Test Determination of Cu(II), Ni(II), and Cr(VI) in a Single Sample

It was shown that Cr(VI), Ni(II), and Cu(II) can be simultaneously adsorbed on a solid phase consisting of two filled fibrous disks and then determined visually using organic reagents. One sorbent disk, a fibrous material filled with an AB-17 anion exchanger, was used to determine chromium by its reaction with 1,5-diphenylcarbazide. Another disk filled with an KU-2 cation exchanger was used for the simultaneous sorption of copper and nickel followed by the consecutive determination of nickel with dimethylglyoxime and copper with sodium diethyldithiocarbamate. The conditions were optimized for the determination of nickel in the presence of copper and of copper in the presence of nickel after decomposing its dimethylglyoxime complex with 1 M HCl. The detection limits were 0.02, 0.1, and 0.05 mg/L for Cr, Ni, and Cu, respectively. The time of analysis was no longer that 20 min.     

Use of Two-Layer Supports for the Sorption–Spectrometric Determination of Chromium(VI), Copper(II), and Nickel(II) from a Single Sample in a Flow System

The determination of three elements from a single sample on a two-layer support in the flow mode was studied. One layer is a disk of a fiber material filled with the AV-17 anion exchanger, and the other is a disk of a material filled with the KU-2 cation exchanger. The method is based on the simultaneous preconcentration of elements by pumping a test sample through two disks in a flow cell, the separation of layers, and subsequent detection of chromium on the support filled with AV-17 using 1,5-diphenylcarbazide. The support filled with KU-2 is used for the sequential determination of nickel with dimethylglyoxime and copper with sodium diethyldithiocarbamate in 1 M HCl. The nickel dimethylglyoximate is decomposed under the action of 1 M HCl; its 10-fold amounts do not interfere with the determination of copper. This method provides the determination of chromium, copper, and nickel at a level below the maximum permissible concentration for potable water; at the ratio Cr : Ni : Cu = 1 : 10 : 20, RSD is lower than 10%. The time of the determination of the three elements from a single sample is 25–30 min.     

Adsorption and determination of bismuth with 4-(2-pyridylazo)resorcinol on a fibrous ion exchanger

The adsorption of bismuth was studied on a fibrous material filled with a Chelex 100 ion exchanger with iminodiacetic groups and a KU-2 cation exchanger, and as thiosulfate and iodide complexes on a fibrous AV-17 (PANV-AV-17) anion exchanger. Bismuth adsorbed on the solid phase was determined with 4-(2-pyridylazo)resorcinol (PAR). The optimal conditions for adsorption and determination were selected and selectivity was studied. The system bismuth-iodide-PANV-AV-17-PAR was proposed for the determination of bismuth in the solid phase. A procedure was developed for the adsorption-spectroscopic determination of 0.04–0.4 mg/L of bismuth in fresh water and urine with a detection limit of 0.03 mg/L and RSD < 20%.     

Determination of vanadium(V) and chromium(VI) in a single sample on a fibrous ion exchanger disk

The determination of vanadium(V) and chromium(VI) in a single sample on a support disk was studied. Polyacrylonitrile fiber filled with an AV-17 anion exchanger was used as a solid phase. After adsorption, the elements were successively detected in the solid phase by color complexation reactions of vanadium with 8-hydroxyquinoline-5-sulfonic acid and chromium with 1.5-diphenylcarbazide. A procedure was developed for the adsorption-spectroscopic determination of 0.04–0.4 μg/mL vanadium(V) and 0.01–0.05 μm/mL chromium(VI) at V: Cr ratios of 1: 1 to 10: 1 in the dynamic mode. The limits of detections for vanadium and chromium were 0.04 and 0.005 μg/mL, respectively. It was shown that the background salt content of potable water had no appreciable effect; no preliminary sample preparation was required.     

