Solvent-Extraction Behavior of Cobalt(II), Nickel(II), Copper(II), and Palladium(II) with Tri-n-butylphosphate

Abstract

A systematic study of the extraction behavior of cobalt(II), nickel(II), copper(II), and palladium(II) with TBP from thiocyanate system in various ranges of acid concentrations has been performed. The thiocyanate medium leads to enhanced extractions in all these cases compared to those in the previously used chloride medium. For palladium, the chloride and nitrate systems have been critically examined. Sixty-two per cent extraction occurs from 4 M hydrochloric acid using 100% TBP in a single run and the extraction becomes quantitative (>99%) after four successive equilibrations. A simpler method has been proposed for rapid extraction of palladium(II) as the thiocyanate complex. Quantitative extraction occurs in the presence of 1.2% thiocyanate solution from 0.5 to 2 M hydrochloric acid (initial) up to pH 8.0. The extractable species of cobalt(II), nickel(II), copper(II), and palladium(II) from thiocyanate medium are probably similar and of the type [M(CNS)₄]^2? [K·TBP·3H₂O]₂ ⁺ (buffer solution) and [M(CNS)₄]^2? [H·TBP·3H₂O]⁺ ₂ (acid solution). A simple extraction scheme has been worked out for the separation of palladium(II) from iron(III), cobalt(II), nickel, manganese(II), copper(II), and platinum.     

Antibacterial Co(II), Cu(II), Ni(II) and Zn(II) Complexes of Thiadiazoles Schiff Bases

Schiff bases were obtained by condensation of 2-amino-l,3,4-thiadiazole with 5-substituted-salicylaldehydes which were further used to obtain complexes of the type [M(L)(2)]Cl(2), where M=Co(II), Cu(II), Ni(II) or Zn(II). The new compounds described here have been characterized by physical, spectral and analytical data, and have been screened for antibacterial activity against several bacterial strains such as Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa. The antibacterial potency of these Schiff bases increased upon chelation/complexation, against the tested bacterial species, opening new aproaches in the fight against antibiotic resistant strains.     

Removal of Cd(II), Pb(II), Cu(II) and Ni(II) from water using modified pine bark

This paper describes the removal of Cd(II), Pb(II), Cu(II), and Ni(II) ions from aqueous solutions using chemically modified pine barks (Pinus nigra). In this article, effects of chemical modification methods on the adsorption capacity have been investigated. Changes of the surface properties were examined by the FTIR, SEM and zeta potential analyses. HCl, NaOH, Fenton reactive, polymerization, acetone, ethanol, chloroform, tetra ethylene glycol, diethyl ether and glycol were used for modification processes. Maximum adsorption capacities were obtained by modification with NaOH (13-20 mg/g), Fenton (12-17 mg/g) and polymerization (12-16.5 mg/g). These modification processes also decreased Chemical Oxygen Demand of water from 1820 mg/L for raw pine barks to 35 mg/L for NaOH modified barks. Adsorption capacities of adsorbents increased from 2 mg/g to 20 mg/g as a result of modification that accordingly increase adsorbent surface activity.     

Stability constants of adipate complexes of copper(II), nickel(II), zinc(II), cobalt(II), uranyl(II) and thorium(IV) determined by electrophoresis

Stability constants of Copper(II), Nickel(II), Cobalt(II), Zinc(II), Uranyl(II) and Thorium(IV) adipates have been determined by paper electrophoresis. Adipic acid (0.005 mol dm^?3) was added to the background electrolyte: 0.1 mol dm^?3 HClO₄. The proportions of (CH₂)₄COOH COO^? and (CH₂)₄C₂O⁼₂ were varied by changing the pH of the electrolyte. These anions yielded the complexes Zn(CH₂)₄COOH COO⁺, Co(CH₂)₄COOH COO⁺, Ni(CH₂)₄COOH COO⁺, Th(CH₂)₄COOH COO³⁺, Th[(CH₂)₄COOH COO]₄, Cu(CH₂)₄ C₂O₄ and UO₂[(CH₂)₄(C₂O₄)]^2?₂, whose stability constants are found to be 10^2.8, 10^2.8, 10^3.2, 10^5.2, 10^15.3, 10^2.7 and 10^11.8 respectively (μ = 0.1, temp. 40°C).     

