The extraction of mercury(II), silver(I), cobalt(II) and cadmium(II) by dioctylarsinic acid in chloroform

Dioctylarsinic acid (HDOAA) in chloroform solution has been investigated as a reagent for the extraction of Hg(II), Ag(I), Co(II), and Cd(II). Silver, cobalt and cadmium are not extracted below pH 7. An extraction coefficient of 1.1, constant over the pH range 1–6.5, was observed for Hg(II). With HCl concentrations of 1–8 M the extractability of mercury decreased slowly, reaching E_a⁰ = 0.05 at 8 M HCl. Silver formed a silver dioctylarsinate precipitate which collected at the interface. The extraction coefficients for Hg(II), Co(II) and Cd(II) increased above pH 7 to values of 20 (pH 9.1), 30 (pH 8.0), and 23 (pH 10), respectively. Reagent- and pH-dependence studies indicated that Co(II) and Cd(II) are extracted as M(DOAA)₂ or M(DOAA)Cl through interaction of HDOAA with M(OH)₂ or M(OH)⁺. Mercury was extracted from solutions of pH 1–6.5 as HgCl₂ (HDOAA)_2.5.     

Cation-Induced dimerization of nickel(II), platinum(II), and palladium(II) meso-tetra(benzo-15-crown-5)porphyrinates

Cation-induced dimerization of nickel(II), platinum(II), and palladium(II) meso-tetra(benzo-15-crown-5)porphyrinates (Ni(II)TCP, Pd(II)TCP, and Pt(II)TCP) on treatment with potassium thiocyanate in a chloroform-methanol solution has been studied by electronic absorption spectroscopy. The formation of [{MTCP}₂(K⁺)₄](SCN^?)₄ in solution induces a hypsochromic shift of the Soret band and a bathochromic shift of the β-band with respect to their positions in the spectrum of MTCP. The equilibrium constants (K) for the 2MTCP + 4K⁺ = [{MTCP}₂(K⁺)₄] processes at 20°C are determined to be as follows: log K _Ni(II)TCP = 27.31 ± 1.67, logK _Pd(II)TCP = 27.16 ± 1.43, and logK _Pt(II)TCP = 26.15 ± 1.56.     

Radiochemical extraction of mercury(II) from acidic chloride solutions using dialkylsulphides

The liquid-liquid extraction behavior of Hg(II) from aqueous acidic chloride solutions has been investigated by tracer techniques using dialkylsulphides (R₂S) namely, dibutylsulphide (DBS) and dioctylsulphide (DOS) as extractants. These extraction data have been analyzed by both graphical and theoretical methods by taking into account complexation of the metal ion in the aqueous phase with inorganic ligands and all plausible complexes extracted into the organic phase. The results clearly indicate that Hg(II) is extracted into xylene as HgCl₂ ^. nDBS/nDOS (where n = 2 and 3). The equilibrium constants of the extracted complexes have been deduced by non-linear regression analysis. The separation possibilities of Hg(II) from other metal ions viz. Ca(II), Mg(II), Ba(II) and Fe((III), which are present in the industrial wastes of the chlor-alkali industry has also been discussed.     

3-(Aryl)-2-sulfanylpropenoates of mercury(II) and phenylmercury(II)

Compounds [HQ]₂[Hg(L)₂] and [HQ][PhHg(L)] [where HQ = diisopropylammonium cation; L = pspa, fspa, tspa, where p = 3-(phenyl), f = 3-(2-furyl), t = 3-(2-thienyl), and spa = 2-sulfanylpropenoato] have been prepared by the reaction of mercury(II) acetate or phenylmercury(II) acetate with the corresponding acid in the presence of diisopropylamine in ethanol. The compounds have been characterized by elemental analysis, FAB mass spectrometry and IR and NMR (¹H, ¹³C) spectroscopy. The crystal structures of the [HQ]₂[Hg(L)₂] compounds show the presence of diisopropylammonium cations and [Hg(L)₂]²⁻ anions. In each anion the Hg atom is in an HgO₂S₂ environment and this can be described as nido-tbp. The crystal structures of the [HQ][PhHg(L)] compounds show the presence of diisopropylammonium cations and [PhHg(L)]⁻ anions in which the Hg atom adopts an HgCOS distorted T-environment. The NMR data suggest that the coordination mode of the ligand L²⁻ determined by X-ray diffractometry in the solid remains in solution.     