Thermal, spectral and magnetic behaviour of 2,3,4-trimethoxybenzoates of Mn(II), Co(II), Ni(II) AND Cu(II)

Four new complexes of 2,3,4-trimethoxybenzoic acid anion with manganese(II), cobalt(II), nickel(II) and copper(II) cations were synthesized, analysed and characterized by standard chemical and physical methods. 2,3,4-Trimethoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II) are polycrystalline compounds with colours typical for M(II) ions. The carboxylate group in the anhydrous complexes of Mn(II), Co(II) and Ni(II) is monodentate and in that of Cu(II) monohydrate is bidentate bridging one. The anhydrous complexes of Mn(II), Co(II) and Ni(II) heated in air to 1273 K are stable up to 505–517 K. Next in the range of 505–1205 K they decompose to the following oxides: Mn₃O₄, CoO, NiO. The complex of Cu(II) is stable up to 390 K, and next in the range of 390–443 K it loses one molecule of water. The final product of its decomposition is CuO. The solubility in water at 293 K is of the order of 10^–3 mol dm^–3 for the Mn(II) complex and 10^–4 mol dm^–3 for Co(II), Ni(II) and Cu(II) complexes. The magnetic moment values of Mn²⁺, Co²⁺, Ni²⁺ and Cu²⁺ ions in 2,3,4-trimethoxybenzoates experimentally determined in the range of 77–300 K change from 5.64–6.57 μB (for Mn²⁺), 4.73–5.17 μB (for Co²⁺), 3.26–3.35 μB (for Ni²⁺) and 0.27–1.42 μB (for Cu²⁺). 2,3,4-Trimethoxybenzoates of Mn(II), Co(II) and Ni(II) follow the Curie–Weiss law, whereas that of Cu(II) forms a dimer.     

New nickel(II), copper(II), platinum(II) and palladium(II) complexes of a multidentate sulfur–nitrogen chelating agent

A new, potentially polydentate sulfur–nitrogen chelating agent, 2,6–bis(N-methyl-S-methyldithiocarbazato)pyridine (L) has been synthesized and characterized. With nickel(II) salts, the ligand yields complexes of empirical formula NiLX2·nH2O (X=Cl−, NCS− or NO3−; n=0 or 1) in which it behaves as a quadridentate NSSN chelating agent, coordinating to the nickel(II) ion via the two amino nitrogen atoms and the two sulfur atoms. Magnetic and spectral evidence support a distorted octahedral structure for these complexes. The ligand reacts with copper(II), platinum(II) and palladium(II) salts to yield homo-binuclear complexes of general formula [M2LX4]·nSol (M=CuII, PtII or PdII; X=Cl− or Br−; n=0.5, 1 or 2; Sol=H2O, MeOH or MeCOMe), in which each of the metal ions is in a square-planar environment. These complexes have been characterized by a variety of physicochemical techniques. This revised version was published online in June 2006 with corrections to the Cover Date.     

Sorption-spectrophotometric determination of zirconium and chromium(VI) from a single sample on a two-layer support using Arsenazo III and 1,5-diphenylcarbazide

The possibility of the sorption-spectrometric determination of zirconium(IV) and chromium(VI) from a single sample using a two-layer support made of polyacrylonitrile fiber filled with a PANF-KU-2 cation exchanger and PANF-AV-17 anion exchanger is studied. After sorption zirconium is determined with Arsenazo III on PANF-KU-2 and chromium is determined with 1,5-dipehnylcarbazide on PANF-AV-17. The sorption of zirconium and chromium is studied in the dynamic mode from solutions of HCl, HNO₃, and H₂SO₄ and the optimal conditions of the simultaneous sorption of zirconium on PANF-KU-2 and chromium on PANF-AV-17 from 0.25 M HCl is chosen. Diffuse reflection spectra of zirconium and chromium complexes have are on the solid phase and the conditions of zirconium determination are optimized. Calibration curves are linear in the range of zirconium and chromium concentration 0.005–0.025 μg/mL; the detection limits are 0.002 μg/mL. The selectivity of zirconium and chromium determination is tested in the presence of interfering ions. A procedure is developed for their determination from a single sample at zirconium to chromium ratios from 3: 1 to 1: 3.     