Thin‐Layer Chromatography of Cu(II), Co(II) and Ni(II)

Abstract

The chromatographic behavior of some heavy metals on thin layer of silica gel was studied. The effect of polarity of mixed developing agent systems on the R_f values of metal complexes was investigated. The linear dependence between the R_f values and the polarity of developing agents was deduced and a series of good separations of Cu(II),Co(II) and Ni(II) were obtained successfully. This method was applied to separate Cu(II) and Ni(II) in a real sample.     

Mono- and multi-component biosorption of lead(II), cadmium(II), copper(II) and nickel(II) ions onto coco-peat biomass

The potential of using coco-peat biomass (CPB) has been assessed for the removal of Pb(II), Cd(II), Cu(II) and Ni(II) ions from single and quaternary solutions. According to Langmuir isotherm, the maximum biosorption capacity of CPB was 0.484, 0.151, 0.383 and 0.181 mmol/g for Pb(II), Cd(II), Cu(II) and Ni(II) ions, respectively. Scanning electron microscopy along with energy-dispersive X-ray spectroscopy and Fourier-transform IR spectroscopy confirmed changes in the biosorbent functionality after metal sorption. Through quaternary isotherm experiments, 16.1%, 48.2%, 32.3% and 46.5% decrease in experimental uptakes were observed for Pb(II), Cd(II), Cu(II) and Ni(II), respectively, in the presence of other metal ions.     

1-Amino-4-aryl-2(1H)-pyrimidinthione: Acidität und Komplexbildung mit Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Pb(II) und Ag(I)

1-Amino-4-aryl-2(1H)-pyrimidinethiones: Acidity and Complex Formation with Nonferrous Metal Ions and Ag(I) Acid dissociation constants of new 2, 3 and already known 1 substituted 1-amino-4-aryl-2(1H)-pyrimidinethiones and stability constants of their nonferrous metal ion and silver complexes have been measured pH-potentiometrically in a 75% (v/v) mixture of dioxane/water. The influence of the substituents on pK_a- and lgβ_n-values is discussed. The X-ray structure analysis of bis[1-(4-toluenesulfonamido)-4-(4-tolyl)-2(1H)-pyrimidinethionatol]-nickel(II) 5 proves that pyrimidinethiones coordinate via their thione sulphur and aminonitrogen. However, the bond lengths are not levelled in the chelating ring.     

Physicochemical studies on square-planar Cu(II), Ni(II) and Co(II) chelate polymers

Chelate polymers of Cu(II), Ni(II) and Co(II) with bis-oxime of 5,5′-methylene bis(salicylaldehyde) have been prepared. The square-planar structure of the complexes was determined on the basis of infrared and electronic spectral measurements in conjunction with magnetic susceptibility measurements. The thermal stability of the chelates, obtained from the TG thermograms has the following order: Co(II) and Ni(II) chelates are found to increase their coordination number by interaction with pyridine at right angles to the plane of the parent molecule. The resulting complex is found to have octahedral structure. The ligand-field and nephelauxetic parameters have been determined from the spectra, using ligand-field theory of spin-allowed transitions which are found consistent with six-coordinate structure for these adducts.     

Cobalt(II), Zinc(II) and Cadmium(II)-Squarate Complexes with N-Methylimidazole

Three M(II)-squarate complexes, [Co(sq)(H₂O)(Nmim)₄] (1), [Zn(μ_1,3-sq)(H₂O)₂ (Nmim)₂] _n (2) and [Cd(μ_1,3-sq)(H₂O)₂(Nmim)₂] _n (3) (sq = squarate, Nmim = N-methylimidazole) have been synthesized and characterized by elemental, spectral (IR and UV–Vis.) and thermal analyses. The molecular structures of the complexes have been investigated by single crystal X-ray diffraction technique. The squarate ligand acts as two different coordination modes as a monodentate (in 1) and bis(monodentate) (O ^1– O ³ ) bridging ligand (in 2, 3). The Co(II) atom has a distorted octahedral geometry with the basal plane comprised of three nitrogen atoms of Nmim ligands and a oxygen atom of squarate ligand. The axial position is occupied by a nitrogen atom of Nmim and one aqua ligand. The crystallographic analysis reveals that the crystal structures of 2 and 3 are one-dimensional linear chain polymers along the c and b axis, respectively. The configuration around each metal(II) ions are distorted octahedral geometry with two nitrogen atoms of trans-Nmim, two aqua ligands and two oxygen atoms of squarate-O¹,O³ ligand. These chains are held together by the C–H···π, π···π and hydrogen-bonding interactions, forming three-dimensional network.     

