Sensitive and Selective Spectrophotometric Determination of Hg(II), Ni(II), Cu(II) and Co(II) Using Iminodibenzyl and 3-Chloroiminodibenzyl as New Reagents and Their Applications to Industrial Effluents and Soil Samples

Iminodibenzyl (IDB) and 3-chloroiminodibenzyl (Cl-IDB) are proposed as a new class of spectrophotometric reagents for the determination of micro amounts of mercury(II), nickel(II), copper(II) and cobalt(II) in the presence of 3-methyl-2-benzothiazoline hydrazone hydrochloride hydrate (MBTH) or 4-aminoantipyrine (AAP) as electrophilic coupling reagents. The reaction is carried out in neutral aqueous medium. The blue colour formed shows maximum absorbance at 660 nm using MBTH and 630 nm with AAP. The methods obey Beer's law. The molar absorptivity and Sandell's sensitivity show different values with different metals and reagents. The blue colour can also be extracted quantitatively which can be exploited as an efficient extractive spectrophotometric technique for the separation of metal ion from other interfering species. As many as 15 cations and 12 anions and/or complexing agents listed do not interfere. Both the methods have good reproducibility and can be satisfactorily applied in the determination of metals in industrial effluents and soil samples.     

The influence of some organic complexing agents on the potential of copper(II) - selective electrodes. application of the silicone rubber-based electrode to the determination of citrate ion and 8-hydroxyquinoline

The behaviour of the silicone rubber-based copper(II)-selective electrode in the presence of complexing agents is discussed. The electrode shows well defined responses to several complexing agents in solutions practically free of copper(II) ions. Titrimetric determinations of citrates and 8-hydroxyquinoline with potentiometric end-point detection are described.     

Indirect Spectrophotometric Determination of Vanadium(IV) by Flow Injection Analysis Based on the Redox Reaction with Copper(II) in the Presence of Neocuproine

Abstract

An indirect photometric method with a continuous-flow analysis is presented for the determination of trace amounts of vanadium(IV). It is based on the redox reaction of copper(II) with vanadium(1V) in the presence of neocuproine. In the presence of neocuproine, copper(I1) is reduced easily by vanadium(I V) to a copper(1)-neocuproine complex, which shows a n absorption maximum at 454 nm. By measuring t h e absorbance of the complex at this wavelength, vanadium(1V) in t h e range 2×10^?6 - 8 × mol dm^?5 mol dm^?3 can be determined at a rate of 120 samples h^?1. The fractional determination of vanadium(1V) and iron(I1) is also studied.     

Evaluation of the copper(II) complexing ability of ultrafiltered humic acid by the solvent extraction method.

A commercial humic acid dissolved in water was fractionated to nine samples by means of ultrafiltration (UF); the nominal molecular weight used for UF membranes was 1 k-200 kDa. Concerning the nine samples, copper(II) complexing capacities (CuCC) and conditional stability constants (beta) of the formed copper(II) complexes were measured by a solvent extraction method. A total organic carbon (TOC) and the UV-VIS absorption ratio (E350 nm/E450 nm) were also measured. From a comparison of these data, it was found that a) humic acids in each fraction formed two kinds of copper(II) complexes with different stability; b) the beta values obtained from each fraction were almost the same; c) large CuCC values were observed in the molecular weight range from 10 kDa to 20 kDa and below 1 kDa; d) molecules with molecular weight higher than 50 kDa scarcely had any copper(II) complexing ability; e) the values of CuCC/TOC of each fraction were in the range from 1.7 to 3.4 x 10(-7) mol mg(-1).     

Determination of uranium, iron, copper, and nickel from ore samples by MEKC using N,N'-ethylene bis(salicylaldimine) as complexing reagent

An analytical procedure has been developed for the separation of dioxouranium(VI), iron(III), copper(II), nickel(II), cobalt(II), cobalt(III), palladium(II), and thorium(IV) by MEKC using N,N'-ethylene bis(salicylaldimine) (H(2)SA(2)en) as a complexing reagent with total runtime <4.5 min. SDS was used as micellar medium at pH 8 with sodium tetraborate buffer (0.1 M). An uncoated fused-silica capillary with an effective length of 50 cm x 75 microm id was used with an applied voltage of 30 kV with photodiode array detection at 231 nm. Linear calibrations were obtained within 0.111-1000 microg/mL of each element with LODs within 37-325 ng/mL. The developed method was tested for analysis of uranium ore samples indicating its presence within 103-1789 microg/g with RSD within 0.79-1.87%. Likewise copper, nickel, and iron in their combined matrix were also simultaneously determined with RSD 0.4-1.6% (n = 6).     