Complexation en solution aqueuse des ions magnesium(II), manganese(II), nickel(II), cuivre(II) et plomb(II) avec la s-carboxymethyl-l-cysteine: Complex formation of magnesium(II), manganese(II), nickel(II), copper(II) and lead(II) with S-carboxymethyl-L-cysteine in aqueous solution

Complex formation of magnesium(II), manganese(II), nickel(II), copper(II) and lead(II) with S-carboxymethyl-L-cysteine in aqueous solution.The complex formation between Mg(II), Mn(II), Ni(II). Cu(II), Pb(II) ions and S-carboxy-methyl-l-cysteine (H₂A) has been studied by measurement of pH at 25°C and constant ionic strength (1 M NaClO₄). Although no interaction occurs with Mg(II), this work provides evidence for a variety of complexes: MnA; CuHA⁺; CuA; CuA₂^2-; NiHA⁺; NiA; NiA₂^2-; PbHA⁺; PbA et PbA(OH)^-. The overall formation constants of all these species are computed and refined. The results allow the determination of the distribution of the complexes as a function of pH; some structural features of the metal complexes in solution are indicated.     

Complexes of dicamba with cadmium(II), copper(II), mercury(II), lead(II) and zinc(II)

New solid complexes of a herbicide known as dicamba (3,6-dichloro-2-methoxybenzoic acid) with Pb(II), Cd(II), Cu(II) and Hg(II) of the general formula M(dicamba)₂·xH₂O (M=metal, x=0-2) and Zn₂(OH)(dicamba)₃·2H₂O have been prepared and studied. The complexes have different crystal structures. The carboxylate groups in the lead, cadmium and copper complexes are bidentate, chelating, symmetrical, in Hg(dicamba)₂·2H₂O - unidentate, and in the zinc salt - bidentate, bridging, symmetrical. The anhydrous compounds decompose in three stages, except for the lead salt whose decomposition proceeds in four stages. The main gaseous decomposition products are CO₂, CH₃OH, HCl and H₂O. Trace amounts of compounds containing an aromatic ring were also detected. The final solid decomposition products are oxychlorides of metals and CuO. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Synergic effect of triphenylphosphine oxide (TPPO) on the extraction of Hg(II), Se(IV), Co(II) and Mn(II) with fluorinated pyrazolone (HPMTFP)

Extraction of Hg(II), Se(IV), Mn(II) and Co(II) has been carried out with 1-phenyl-3-methyl-4-trifluoroacetyl-2-pyrazolin-5-one (HPMTFP) and triphenylphosphine oxide (TPPO) into chloroform from pH 1–10. Quantitative extraction of Hg(II), Mn(II) and Co(II) at pH 4 with equimolar 0.05M (PMTFP+TPPO) in chloroform was observed. Se(IV) remains unextracted at this pH range. The stoichiometric composition of the extracted complexes M(PMTFP)₂·nH₂O (M=Mn, Hg), M(PMTFP)₂·2TPPO (M=Mn and Co) and Co(PMTFP)₂·TPPO·H₂O at less than 0.1M TPPO has been established. The formation constantsK _m,0 andK _m,n and stability constants _m,n have been computed. The analytical method developed was applied to the IAEA standard reference material (SRM) potato fluor V-4 for the determination of these elements using NAA technique.     