Sequential extraction for the speciation of some heavy metals in soils

The five step sequential extraction for speciation of copper and nickel originally designed for sediments has been applied to soil samples. The extractant solutions were: 1 mol/l ammonium acetate, 1 mol/l hydroxylammonium chloride in 25% acetic acid (1∶1), 0.1 mol/l hydrochlorid acid, 0.5 mol/l sodium hydroxide and 8 mol/l nitric acid. The residue was decomposed by HF and HNO₃. Using this procedure the metal fraction bound to the organic matter can be distinguished. The concentrations of analytes were determined in the soil extracts by FAAS and ETAAS. Accuracy was assessed by comparing the sum of the contents of copper and nickel in soil extracts with the total certified values of CRMs of soils. The overall recovery values for nickel was 84–105% and for copper 105–114%.     

Liquid chromatographic determination of chelates of cobalt (II), copper (II) and iron (II) with 2-thiophonaldehyde-4-phenyl-3-thiosemicarbazone

Summary A new chelating reagent 2-thiophenaldehyde-4-phenyl-3-thiosemicarbazone (TAPT) has been examined for high performance liquid chromatographic (HPLC) separations of cobalt (II), copper(II) and iron (II) or cobalt (II), nickel (II), iron (II), copper (II) and mercury (II) as metal chelates on a C₁₈, 5μm column (250×4 mm i.d.) The chelates were eluted isocratically with methanol: acetonitrile: water containing sodium acetate and tetrabutylammonium bromide (TBA), and detected at 254 nm. A solvent extraction procedure was developed for simultaneous determination of the metals with detection limits within 0.02–2.5 μ g.mL⁻¹. The method was applied to the determination of copper, cobalt and iron in natural waters.     

Complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with 4-chloro-2-methoxybenzoic acid anion

The complexes of 4-chloro-2-methoxybenzoic acid anion with Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ were obtained as polycrystalline solids with general formula M(C₈H₆ClO₃)₂·nH₂O and colours typical for M(II) ions (Mn – slightly pink, Co – pink, Ni – slightly green, Cu – turquoise and Zn – white). The results of elemental, thermal and spectral analyses suggest that compounds of Mn(II), Cu(II) and Zn(II) are tetrahydrates whereas those of Co(II) and Ni(II) are pentahydrates. The carboxylate groups in these complexes are monodentate. The hydrates of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) heated in air to 1273 K are dehydrated in one step in the range of 323–411 K and form anhydrous salts which next in the range of 433–1212 K are decomposed to the following oxides: Mn₃O₄, CoO, NiO and ZnO. The final products of decomposition of Cu(II) complex are CuO and Cu. The solubility value in water at 293 K for all complexes is in the order of 10^–3 mol dm^–3. The plots of χ_M vs. temperature of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II) follow the Curie–Weiss law. The magnetic moment values of Mn²⁺, Co²⁺, Ni²⁺ and Cu²⁺ ions in these complexes were determined in the range of 76−303 K and they change from: 5.88–6.04 μ_B for Mn(C₈H₆ClO₃)₂·4H₂O, 3.96–4.75 μ_B for Co(C₈H₆ClO₃)₂·5H₂O, 2.32–3.02 μ_B for Ni(C₈H₆ClO₃)₂·5H₂O and 1.77–1.94 μ_B for Cu(C₈H₆ClO₃)₂·4H₂O.     

Color reactions of vanadium(V) with 8-hydroxyquinoline-5-sulfonic acid and ascorbic acid on PANV–AV-17 disks

The adsorption of vanadium(V) and 8-hydroxyquinoline-5-sulfonic acid (HQS) on polyacrylonitrile fiber disks filled with an AV-17 (PANV–AV-17) anion exchanger is studied by diffuse reflection spectroscopy. Vanadium(V) at pH 5?7 is adsorbed on PANV–AV-17; when a HQS solution is applied to the disk, a yellowish green complex compound formed, which changed color to almost black after the treatment of the disk with a HCl solution. The presence of sulfo groups in the HQS molecule ensures the preconcentration of the reagent on PANV–AV-17 disks with the registration of an analytical signal after the treatment of the disk with NaVO₃ and 0.1 M HCl solutions. A linear dependence of the analytical signal is observed in the HQS concentration range of 1?10 μg/mL. The presence of 20-fold amounts (by weight) of 8-hydroxyquinoline (HOQ) does not interfere with the determination. When ascorbic acid is applied to the disk with a vanadium(V)?HQS?HCl complex, the color changes from black to green. A test method for the determination of ascorbic acid is proposed. 8-Hydroxyquinoline can be determined by the intrinsic color of the adsorbate on PANV–KU-2 in the range of concentrations of HOQ solution in two drops 5?100 μg.     