Conductometric studies of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) tetrafluoroborates in N,N—dimethylacetamide solutions

Results are reported for the molar conductivities at 25°C of N,N—dimethylacetamide (DMA) solutions of Bu₄NBF₄ and Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) tetrafluoroborates. The limiting molar conductivities of [M(DMA)₆]²⁺ (M  MN, Co, Ni, Cu, Zn) and BF^?₄, as well as association constants for Co(BF₄)₂ in DMA solutions have been calculated. The slight differences between conductometric curves of different metal ions are discussed.     

Synthesis, Characterization and Biological Evaluation of Co(II), Cu(II), Ni(II) and Zn(II) Complexes With Cephradine

Some Co(II), Cu(II), Ni(II) and Zn(II) complexes of antibacterial drug cephradine have been prepared and characterized by their physical, spectral and analytical data. Cephradine acts as bidentate and the complexes have compositions, [M(L)(2)X(2)] where [M = Co(II), Ni(II) and Zn(II), L = cephradine and X = Cl(2)] showing octahedral geometry, and [M(L)(2)] where [M = Cu(II), L = cephradine] showing square planar geometry. In order to evaluate the effect of metal ions upon chelation, eephradine and its complexes have been screened for their antibacterial activity against bacterial strains, Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa.     

Calcium silicate hydrate (II) (“C-S-H(II)”)

This semicrystalline phase, originally named ‘calcium silicate hydrate(II)’ by Taylor (1950), has been studied with X-rays, electron optics, chemical investigation of silicate anion type, infrared spectra, and thermal methods. It is structurally related to jennite (C₉S₆H₁₁) and probably also to the fibrous CSH of cement pastes, the three phases forming a sequence of decreasing crystallinity. The specimen studied had approximate composition C₂SH_3.2 after standing over saturated CaCλ₂ at about 15°C. CSH(II) contains metasilicate chains and pyrosilicate groups and has a disordered layer structure. Much of the water can be lost reversibly without significant change in lattice parameters.     

Adsorption of Cr(III), Ni(II), Zn(II), Co(II) ions onto phenolated wood resin

In this study, phenolated wood resin was used an adsorbent for the removal of Cr(III), Ni(II), Zn(II), Co(II) ions by adsorption from aqueous solution. The adsorption of metal ions from solution was carried at different contact times, concentrations and pHs at room temperature (25°C). For individual metal ion, the amount of metal ions adsorbed per unit weight of phenolated wood resin at equilibrium time increased with increasing concentration and pH. Also, when the amounts of metal ions adsorbed are compared to each other, it was seen that this increase was order of Cr(III) > Ni(II) > Zn(II) > Co(II). This increase was order of Cr(III) > Ni(II) > Co(II) > Zn(II) for commercial phenol–formaldehyde resin. Kinetic studies showed that the adsorption process obeyed the intraparticle diffusion model. It was also determined that adsorption isotherm followed Langmuir and Freundlich models. Adsorption isotherm obtained for commercial phenol–formaldehyde resin was consistent with Freundlich model well. Adsorption capacities from Langmuir isotherm for commercial phenol–formaldehyde resin were higher than those of phenolated wood resin, in the case of individual metal ions. Original adsorption isotherm demonstrated the monolayer coverage of the surface of phenolated wood resin. Adsorption kinetic followed the intraparticle diffusion model. The positive values of ΔG° determined using the equilibrium constants showed that the adsorption was not of spontaneous nature. It was seen that values of distribution coefficient (K_D) decreasing with metal ion concentration in solution at equilibrium (C_e) indicated that the occupation of active surface sites of adsorbent increased with metal ions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2838–2846, 2006     

THE BEHAVIOUR-STRUCTURE RELATIONS IN THE EXTRACTION OF COBALT(II), NICKEL(II), COPPER(II) AND CALCIUM(II) BY KONOACIDIC ORGANOPHOSPHORUS EXTRACTANTS

The reaction stoichiometrics were studied in the extraction of Co(II), Ni(II), Cu(II) and Ca(II) by n-octyl, 1-methylheptyl and 2-ethylhexyl hydrogen styrylphosphonates and di-2-ethylhexylphosphoric acid and 2-ethylhexyl hydrogen 2-ethylhexylphosphonate. The ultraviolet-visible and infrared spectra were recorded for these extractants and their complexes with the above metals. Based on the experimental data, an empirical relationship was established between the structure of the extractants and the extracting behavior: pH_½ = ApKa + Bν_p=0 - c where pKa and ν_p=0 are the acid dissociation constant of the extractants and the characteristic frequency of infrared absorption for the P=0 group, respectively. The values of A, B and C depend on the extracted metals. The analysis of the relationship between the steric effect of substituting groups and extracting power seems to indicate that the steric effect has been implied in the coefficients A, B and C.     