Homoligand and mixed-ligand complexes of mercury(II) with aspartic acid and iminodiacetic acid and its derivatives

The formation of homoligand mercury(II) complexes with aspartic acid (H₂Asp) and aspartate-chelant mixed-ligand mercury(II) complexes with iminodiacetic acid (H₂Ida, IDA), 2-hydroxyethyliminodiacetic acid (H₂Heida, HEIDA), and nitrilotriacetic acid (H₃Nta, NTA) in an aqueous perchlorate medium was studied by spectrophotometry and pH-potentiometric titration. The following complexes were identified: [Hg(OH)Asp]^?, [HgAsp₂]^2?, [Hg(Asp)Ida]^2?, [Hg(Asp)Heida]^2?, and [Hg(Asp)Nta]^3?. The logarithms of their stability constants are, respectively, 11.74 ± 0.12, 20.18 ± 0.17, 20.11 ± 0.10, 19.82 ± 0.09, 19.48 ± 0.11, and 20.58 ± 0.07 (μ = 0.1 (NaClO₄), t = (20 ± 2)°C). The hydrogen and hydroxyl competition regions were located in the systems, and relationships between the molar yields of complex species and the reactant concentrations were established. The protonation and dissociation constants of aspartic acid were derived from pH-potentiometric titrations. Experimental data were analyzed using mathematical models allowing one to judge the existence of various complex species in the solution and to identify the species that are sufficient to reproduce the observed data.     

Synthesis,characterization, cyclic voltammetry and biological studies of Zn (II), Cd (II), Hg (II) and UO22+ complexes of thiosemicarbazone salt

Zn (II), Cd (II), Hg (II) and U (VI)O₂²⁺ complexes of water‐soluble thiosemicarbazone ligand (NaH₃PyTSC) have been prepared and characterized using various techniques. Fourier transform‐infrared (FT‐IR) demonstrated that NaH₃PyTSC ligand behaves as a binegative NOS tridentate in [Hg(H₂PyTSC)(H₂O)]₂ and [UO₂(H₂PyTSC)(H₂O)]₂ complexes via the deprotonated SH, (C=N)_az groups from one molecule and SO₃^? group from another molecule, while it behaves as a binegative NNSO tetradentate in [Cd(H₂PyTSC)(H₂O)₂]₂ complex through the deprotonated SH group, the SO₃^? group and the nitrogen of both the (C=N)_az and (C=N)_py. Finally, it behaves as a binegative OO bidentate in [Zn(H₂PyTSC)(H₂O)₂]₂·2H₂O complex by the deprotonated OH group from one molecule and SO₃^? group from another ligand molecule. The spectral data suggest a tetrahedral coordination around Hg (II) and Zn (II) ions, and an octahedral coordination around Cd (II) and U (VI)O₂²⁺ ions. The NaH₃PyTSC ligand exhibited maximum luminescent intensity at 501 nm, while Zn (II), Cd (II) and Hg (II) chelates show emission bands at 459, 458 and 358 nm, respectively. Two comparable methods were used to estimate various thermodynamic parameters. Cyclic voltammetry has been studied for Cd (II) complex in solution. Different biological applications of the isolated complexes have been estimated. It was found that [Cd(H₂PyTSC)(H₂O)₂]₂ showed the most effective antioxidant and anticancer activity.     

Preparation,infrared, Raman and N.M.R. spectra of N,N′-Diethylthiourea complexes with zinc(II), cadmium(II) and mercury(II) halides

Several complexes of N,N′-diethylthiourea (Dietu) with zinc(II), cadmium(II) and mercury(II) halides were prepared and characterized by i.r. (4000–60 cm^?1), raman (400–60 cm^?1), in the solid state and n.m.r. and conductometric methods in solution. The complexes Zn(Dietu)₂X₂, Cd(Dietu)₂X₂ (X ? Cl, Br, I) and Hg(Dietu)₂X₂ (X ? Br, I) are tetrahedral species in which intramolecular ? NH …? X interactions have been observed. The 1:1 mercury(II) complexes, Hg(Dietu)X₂ (X ? Cl, Br), appear to have a dimeric tetrahedral halide-bridged structure in the solid state. In all these complexes N,N′-diethylthiourea is sulphur-bonded to the metal.     

