Voltammetric determination of traces of cobalt(II) with a chemically modified carbon paste electrode

Summary A new preconcentration and voltammetric determination method for cobalt(II) in aqueous solution with a chemically modified electrode is proposed. The accumulation behaviour and voltammetry of cobalt(II) has been investigated with a carbon paste electrode modified with cationexchanger and 1,10-phenanthroline. The electrochemical response is characterized with respect to carbon paste composition, pH, preconcentration time, cobalt(II) concentration and other variables. For a 3-min preconcentration time, the electrode gives good linearity for 1×10^–7 to 4×10^–6 mol/l Co(II), a detection limit of 8×10^–8 mol/l. The response can be reproduced with a 4.0% relative standard deviation. The method is fairly free from many coexisting ions interferences. A rapid and convenient renewal procedure allows the use of a single electrode in multiple analytical determinations over several days. Satisfactory results are obtained for the determination of cobalt in a variety of certified standard reference materials.     

Synthesis and magnetism of tetrachlorophthalato-bridged cobalt(II) binuclear complexes

Three new cobalt(II) binuclear complexes have been prepared and characterized, namely [Co2(TCPHTA)(L)4](ClO4)2 [L=1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline(NO2-phen) and 2, 2-bipyridyl (bipy), respectively], where TCPHTA is the tetrachlorophthalate dianion. Based on i.r. spectra, elemental analyses and conductivity measurements, tetrachlorophthalato-bridged structures consisting of two cobalt(II) ions in which each cobalt(II) ion has a distorted octahedral environment are proposed for these complexes. The temperature dependence of the magnetic susceptibility for [Co2(TCPHTA)(L)4](ClO4)2·nH2O (L=phen, NO2-phen and bipy) has been measured over the 77–300 K range and the observed data successfully simulated by an equation based on the spin Hamiltonian operator (H=–2JS1S2), giving the exchange integral J=–2.92, –3.45, –4.03 cm–1, respectively. This result indicates the presence of a weak antiferromagnetic spin exchange interaction between the metal ions.     

Spectrophotometric study of thiocyanato complexation of cobalt(II) and nickel(II) ions in micellar solutions of a nonionic surfactant triton X-100

Complexation of cobalt(II) and nickel(II) with thiocyanate ions has been studied by precise spectrophotometry in aqueous and micellar solutions of a nonionic surfactant Triton X-100 of varying concentrations (20–100 mmol-dm^–3). With regard to cobalt(II), the formation of [Co(NCS)]⁺, [Co(NCS)₂], and [Co(NCS)₄]^2– was established. The formation constant of [Co(NCS)₄]^2–, is increased with increasing concentration of the surfactant, suggesting that the [Co(NCS)₄]^2– complex is formed in micelles. In contrast, the formation constants of [Co(NCS)]⁺ and [Co(NCS)₂] are remained practically unchanged. On the other hand, with nickel(II), the formation of sole [Ni(NCS)]⁺ and [Ni(NCS)₂] was established in both aqueous and micellar solutions examined, their formation constants being also remained unchanged. Interestingly, no higher complex was confirmed in the nickel(II) system, unlike cobalt(II). The unusual affinity of the [Co(NCS)₄]^2– complex with micelles will be discussed from thermodynamic and structural points of view.     

Extraction of cobalt (II) and nickel (II) by a solvent impregnated resin containing bis(2,4,4-trimethylpentyl)monothiophosphinic acid

In the present work, studies have been conducted on the equilibrium distribution of cobalt (II) and nickel (II) between aqueous hydrochloric solution and macromolecular resin impregnated with bis(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex302, HL). Effects of extraction time, pH values, metal ion concentration, and temperature were investigated. Analysis of the results shows that the extraction of the two metal ions can be explained assuming the formation of metal complexes in the resin phase with a general composition ML ₂. An extraction reaction is proposed and the equilibrium constants of the complexes were determined. The Freundlich isotherm and thermodynamic quantities, i.e., ΔG, ΔH and ΔS were also obtained. Both of the extraction reactions of cobalt (II) and nickel (II) are endothermic ones. The efficiency of the resin in the separation of cobalt (II) and nickel (II) is provided according to the separation factors. Under the experimental conditions employed, pH₅₀ values for cobalt (II) and nickel (II) are 3.76, 5.01, respectively. The logarithmic value of separation factor was calculated as 2.50.     