Examination of the range of copper complexing ligands in natural waters using a combination of cathodic stripping voltammetry and computer simulation

Knowledge of the detection capabilities of speciation techniques, gained by calculation and computer simulation, can be combined with experimental measurements to arrive at an understanding of trace metal speciation which is less dependent on operational factors than other approaches. Examples of the application of this means of measuring copper speciation to samples from the Humber Estuary are given. Although concentrations of total dissolved copper can approach the estuarine Environmental Quality Standard value of 5 μg 1^?1, there is evidence for a substantial excess of complexing ligands at all locations except the outer estuary, where copper levels are much reduced by dilution. Dissolved copper is therefore present almost totally in the form of organic complexes. The range of different types of ligand is also assessed. In sea water, there appears to be a range of ligands of differing affinities for copper; the complexing capacity ranges from 20 nM [conditional stability constant of the copper complex (K′) > 10¹⁴] to 70 nM (K′) > 10⁸). For estuarine samples, ligands with a high affinity for copper seem to be predominant and the overall complexing capacity rises to over 200 nM. In freshwater samples, it is likely that the potential for varying combinations of weak and strong complexes will depend on the water quality, but a capacity to complex over 200 nM copper is not unusual.     

Evaluation of powdered infant formula milk as chelating agent for copper under simulated gastric conditions of a baby's stomach.

The objective of this study was to determine the complexing capacity of four types of powdered commercial milks with copper(II) using square wave adsorptive stripping voltammetry. Two were types of cow milk adapted for babies under one year (A and B), one was soymilk (C) and the other was normal milk (D). Milk solutions were prepared following the instructions shown on the milk container, and they were mixed with a pepsin solution simulating a baby's stomach conditions (pepsin and salts concentration, pH and temperature). Complexing capacity was determined by titrating milk samples with aliquots of a standard copper solution until the peak current due to solvated or free copper ions was increasing. Assuming a 1:1 copper-milk complex, the apparent stability constant was found using the pseudopolarogram method. The log K'(Cu-milk) values were 4.9, 5.0, 3.0 and 5.1 for A, B, C and D types of milk, respectively. Voltammograms of the milk solution as a function of copper added show that the binding properties of the four types of powdered milk studied were different and that saturation of the four types, occurs at different copper concentrations. Concentrations obtained were: 4.9, 5.8, 1.1 and 10.1 mM for A, B, C and D types, respectively. The best complexing agent was the solution prepared with powdered milk D and the worst was that of C. This is important for the bioavailability of this element as a micronutrient.     

A simple spectrophotometric determination of hydrogen peroxide at low concentrations in aqueous solution

The procedure described for the determination of hydrogen peroxide in aqueous solution, at concentrations in the rnage 1?120×10^?6 mol l^?1, is based on reduction of copper (II) ions by hydrogen peroxide in the presence of excess of 2,9-dimethyl-1,10-phenanthroline (DMP) to form the copper (I)-DMP complex. The copper (I)-DMP complex is determined directly by spectrophotometric measurement at 454 nm.     

Sorption and filtration of Hg(II) ions from aqueous solutions with a membrane containing poly(ethyleneimine) as a complexing polymer

The performances of a PVA/PEI complexing membrane for the removal of Hg(II) from aqueous solutions were investigated by performing sorption and filtration experiments. This membrane, that was previously shown to ensure efficient sorption of the heavy metal ions Pb(II), Cd(II) and Cu(II) at pH 5, presented a higher affinity for Hg(II) at pH 2.5. The sorption equilibrium was satisfactorily represented by the Langmuir model. In view of possible application to the treatment of industrial wastewaters, the effects of parameters such as pH, temperature, water hardness, and the presence of complexing chloride anions were investigated. The effect of increasing temperature was not straightforward: the complexation equilibrium constant decreased, but the mass of mercury sorbed increased, probably due to the higher mobility of the polymer chains that made internal sites available for complexing mercury. The maximum retention capacity of the membrane was 311 mg Hg g⁻¹. Also, operating at large calcium or chloride concentrations was not detrimental to the membrane performances. For regeneration of the membrane, a 0.05 M solution of EDTA is recommended on the basis of limited performance loss. When used in the filtration mode, the elimination ratio of Hg(II) was close to 99%.     