Zinc(II), Cadmium(II), Mercury(II), and Lead(II) Complexes of N-Carboxymethyl-D,L-threonine in Aqueous Solution

The formation of complexes of Zn(II), Cd(II), Hg(II), and Pb(II) and N-carboxymethyl-D,L-threonine (H₂CMT, H₂L) in aqueous solutions has been studied by spectrophotometric and potentiometric methods. The complexation model for each system has been established by the HYPERQUAD program from the potentiometric data. Three different behaviors are found: ML₂H, MLH, ML, MLOH, and ML₂ complexes are formed by Zn(II) and Cd(II) ions, ML₂H, ML, MLOH, and ML₂ are formed by Hg(II) ion, and only 1/1 complexes MLH, ML, and MLOH are formed by the Pb(II) ion. The formation constants determined for all these complexes allow simulation of experimental titration curves with good agreement. The speciation of multimetal systems with H₂CMT shows that this compound is a good and selective ligand at low pH for the Hg(II) ion.     

Spectrophotometric flow-injection analysis of mercury(II) in pharmaceuticals with p-nitrobenzoxosulfamate

A new, simple and rapid spectrophotometric FI method for the accurate and precise determination of Hg(II) in pharmaceutical preparations has been developed. The method is based on the measuring the decrease of absorbance intensity of p-nitrobenzoxosulfamate (NBS) due to the complexation with Hg(II). The absorption peak of the NBS, which is decreased linearly by addition of Hg(II), occurs at 430 nm in 2×10⁻⁴ mol l⁻¹ HNO₃ as a carrier solution. Optimization of chemical and FI variables has been made. A micro column consisting of several packing materials applied instead of reaction coil was also investigated. A background level of Fe(III) maintained in reagent carrier solution with NBS was found useful for sensitivity and selectivity. Under the optimized conditions, the sampling rate was over 100 h⁻¹, the calibration curve obtained were linear over the range 1-10 μg ml⁻¹, the detection limit was lower than 0.2 μg ml⁻¹ for a 20 μl injection volume, and the precision [S_r=1% at 2 μg ml⁻¹ Hg(II) (n=10)] was found quite satisfactory. Application of the method to the analysis of Hg(II) in pharmaceutical preparations resulted a good agreement between the expected and found values.     

Synthesis and structural studies of 2-acetylthiophene-2-thenoylhydrazone complexes of oxovanadium(IV), manganese(II), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II) and mercury(II)

Complexes with chemical compositions VO(Hatth)₂SO₄, VO(Hatth)₂SO₄·py, [M(Hatth)₂Cl·H₂O]Cl [M = Mn(II), Co(II) and Ni(II)], [Cu(Hatth)₂Cl]₂Cl₂, [Cu(Hatth)₂· Cl·py]Cl, [Cd(Hatth)₂Cl]Cl, M(Hatth)₂Cl₂ [M = Zn(II) and Hg(II)], VO(atth)₂, VO(atth)₂py, M(atth)₂(py)₂ [M = Mn(II) and Cu(II)], M(atth)₂(H₂O)₂ [M = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)], Hatth = 2-acetylthiophene-2-thenoylhydrazone, and atth, its deprotonated form, have been prepared and characterized by analytical data, molar conductance, magnetic susceptibility, electronic and photoacoustic, ESR, IR and NMR spectral studies. X-ray diffraction study has been used to determine the shape and the dimensions of the unit lattice of copper(II) complexes.     

Kinetics and mechanism of zinc(II), cadmium(II), and mercury(II) incorporation into meso tetrameta-tolueneporphyrin

The kinetics of Zn(II), Cd(II), and Hg(II) incorporation into meso tetrameta-tolueneporphyri n (H₂T(m-CH₃)PP) in acetone have been studied by means of stopped-flow method. A unified reaction mechanism was proposed and the kinetic parameters were obtained by nonlinear least-square methods. The effect of ionic strength (I) on Cd(II)/H₂T(m-CH₃)PP was investigated. It has been found that there is a negative kinetic salt effect and the relationship of rate constants with ionic strength was obtained. Some solvent effects have also been investigated in this article. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 277–283, 1998.     