Simultaneous spectrophotometric determination of copper(II), lead(II) and cadrnium(II)

The full spectrum technique in the fourier domain was studied for simultaneous determination of Cu(II), Pb(II) and Cd(II) with 4-(2-pyridylazo) resorcinol (PAR). A program called SPGRFSQ. was designed to perform the calculations. Seven error functions were calculated for deducing the number of factors. Data reduction was performed using principal component analysis (PCA) algorithm. Experimental results showed the method to be successful even where there was severe overlap of spectra.     

Studies on Ambient Cured Biobased Mn(II), Co(II) and Cu(II) Containing Metallopolyesteramides

In this paper linseed oil based metallopolyesteramides (Mn(II)-/Co(II)-/Cu(II)-LPEA) containing metals [with half filled (d ⁵) and partially filled (d ⁷ and d ⁹) d orbitals] were synthesized via green route for the application of eco-friendly protective green material. This paper also described the role of occupancy of d orbitals on the performance of such polymers. The synthesis reaction was carried out in situ through condensation polymerization among linseed fatty amide diol (HELA), phthalic anhydride and respective metal acetates [M (OCOCH₃)₂; M = Mn(II), Co(II), Cu(II); different mole ratios] in absence of any harmful organic solvent. The structural determination (FTIR, ¹H-NMR and ¹³C-NMR), curing, thermal, physico-chemical, physico-mechanical, anticorrosive/chemical resistance, antibacterial properties of Mn(II)-/Co(II)-/Cu(II)-LPEA were carried out. The curing mechanism of the resin was confirmed by the comparison of FTIR spectra of uncured and cured resin. The curing mechanism of Mn(II)-/Co(II)-/Cu(II)-LPEA is found to be contrary to that of reported oil based polymer that involves the lipid autoxidation (slow process) in which driers are required to speed up the room temperature curing process. The incorporation of metals in Mn(II)-/Co(II)-/Cu(II)-LPEA improved the thermal stability as compared to virgin linseed oil based polyesteramide (LPEA). Mn(II)-/Co(II)-/Cu(II)-LPEA also show excellent antibacterial performance against Staphylococcus aureus and Escherichia coli. The observed diversity in material properties suggests that Mn-LPEA may be useful as an eco-friendly protective green material with thermal stability up to 320–330 °C.     

Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of Some N-Alkyl-N-Phenyl-Dithiocarbamates

The thermal decomposition of Zn(II), Cd(II) and Hg(II) complexes of N-ethyl-N-phenyl and N-butyl-N-phenyl dithiocarbamates have been studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The products of the decomposition, at two different temperatures, were further characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The results show that while the zinc and cadmium complexes undergo decomposition to form metal sulphides, and further undergo oxidation forming metal oxides as final products, the mercury complexes gave unstable volatiles as the final product.     

Synthesis, Characterization and Antiproliferative Activity of the Co(II), Ni(II), Cu(II), Pd(II) and Pt(II) Complexes of 2-(4-Thiazolyl)Benzimidazole (Thiabendazole)

Complexes of 2-(4-thiazolyi)benzimidazole (thiabendazole, THBD) with Co(II), Ni(II), Cu(ll) of general formula ML(2)(NO(3))(2) H(2)O and complexes of Pd(II) and Pt(II) of general formula ML2Cl(2) H(2)O have been obtained and characterized by elemental analyses, IR and far IR spectroscopy and magnetic measurements. The X-ray crystal structure of the copper(II) complex has been determined. The in vitro cell proliferation inhibitory activity of these compounds was examined against human cancer cell lines A 549 (lung carcinoma), HCV-29 T (urinary bladder carcinoma), MCF-7 (breast cancer), T47D (breast cancer), MES-SA (uterine carcinoma) and HL-60 (promyelocytic leukemia). Pt-THBD has been found to exhibit an antileukemic activity of the HL-60 line cells matching that of an arbitrary criterion.