-140. The substrate is believed to coordinate to the two vacant coordination sites as the dianion. The protein fold is similar to enzymes of the cupin superfamily. 

Katiyar, G. S. Haidar, B. C. Rapid extraction and direct spectrophotometric determination of nickel(II) with isonitrosothiocamphor. Indian J. Chem. 1983, 22A, 1084-1085. 

RengCT F, Svancara I, Suska M (1992) Voltammetric determination of nickel(II) and cobalt (n) at a carbon paste electrode and its applicatimi under expedition conditions. Sb Ved Pr, Vys Sk Chcanickoteclmol, Pardubice 56 5-19... 

The well-known reaction of Ni(II) with dimethylglyoxime (H Dm) in alkaline medium under the influence of such oxidants as persulphate and iodine is widely used for the photometric determination of nickel. The red product (RP) of this reaction is used for this purpose. However, the nature of this red compound has not been defined yet. Using of peroxyacids makes it possible to obtain additional data concerning the conditions and mechanism of generation of RP as well as to improve the metrological pai ameters of the method. 

Since the octahedral and tetrahedral configurations have the same number of unpaired electrons (that is, 2 unpaired electrons), we cannot use magnetic properties to determine whether the ammine complex of nickel(II) is Octahedral or tetrahedral. But we can determine if the complex is square planar, since the square planar complex is diamagnetic with zero unpaired electrons. 

Two polarographic methods have been developed for the determination of cohalt(II) at concentrations ranging from approximately 1 to 80 mM in an aqueous sample. For the first method [15], which is suitable for samples containing large amounts of nickel]11), the cobalt(II) is oxidized to Co(NH3)6 in an ammoniacal medium with the aid of sodium perborate, after which the cobalt(III) species is determined. A second procedure [16] entails the use of lead dioxide in an acetic acid-acetate buffer containing oxalate to convert cobalt(II) to the 0(0204)3 ion, which can be subjected to polarographic reduction. This latter approach is well suited to the determination of cobalt in the presence of copper(II), iron(III), nickel(II), tin(IV), and zinc(II), whereas the chief interferences are cerium, chromium, manganese, and vanadium. 

The coordination process may either stabilize or destabilize aromatic Schiff bases. If nickel (II) salts are added to ammoniacal solutions of salicylaldehyde, the precipitate obtained is the inner complex salt of nickel (II) and salicylaldimine (61). If beryllium chloride is added to the Schiff base derived from 2-hydroxy-l-naphthaldehyde and ethylamine, however, the Schiff base is decomposed and the inner complex of beryllium (II) and 2-hydroxy-1-naphthaldehyde is obtained (59). Here the strength of the coordinate bonds formed with the metal seems to determine which complex will be formed. 

Apart from the activation of the anode no reagent has to be produced. Nickel peroxide, however, has to be prepared by oxidation of nickel(II)sulfate with sodium hypochlorite. Subsequently the reagent has to be carefully dried and the amount of active oxygen determined by iodometric titration. This must be kept in mind, because small amounts of alcohol need already a relative large amount of nickel peroxide, e.g. 100 mmol alcohol more than 75 g nickel peroxide. For that reason the use of the relative expensive, commercial nickel peroxide is restricted. 

Many 1,2,4-triazines form complexes with metal ions and can be used for their determination. Thus, 3- and/or 5-(2-pyridyl)-substituted 1,2,4-triazines (e.g. 820) can be used for the determination of iron (II), cobalt(II), nickel(II), zinc(II) and copper(I) ions, thallium and palladium ions can be analyzed by 6-phenyl- (821a) and 5,6-diphenyl-l,2,4-triazine-3-thione (821b), while osmium can be determined by 3-thioxo-l,2,4-triazin-5-one (822), 3-thioxo-dihydro-l,2,4-triazin-5-one (823), 6-mercapto-l,2,4-triazine-3,5-dione (824a), 6-mercapto-5-thioxo-l,2,4-triazin-3-one (824b) and 3,5-dithioxo-l,2,4-triazine-6-carboxyl-ates (825) <78HC(33)189, p. 1004). 

Numerous nickel(II) complexes with a variety of phosphine and arsine oxides have been reported, but only a few X-ray crystal structures have been determined. In some cases the structures assigned to the complexes are not completely certain.1800 A selection of nickel(II) complexes is reported in Table 86. 

It has invariably been found that in all of the amide complexes of nickel(II) the ligands coordinate through the oxygen atom, as inferred from IR evidence (v(CO) stretching in the range 1630-1650 cm-1) and confirmed by the structural determination of the two complexes [Ni(DMF)4(NCSe)2]1901 and [Ni(acetamide)4(H20)2jQ2.1903 All of the reported complexes are six-coordinate and high-spin. NMR studies on nickel(II) complexes with a variety of amides were carried out.1904... 

The structures determined by X-ray analysis of the complexes [Ni(Me3[12]eneN3)2](NCS)2 (Me3[12]eneN3 = 2,4,4-trimethyl-l,5,9-triazacyclododec-l-ene) and [Ni(TRI)(H20)N03]N03 (TRI = tribenzo[b,/,/][l,5,9]triazacyclododecane) show that the two triaza macrocycles coordinate facially in both square pyramidal2721 and octahedral complexes.2724 Other complexes with triaza macrocycles have been prepared and are assumed to be either live- or six-coordinate.2721-2725 Selected examples of nickel(II) complexes with unsaturated macrocydes are reported in Table 106. 

Nickel is deposited quantitatively from ammoniacal solutions, incompletely from weakly acidic solutions, and not at all from strongly acidic ones. (A quantitative separation of copper from nickel requires that the acid concentration be kept high.) Among the important interferences in the determination of nickel are silver, copper, arsenic, and zinc, which can be removed by precipitation with hydrogen sulfide. Iron(II) and chromates are objectionable, but can be removed by precipitation of the hydrous oxides. 

Hydrogen bonding between coordinated amino groups and CIO4 anions in the crystal of nickel(II) sarcophaginate was determined by X-ray crystallography (Fig. 34) [176]. 

Several amine adducts of j -isopropyltropolone complexes of nickel(ii) have been isolated NiL2(py)2, NiL2(y-pic)2, NiLjfa-pic), NiLjY (Y = piperidine, or diethyl-amine /I = 1 or 2). The complexes are octahedral and probably trimeric. The crystal structure of bis(diphenyldipyrazolylborato)nickel(ii), (Ph2B(C3H3N2)2 Ni has been determined. ... 

An X-ray study of the structure of the phthalocyanines. Part I. The metal-free, nickel, copper, and platinum compounds, J. M. Robertson, J. Chem. Soc., 1935,615, An X-ray study of the phthalocyanines. Part II. Quantitative structure determination of the metal-free compound, J. M. Robertson, J. Chem. Soc., 1936, 1195 An X-ray study of the phthalocyanines. Part III. Quantitative structure determination of nickel phthalocyanine, J. M. Robertson and I. Woodward, J. Chem. Soc., 1937, 219 An X-ray study of the phthalocyanines. Part IV. Direct quantitative analysis of the platinum compound, J. M. Robertson and I. Woodward, J. Chem. Soc., 1940, 36. 

The sensitivity of Ni(COD)2 to oxygen led to an investigation to determine if nickel(II) complexes were suitable due to their high stability and ease of reduction by organoaluminum compounds. Although the preliminary results were promising, no other source of nickel has been as successful as Ni(COD)2 itself... 

---