Chelating resin containing s-bonded dithizonefor the separation of copper(II), nickel(II) and zinc(II)

Analytical and physicochemical properties of a crosslinked poly (vinyl pyridine) based resin containing dithizone were examined. The resin was further used for the preconcentration of copper, nickel and zinc at batch and column level. Various conditions such as pH, equilibration time, temperature were optimised for the maximum loading of copper, nickel and zinc. The loading capacities of the resin for copper, nickel and zinc were observed to be 0.51, 0.59 and 0.65 mmol g⁻¹ of dry resin respectively. Elution of loaded copper, nickel and zinc from the resin was done by using 0.1 M HCl, 0.1 M H₂SO₄ and 0.1 M HNO₃ respectively. Separation of copper, nickel and zinc in binary and ternary mixtures was achieved without any cross contamination.     

Copper(II) extraction with 1-{[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]-methyl}-1H-1,2,4-triazole from hydrochloric acid solutions

Copper(II) extraction with 1-“[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]-methyl”-1H-1,2,4-triazole in toluene from hydrochloric acid solutions is studied. It is shown that copper(II) is most efficiently extracted with this reagent from 3–5 M HCl solutions. For aqueous acidity of 3 mol/L HCl, the extraction is an exothermal process and follows the coordination mechanism. The anion-exchange extraction mechanism predominates where HCl concentrations is greater than 6 mol/L. The studied reagent can be used for the selective separation of copper(II) from nickel(II) and cobalt(II) at aqueous acidities of up to 4 mol/L HCl.     

Dynamics of Copper(II), Nickel(II), and Iron(III) Ion Exchange

The degree of utilization of the static exchange capacity of KU-2×8×12 cation exchanger with respect to copper(II), nickel(II), and iron(III) cations was considered as a function of the solution flow velocity through the column cross section.     

Spectroscopic studies of bridged binuclear complexes of Co(II), Ni(II), Cu(II) and Zn(II)

Binuclear cobalt(II), nickel(II), copper(II) and zinc(II) complexes of general composition [M₂L^1-2(μ-Cl)Cl₂] · nH₂O with the Schiff-base ligands (where L¹H and L²H are the potential pentadentate ligands derived by condensing 2,6-diformyl-4-methylphenol with 4-amino-3-antipyrine and 2-hydroxy-3-hydrazinoquinoxiline, respectively) have been synthesized and characterized. Analytical and spectral studies support the above formulation. ¹H-NMR and IR spectra of the complexes suggest they have an endogenous phenoxide bridge, with chloride as the exogenous bridge atom. The electronic spectra of all the complexes are well characterized by broad d–d and a high intensity charge-transfer transitions. The complexes are chloro-bridged as evidenced by two intense far-IR bands centered around 270–280 cm⁻¹. Magnetic susceptibility measurements show that complexes are antiferromagnetic in nature. The compounds show significant growth inhibitory activity against fungi Aspergillus niger and Candida albicans and moderate activity against bacteria Bacillus cirroflagellosus and Pseudomonas auresenosa.     

Spontaneous passivity of amorphous bulk Ni–Cr–Ta–Mo–Nb–P alloys in concentrated hydrochloric acids

Rod-shaped amorphous bulk Ni–Cr–Mo-22 at.%Ta-14 at.%Nb–P alloys resistant to concentrated hydrochloric acids were prepared by copper-mold casting. Alloys of amorphous single phase and mixture of nanocrystalline phases in the amorphous matrix were all spontaneously passive in 6 and 12 M HCl and were immune to corrosion in 6 M HCl, although the corrosion weight loss was detected for heterogeneous alloys in 12 M HCl. Spontaneous passivation is due to presence of stable air-formed films in which chromium was particularly concentrated in addition to enrichment of tantalum and niobium. The angle resolved X-ray photoelectron spectroscopy revealed that chromium and molybdenum are rich in the inner part of the film. The major molybdenum species is in the tetravalent state, although penta- and hexavalent state molybdenum is also included. The high corrosion resistance was interpreted in terms of the high stability of the outer triple oxyhydroxide, Cr_1−x−yTa_xNb_yO_z(OH)_3+2x+2y−2z, and the effective diffusion barrier of the inner Mo⁴⁺ and Cr³⁺ oxide layer. Contribution to the Fall Meeting of the European Materials Research Society, Symposium D: 9th International Symposium on Electrochemical/Chemical Reactivity of Metastable Materials, Warsaw, 17th-21st September, 2007.     