Chemical species produced in the reaction between ethanedial (glyoxal) and 5-amino-1,10-phenanthroline and their iron(II) complexes: electrochemical studies and analytical applications

The cyclic voltammetric behavior of carbon paste electrodes modified by direct admixing with the products of the reactions between ethanedial (glyoxal) and 5-amino-1,10-phenanthroline at 100°C and that of their iron(II) complexes is reported. The ligand(s) produced in absence of iron(II) are able to complex iron(II) and copper(II) ions reversibly, but other ions such as nickel(II), cobalt(II), cadmium(II) and manganese(II), if complexed, show no electrochemical activity. Admixing with the products of the reaction in the presence of excess of iron(II) ion, because of high insolubility and fast electron exchange, produces surfaces useful for amperometric detection in continuous-flow systems. The voltammetric and amperometric behavior in the presence of HSO^?₃ ions is reported in order to illustrate this application.     

Simultaneous determination of iron(III) and cobalt(II) withN-phenylcinnamohydroxamic acid and thiocyanate by extraction and spectrophotometry

Simple, precise, sensitive, and highly selective methods for the separate determination of iron(III) and cobalt(II) and for the simultaneous determination of both metal ions are described. Iron(III) and cobalt(II) react with thiocyanate in the presence ofN-phenylcinnamohydroxamic acid (PCHA) to form pinkish red and blue coloured complexes, respectively. Both the iron(III) and cobalt(II) complexes having stoichiometric composition of 122 (FeSCN^–PCHA) and 14 (CoSCN^–), respectively, are quantitatively extractable into ethylacetate from 0.5–1.5 M hydrochloric acid solutions. The spectra of iron(III) and cobalt(II) complexes in the visible region exhibit absorption maxima at 495 and 625 nm, respectively. The coloured systems obey Beer's law in the concentration range of 0.2–4.0g/ml of iron and 2–40g/ml of cobalt. The effects of foreign ions and of various experimental parameters were studied to establish the optimum conditions for the extraction and determination of iron and cobalt. The methods have been applied successfully to the analysis of blood, vitamin B₁₂, and standard steels for iron and cobalt.     

Iron(II), cobalt(III), nickel(II) and copper(II) chelates of furan and thiophene azo-oximes

Summary Complexes of furan and thiophene azo-oximes with iron(II), cobalt(III), nickel(II) and copper(II) have been prepared and characterised. Iron(II), cobalt(III) and copper(II) complexes are diamagnetic in the solid state. The diamagnetism of the copper(II) chelates is suggestive of antiferromagnetic interaction between two copper centres.¹H n.m.r. spectral data suggest atrans-octahedral geometry for the tris-chelates of cobalt(III). Nickel(II) complexes are paramagnetic, in contrast to the diamagnetism of the analogous complexes of arylazooximes. The electronic spectra are suggestive of octahedral geometry for the iron(II), cobalt(III) and nickel(II) complexes, andD _4h -symmetry for copper(II). Infrared data indicate N-bonding of the oximino-group to the metal ions.     

Synthesis and characterization of manganese(II), nickel(II), copper(II) and zinc(II) Schiff-base complexes derived from 1,10-phenanthroline-2,9-dicarboxaldehyde and 2-mercaptoethylamine

The synthesis of a new Schiff base containing 1,10-phenanthroline-2,9-dicarboxaldehyde and 2-mercaptoethylamine is described. The reaction of 1,10-phenanthroline-2,9-dicarboxaldehyde with 2-mercaptoethylamine leads to 2,9-bis(2-ethanthiazolinyl)-1,10-phenanthroline (I) which undergoes rearrangement when reacted with manganese, nickel, copper or zinc ions to produce complexes of the tautomeric Schiff base 2,9-bis[2-(2-mercaptoethyl)-2-azaethene]-1,10-phenanthroline (L). The [M(L)Cl₂] complexes [where M = Mn(II), Ni(II), Cu(II) and Zn(II) ions] were characterized by physical and spectroscopic measurements which indicated that the ligand is a tetradentate N₄ chelating agent.     