Studies of Co(II), Ni(II), Cu(II) and Cd(II) chelates with different phosphonic acids

Co(II), Ni(II), Cu(II) and Cd(II) chelates with 1-aminoethylidenediphosphonic acid (AEDP, H₄L¹), α-amino benzylidene diphosphonic acid (ABDP, H₄L²), 1-amino-2-carboxyethane-1,1-diphosphonic acid (ACEDP, H₅L³), 1,3-diaminopropane-1,1,3,3-tetraphosphonicacid (DAPTP, H₈L⁴), ethylenediamine-N,N′-bis(dimethylmethylene phosphonic)acid (EDBDMPO, H₄L⁵), O-phenylenediamine-N,N′-bis(dimethyl methylene phosphonic)acid (PDBDMPO, H₄L⁶), diethylene triamine-N,N,N′,N′,N″N″-penta(methylene phosphonic)acid (DETAPMPO, H₁₀L⁷) and diethylene triamine-N,N″-bis(dimethyl methylene phosphonic)acid (DETBDMPO, H₄L⁸) have been synthesised and were characterised by elemental and thermal analyses as well as by IR, UV–VIS, EPR and magnetic measurements. The first stage in the thermal decomposition process of these complexes shows the presence of water of hydration, the second denotes the removal of the coordinated water molecules. After the loss of water molecules, the organic part starts decomposing. The final decomposition product has been found to be the respective MO·P₂O₅. The data of the investigated complexes suggest octahedral geometry with respect to Co(II) and Ni(II) and tetragonally distorted octahedral geometry with respect to Cu(II). Antiferromagnetism has been inferred from magnetic moment data. Infrared spectral studies have been carried out to determine coordination sites.     

Metallatriazadiphosphorines of zinc(II), cadmium(II) and mercury(II)

Metallatriazadiphosphorine complexes corresponding to [{N(PPh₂NR)₂}M(OAc)] and [{N(PPh₂NR)₂}₂M], (R = Ph or SiMe₃; M = Zn, Cd or Hg) have been synthesized under strictly anhydrous and inert conditions by the reaction of the acyclic bis-silylated phosphazene ligand, [HN(PPh₂NSiMe₃)₂], or the bis-phenylated phosphazene ligand, [HN(PPh₂NPh)₂], with Zn, Cd and Hg acetate in 1:1 and 2:1 molar ratios. These complexes are highly soluble in common organic solvents, but unstable hydrolytically as well as thermally, even under reduced pressure. Molecular weight determinations in benzene indicated the monomeric nature of these complexes. Further, they have been characterized on the basis of elemental analysis and spectral studies: i.r. and n.m.r. (¹H, ¹³C and ³¹P) that plausibly reveal a trigonal planar and tetrahedral geometry around the metal atom in the complexes.     

Synthesis and characterization of some metal complexes of cystine: [Mn(C6H10N2O4S2)]; where MII = Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II)

Cystine forms metal complexes of general formula [M^II(C₆H₁₀N₂O₄S₂)]; where M^II = Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) in the aqueous medium. Before reacting with metal salts the ligand solution was neutralized by NaHCO₃ solution. The complexes were formulated by comparing the C, H, N, S and metal analysis data. The prepared complexes were characterized by different physicochemical methods. The UV-vis, FTIR spectral analysis, magnetic susceptibility of these complexes are discussed. Cyclic voltammetric studies of some of the complexes are also reported.     

On-line determination of mercury(II) by membrane separation flow injection analysis

A rapid and inexpensive gas-diffusion (GD) flow injection method for the on-line determination of Hg(II) in aqueous samples is described. The analytical procedure involves the injection of a Hg(II) sample into a 1.5 M H₂SO₄ carrier stream which is merged with a reagent stream containing 0.6% SnCl₂ and 1.5 M H₂SO₄. Under these conditions Hg(II) is reduced to metallic mercury which partially evaporates through a Teflon membrane into an acceptor stream containing 1.75×10⁻⁴ M KMnO₄ in 0.3 M H₂SO₄. The decrease in the absorbance of the acceptor stream at 528 nm corresponding to the absorption maximum of the permanganate anion can be related to the original concentration of Hg(II) in the sample. The method is characterized by a detection limit of 4 μg l⁻¹ and a sampling frequency of 8 h⁻¹. The flow system was successfully applied to the analysis of river samples spiked with Hg(II).     

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.