Separation of copper(II) and aluminium(III) from fresh waters by solid phase extraction on a complexing resin column

The solid‐phase extraction (SPE) of copper(II) and aluminium(III) from fresh waters on an ion‐exchange complexing resin containing iminodiacetic groups (Chelex 100) has been examined. Quantitative recovery of the metal ions was related to the breakthrough profile that, for some samples, could not be evaluated directly. A method is suggested for evaluation, instead, of the sorption curves, on the basis of passing different volumes of sample through the column. This enables evaluation of important properties, for instance the central point of the breakthrough curve, V_f. The column used was a small one, containing 0.10 g dry Chelex 100. The metal ion was eluted with a small volume of acid solution, 10 mL of 0.5 mol L^–1 HNO₃; this resulted in good preconcentration factors. For copper(II) it was found that fresh waters of similar composition could have different V_f in the same column. This was ascribed to different reaction coefficients (α_M(I)) of copper(II) in the considered samples, which affects V_f. By use of the proposed SPE procedure it is possible to evaluate the reaction coefficient of copper(II). The values of α_M(I) for two different drinking waters at pH 7.7 were found to be 3.70×10¹² and less than 4.40×10¹¹. Similar results were obtained for aluminium(III).     

The influence of complexing agents on the effectiveness of electrochemical masking with anionic surfactants in anodic stripping voltammetry

The influence of sodium dodecyl sulphate, sodium dodecyl sulphonate and sodium stearinate on the anodic stripping peaks of Tl(I), Pb(II), Cd(II), Cu(II) and In(III) was investigated. The supporting electrolytes were 0.5M sodium sulphate solution, 0.2M citrate solution (pH 3.7, 4.6 and 7.3), 0.5M tartrate solution (pH 4.4) and 0.1M solution of EDTA (pH 4.4). The composition of complex compounds forming in a solution under experimental conditions was defined. The conditions of ion reduction of metals on hanging mercury electrode during the electrolytical deposition were investigated. The investigation included an analysis of voltammetric curves of the metal ions. The obtained results suggest that "electrochemical masking" is much stronger in electrolytes containing a complexing agent than in the sodium sulphate solution. The influence of the complexing agent may not be explained in terms of the interaction between the form of the complex and the charge of the adsorbed surfactant particles; rather the complexing process is connected with indirect inhibition, i.e., by decreasing the rate of charge transfer reaction.     

Voltammetric Sensing of Mercury and Copper Cations at Poly(EDTA‐like) Film Modified Electrode

Complexing polymer‐coated electrodes have been synthesized by oxidative electropolymerization of ethylenediamine tetra‐N‐(3‐pyrrole‐1‐yl)propylacetamide (monomer L ). The presence of four polymerizable pyrrole fragments on the same EDTA skeleton was thought to confer enhanced rigidity and controlled dimensionality to the resulting complexing materials, which were used for the electrochemical detection of Hg(II), Cu(II), Pb(II) and Cd(II) ions by means of the chemical preconcentration‐anodic stripping technique. The polyamide electrode material showed particularly a significant selectivity towards mercury ions, even in the presence of a large excess of other metal cations. Moreover, the use of imprinted polymer‐coated electrodes prepared by electropolymerization of L in the presence of metal cations turned out to significantly improve the detection limits, down to 5×10^?10 mol L^?1 for Hg(II) and Cu(II) species.     

Solid phase extraction of copper(II) by fixed bed procedure on cation exchange complexing resins

The efficiency of the metal ion recovery by solid phase extraction (SPE) in complexing resins columns is predicted by a simple model based on two parameters reflecting the sorption equilibria and kinetics of the metal ion on the considered resin. The parameter related to the adsorption equilibria was evaluated by the Gibbs–Donnan model, and that related to the kinetics by assuming that the ion exchange is the adsorption rate determining step. The predicted parameters make it possible to evaluate the breakthrough volume of the considered metal ion, Cu(II), from different kinds of complexing resins, and at different conditions, such as acidity and ionic composition.     

Evaluation of micromolar compleximetric titrations for the determination of the complexing capacity of natural waters

The titration of micromolar levels of complexing agents with metal ion titrants, and voltammetric methods to locate the equivalence point, has been evaluated experimentally and theoretically. Both anodic stripping voltammetry and differential pulse polarography give systematically low results if labile metal ions are used as titrants. Low-temperature (0 °C) dual-cell anodic stripping voltammetry greatly minimizes the effects of metal complex lability but the mercury film electrodes deteriorate rapidly because of temperature cycling. A micromolar compleximetric titration with a voltammetric end-point is not a practical method for determining the complexing capacity of natural waters.     