Preparation and reactivity of metal-containing monomers. 11. Complexes of nickel(II), cobalt(II), and chromium(III) acrylates with 2,2′-dipyridyl and 1,10-phenanthroline

A procedure has been developed for the synthesis of complexes of nickel(II), cobalt(II), and chromium(III) with 2,2-dipyridyl and 1,10-phenanthroline. On the basis of data obtained by elemental analysis, DTA, IR and UV spectroscopy, and magnetochemistry, it has been established that the coordination unit for these compounds has an octahedral structure, and splitting parameters have been calculated in the approximation of O_h symmetry. It has been shown that, in comparison with the acrylate complexes, their saturated analogs have longer metal-ligand bonds and lower degrees of covalency.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2468–2474, November, 1989.     

Complexes of cobalt(II), nickel(II) and copper(II) with the benzenedicarboxylic acids. Thermal properties

The thermal properties of the complexes of phthalic, isophthalic and terephthalic acid with cobalt(II), nickel(II) and copper(II) are determined by thermogravimetry (TG), differential thermogravimetry (DTG) and differential scanning calorimetry (DSC).The thermal stability of the anhydrous compounds gives, for the metal ions, a sequence Co > Ni > Cu.The thermal stability series as a function of the ligand for each metal is terephthalate > isophthalate > phthalate.     

The relaxation spectra of nickel(II) and cobalt(II) arginine complexes

The temperature-jump method has been used to determine the nickel(II)- and cobalt(II)-arginine complexation kinetics. In the pH range studied, the neutral form of the ligand, HL, is the attacking, as well as the complexed, ligand species. The reactions reported on are of the type where n = 1, 2, 3 and M is Ni or Co. At 25° and ionic strength 0.1M the association rate constants are: for nickel(II) k₁ = 2.3 × 10³(±20%), k₂ = 2.4 × 10⁴(±20%), k₃ = 3.5 × 10⁴(±40%) M^?1 sec^?1; for cobalt(II) k₁ = 1.5 × 10⁵(±20%), k₂ = 8.7 × 10⁵(±20%), k₃ = 2.0 × 10⁵(±40%) M^?1 sec^?1. Arginine binds to metal ions less well than homologous chelating agents due to the electrostatic repulsion arising from the positively charged terminus of the zwitterion. Kinetically, the effect appears in the association rate constants with nickel reactions more strongly influenced than cobalt.     

Copper(II), nickel(II) and cobalt(III) complexes of the macrocyclic ligand C-meso-7,14-diphenyl-5,6-butano-12,13-butano-1,4,8,11-tetraazacyclotetradeca-4,11-diene

Summary Metal complexes of the macrocyclic tetraaza ligand C-meso-7,14-diphenyl-5,6-butano-12,13-butano-1,4,8,11-tetraazacyclotetradeca-4,11-diene (L) are described. The copper(II) and nickel(II) complexes, isolated as their perchlorate salts, are 4-coordinate species. Several cobalt(III) complexes,trans-[CoLX₂]⁺(X = Cl^–, Br^–, NO ₂ ^– or N ₃ ^– have also been characterised. The most probable stereochemistry of the ligand in the metal complexes is the C-meso-N-meso arrangements of the chiral centres. The N-meso stereochemistry leads to the bulky phenyl groups lying in equatorial positions. I.r. and d-d spectra are reported for the various complexes described.     

Etude des complexes sulfosalicylate de cuivre(III), nickel(II), cobalt(II) et uranyle(II) a l'aide d'une resine echangeuse de cations: Study of the sulphosalicylate complexes ofcopper(II), nickel(II), cobalt(II) and uranyl(II) by means of cation-exchange resins.

Study of the sulphosalicylate complexes of copper(II), nickel(II), cobalt(II) and uranyl(II) by means of cation-exchange resins.The conditional stability constants of the 1:1 complexes of the sulphosalicylate ions (L^3-) with copper(II), nickel(II), cobalt(II) and uranyl ions have been determined in a sodium perchlorate solution (0.1 M) and at various pH values by a cation-exchange method based on Schubert's procedure. The limits of application of the method are discussed. The variation with pH of the conditional stability constants can be explained by the existence of the complexes: CuH₂L, CuHL, CuL^-; NiH₂L⁺, NiHL, NiL^-; CoHL, CoL^-; UO₂H₂L⁺, UO₂HL, UO₂L^-, UO₂LOH^2-. The stability constants of these complexes are reported. Distribution diagrams of the various complexes of each element with pH and total concentration of sulphosalicylate parameters are given.     