Synthesis and characterization of complexes of Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) with macrocycle 3,4,11,12-tetraoxo-1,2,5,6,9,10,13,14-octaaza-cyclohexadeca-6,8,14,16-tetraene and their biological screening

A new series of complexes is synthesized by template condensation of glyoxal and oxalyldihydrazide in methanolic medium in the presence of divalent cobalt, nickel, copper, zinc and cadmium salts forming complexes of the type: [M(C₈H₈N₈O₄)X₂] where M = Co^(II), Ni^(II), Cu^(II), Zn^(II), Cd^(II) and X = Cl⁻¹, Br⁻¹, NO ₃ ⁻¹ , OAc⁻¹. The complexes have been characterized with the help of elemental analyses, conductance measurements, magnetic susceptibility measurements, electronic, n.m.r., infrared and far infrared spectral studies. On the basis of these studies, a six coordinate octahedral geometry for these complexes has been proposed. The biological activities of the metal complexes have been tested in vitro against a number of pathogenic bacteria to assess their inhibiting potential. Most of the compounds have been found to exhibit remarkable antibacterial activities.     

Oxidation kinetics of nickel nano crystallites obtained by controlled thermolysis of diaquabis(ethylenediamine)nickel(II) nitrate

The metal complex, [Ni(en)₂(H₂O)₂](NO₃)₂ (en = ethylenediamine), was decomposed in a static furnace at 200 °C by autogenous decomposition to obtain phase pure metallic nickel nanocrystallites. The nickel metal thus obtained was studied by XRD, IR spectra, SEM and CHN analysis. The nickel crystallites are in the nanometer range as indicated by XRD studies. The IR spectral studies and CHN analyses show that the surface is covered with a nitrogen containing species. Thermogravimetric mass gain shows that the product purity is high (93%). The formed nickel is stable and resistant to oxidation up to 350 °C probably due to the coverage of nitrogen containing species. Activation energy for the oxidation of the prepared nickel nanocrystallites was determined by non-isothermal methods and was found to depend on the conversion ratio. The oxidation kinetics of the nickel crystallites obeyed a Johnson–Mehl–Avrami mechanism probably due to the special morphology and crystallite strain present on the metal.     

Determination of minor and trace elements in silicate rocks by inductively-coupled plasma emission spectrometry

Samples (0.5 g) are decomposed with mixed acids in a sealed teflon vessel. After suitable treatment, barium, cobalt, chromium, copper, lithium, nickel, scandium. strontium, vanadium and zirconium are determined sequentially. The method is satisfactory for a variety of standard silicate materials.     

Separation and determination of trace amounts of aluminium(III), vanadium(V), iron(III), copper(II) and nickel(II) with CALKS and PAR by RP-HPLC.

An RP-HPLC method for the separation and determination of aluminium(III), vanadium(V), iron(III), copper(II) and nickel(II) with CALKS (Chromazol KS) and PAR ([4-(2-pyridylazo)resorcinol]) chelating on a YWG-ODS column was developed. A mixture of methanol-tetrahydrofuran(THF)-water (60:5:35 v/v) containing 0.2 mol/L LiCl, 5 x 10(-5) mol/L CALKS, 5 x 10(-5) mol/L PAR and acetate buffer solution (pH 4.9) was selected as mobile phase. The method has high sensitivity, with the detection limits being 6 ng/mL for aluminium(III), 3.5 ng/mL for vanadium(V), 10.4 ng/mL for iron(III), 6.3 ng/mL for copper(II) and 8.7 ng/mL for nickel(II). It also has good selectivity, so that most foreign metal ions do not interfere under the optimum conditions. The method can be applied to the simultaneous determination of trace amounts of aluminium, vanadium, iron, copper and nickel in rice and flour samples.