A potentiometric study of the oxidation of cobalt(II) with gold(III) chloride in presence of 1,10 phenanthroline or 2,2'-bipyridine : A new titration of cobalt (II) and its application to nickel-base alloys

The redox reaction between cobalt(II) and gold(III) chloride in the presence of 1.10-phenanthroline or 2,2'-bipyridine was studied, and a titration of the cobalt(II) complex with a gold(III) chloride solution was developed. A 4-fold amount of 1,10-phenanthroline or 2,2'-bipyridine was necessary for rapid quantitative reaction; the permissible pH range was 1.5–5. The oxidation of the cobalt(II) complex proceeds rapidly at 40–50°C, and a direct potentiometric titration was possible. The following maximum errors were obtained: 3.3% for 0.2–1.0 mg Co, 2.0% for 1–5 mg Co, and 0.70% for 10–40 mg Co. The following ions did not interfere: Ni(II), Zn(II), Pb(II), Cd(II), Mn(II), Fe(II), Cr(III), Al(III), Th(IV), Se(IV), Ti(IV), U(VI), Mo(VI), SO^2-₄ and PO^3-₄. Even small quantities of silver(I), copper(II), palladium(II), mercury(II)and iron(III) interfered. The method was applied to the determination of high cobalt contents in high-temperature nickel-base alloys.     

Gas chromatography of ternary complexes of manganese(II), iron(II), cobalt(II) and nickel(II) with hexafluoroacetylacetone and DI-n-butylsulphoxide

The gas Chromatographic behaviour of the ternary complexes of selected bivalent first-row transition metal ions with 1,1,1,5,5,5-hexafluoro-2,4-pentanedione H(HFA), and di-n-butylsulphoxide, DBSO, was studied. Calibration plots of peak area vs. amount of metal injected were linear over a range of 60–900 ng for manganese(II), iron(II), cobalt(II) and nickel(II). The average relative standard deviation was less than 3·0% for all the metals studied. Detection limits of 60, 109, 112 and 115ng for cobalt(II), nickel(II), iron(II) and manganese(II), respectively, were obtained with flame-ionization detection. Various liquid phases, including OV-1, SE-30, and Dexsil 300 were used. The best results were obtained on columns of 5% Dexsil 300. No appreciable thermal decomposition was observed on stainless-steel or glass columns, but the best formed peaks were obtained on all-glass columns. The elution of the metallic species was confirmed by venting the exit gases from the gas chromatograph directly into an atomic-absorption spectrophotometer.     

Novel heteroligand complexes of Co(II), Cu(II), Ni(II) and Mn(II) formed by 2,2′-dipyridyl or 1,10-phenanthroline and phosphortriamide ligands: Synthesis and structure

This paper presents examples of mixed-ligand Co(II), Cu(II), Ni(II) and Mn(II) complexes, with a distorted octahedral coordination geometry, with 2,2′-dipyridyl or 1,10-phenanthroline and phosphortriamide ligands. The complexes of the general type ML₂·Lig (where M = Co(II), Cu(II), Ni(II), Mn(II); L⁻ = {Cl₃C(O)NP(O)R₂}⁻ (R = NHBz, NHCH₂CHCH₂, NEt₂); Lig = 2,2′-dipyridyl or 1,10-phenanthroline) were synthesised and characterised by means of X-ray diffraction, IR and UV–Vis spectroscopy. The phosphortriamide ligands are coordinated via oxygen atoms of phosphoryl and carbonyl groups involved in six-membered metal cycles. The additional ligands 2,2′-dipyridyl or 1,10-phenanthroline are coordinated to the central atom, forming five-membered cycles.     

Synthesis and structural characterization of new trinuclear cobalt(II) and nickel(II) complexes possessing five- and six-coordinated geometry

Tri-nuclear cobalt and nickel complexes ([(CoL)₂(OAc)₂Co]?·?THF (I) and [(NiL)₂(OAc)₂(THF)₂Ni]?·?THF (II)) have been synthesized by reaction of a new Salen-type bisoxime chelating ligand of 2,2′-[ethylenedioxybis(nitrilomethylidyne)]dinaphthol(H₂L) with cobalt(II) acetate tetrahydrate or nickel(II) acetate tetrahydrate, respectively. Complexes I and II were characterized by elemental analyses, IR, TG-DTA and ¹H-NMR etc. The X-ray crystal structures of I and II reveal that two acetate ions coordinate to three cobalt or nickel ions through M–O–C–O–M (M?=?Co or Ni) bridges and four μ-naphthoxo oxygen atoms from two [ML] units also coordinate to cobalt(II) or nickel(II). Complex I has two distorted square-pyramidal coordination spheres and an octahedral geometry around Co1. In complex II all three nickel ions are six-coordinate.     

Extraction-polarographic determination of cobalt(II) and nickel(II) as 2,2′-bipyridine complexes in acetonitrile

The tris(2,2′-bipyridine)cobalt(II) complex gives a reversible d.c. wave with E$\text{1}\text{2}$ = ?1.02 V vs. SCE and a sharp differential pulse peak at E_p = ?1.03 V in a salted-out acetonitrile phase. A simple selective method is described for the determination of cobalt(II); down to 0.25 μg of cobalt(II) can be determined in presence of large amounts of Ni, Zn, Cd, Pb, and Cu; iron(III) can be masked with sodium fluoride. The method is applicable to the determination of >0.0l% cobalt in nickel salts and >5 × 10^?5% cobalt in iron salts. Nickel(II) can also be extracted from aqueous solution and determined by differential pulse polarography, even in presence of a 20-fold amount of cobalt(II) by masking with EDTA; >0.01% of nickel in cobalt salts can be determined reproducibly.     

Synthesis,characterization and catalytic studies of iron(III), cobalt(II), nickel(II) and copper(II) complexes containing triphenylphosphine and β-diketones

A series of new β-diketonato complexes have been synthesized from the reactions of iron(III), cobalt(II), nickel(II) and copper(II) Ph₃P complexes with β-diketones (acetylacetone, benzoylacetone and dibenzoylmethane). All the complexes have been characterized by elemental analyses, spectral studies (i.r., electronic., magnetic., e.p.r., ¹H-n.m.r.) and cyclic voltammetry. The new complexes have been used as catalysts for aromatic coupling and oxidation reactions. Higher catalytic activity has been observed for the nickel(II) complexes compared to the other complexes.     

Coordination chemistry of amine bis(phenolate) cobalt(II), nickel(II), and copper(II) complexes

Cobalt(II), nickel(II), and copper(II) (1, 2, and 3) complexes of the dianionic form of the bis(phenolate) ligand N,N-bis(3,4-dimethyl-2-hydroxybenzyl)-N',N'-dimethylethylenediamine (H2L) have been synthesized by electrochemical oxidation of the appropriate metal in an acetonitrile solution of the ligand. When copper is used as the anode, the addition of 1,10-phenanthroline to the electrolytic phase gave rise to a different compound [CuL]2.2CH3CN (4). The compounds [CoL]2.2CH3CN (1), [Ni2L2(H2O)].H2O (2), [CuL]2.3H2O (3), and [CuL]2.2CH3CN (4) were characterized by microanalysis, IR, electronic spectroscopy, FAB mass spectrometry, magnetic measurements and by single-crystal X-ray diffraction. The crystal structures show that the complexes have a dinuclear structure. In compounds 1, 3, and 4, two metal ions are coordinated by the two amine nitrogens and the two phenol oxygen atoms of a deprotonated pendant phenol ligand, with one phenolic oxygen atom from ligand acting as a bridge. In compounds 1 and 3, each metal center has a geometry that is closest to trigonal bipyramidal. Magnetic susceptibility data for both compounds show an antiferromagnetic coupling with 2J = -15 cm(-1) for the cobalt(II) complex and a strong antiferromagnetic coupling with 2J = -654 cm(-1) for the copper(II) complex. However, in 4 the geometry around the metal is closer to square pyramidal and the compound shows a lower antiferromagnetic coupling (2J = -90 cm(-1)) than in 3. The nickel atoms in the dimeric compound 2 are hexacoordinate. The NiN2O4 chromophore has a highly distorted octahedral geometry. In this structure, a dianionic ligand binds to one nickel through the two amine nitrogen atoms and the two oxygen atoms and to an adjacent nickel via one of these oxygen atoms. The nickel atoms are linked through a triple oxygen bridge involving two phenolic oxygens, each from a different ligand, and an oxygen atom from a water molecule. The two nickel ions in 2 are ferromagnetically coupled with 2J = 19.8 cm(-1).