Comparative distribution coefficients and cation-exchange behaviour of the alkaline earth elements with various complexing agents

Equilibrium distribution coefficients are presented for the alkaline earth metals Be(II), Mg(II), Ca(II), Sr(II) and Ba(II) with the complexing agents acetate, formate, lactate, citrate, tartrate, alpha-hydroxyisobutyrate, malonate, malate, acetylacetonate, EDTA, EGTA and DCTA, and the AG50W-X8 cation-exchange resin. Coefficients in HCl, HNO(3), HClO(4) and NH(4)Cl are included for the sake of completeness. The merits of the various complexing agents for the separation of adjacent element pairs are discussed and experimental elution curves are presented for selected separations. Separation factors for adjacent elements are calculated at eluting agent concentrations corresponding to a distribution coefficient of 10 for the less strongly absorbed element and are presented together with the eluting agent concentrations to form a basis for comparison.     

Chromatographic study of anionic complexes

Summary In this paper we have reported our results on the attempted separation of copper(II), nickel(II), cobalt(II) and iron(III) in mixtures by filter paper strip chromatography, using aqueous ethanol as solvent. The effect of the presence of varying concentrations of citrate ion as a complexing agent in the mixtures has been studied. The complexing agent has been added in the metal solution, and not in the solvent as usually done by previous workers.     

2,4,6-triaminopyrimidine and its associates with bis(hydroxymethyl)phosphinic acid. State in solution, protolytic, and complexing properties

Protolytic and complexing properties of 2,4,6-triaminopyrimidine and its associates with bis (hydroxymethyl)phosphinic acid in aqueous solution were studied using pH measurements, spectrophotometry (298 K), and mathematical simulation of equilibria (CPESSP software). The stability constants of the associates formed in solution were calculated. It was found that the said associates and the nitrogen base in their composition did not form innner-sphere complexes with typical complexing agents like doubly charged cations of d-elements and lanthanum(III). 2,4,6-Triaminopyrimidine forms an outer-sphere complex with copper(II) ions to affording tetrachlorocuprate(II) with diprotonated 2,4,6-triaminopyrimidine.     

Liquid chromatographic determination of cobalt(II), copper(II) and iron(II) using 2-thiophenaldehyde-4-phenyl-3-thiosemicarbazone as derivatizing reagent

The complexing reagent 2-thiophenaldehyde-4-phenyl-3-thiosemicarbazone (TAPT) was 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 Microsorb C-18, 5-mum column (150x4.6 mm i.d.) (Rainin Instruments Woburn, MA, USA). The complexes were eluted isocratically with methanol:acetonitrile:water containing sodium acetate and tetrabutyl ammonium bromide (TBA). UV detection was at 254 nm. The solvent extraction procedure was developed for simultaneous determination of the metals, with detection limits within 0.5-2.5 mug ml(-1) in the final solution. The method was applied for the determination of copper, cobalt and iron in pharmaceutical preparation.     

A simple spectrophotometric method for the determination of copper in industrial, environmental, biological and soil samples using 2,5-dimercapto-1,3,4-thiadiazole.

A simple spectrophotometric method is presented for the rapid determination of copper at a trace level using 2,5-dimercapto-1,3,4-thiadiazole (DMTD) as a new spectrophotometric reagent. The method is based on the reaction of non-absorbent DMTD in a slightly acidic (0.002-0.014 mol dm(-3) sulfuric acid) aqueous solution with copper(II) to produce a highly absorbent greenish-yellow chelate product that has an absorption maximum at 390 nm. The reaction is instantaneous and the absorbance remains stable for 24 h. The average molar absorption coefficient and Sandell's sensitivity were found to be 5.65 x 10(4) dm3 mol(-1) cm(-1) and 10 ng cm(-2) of CuII, respectively. Linear calibration graphs were obtained for 0.1-20 microg cm(-3) of CuII; the stoichiometric composition of the chelate is 1:2 (Cu:DMTD). A large excess of over 50 cations, anions and complexing agents (e.g. tartrate, oxalate, citrate, phosphate, thiourea, SCN-) do not interfere in the determination. The method was successfully used for the determination of copper in several Standard Reference Materials as well as in some environmental water samples, biological samples, soil samples and solutions containing both copper(I) and copper(II) and complex synthetic mixtures. The method has high precision and accuracy (s = +/-0.01 for 0.5 microg cm(-1)).     

A new selective and high affinity polymeric complexing agent for transition metal ions

Summary The synthesis and characteristics of a new chelating glycinohydroxamate-containing polymer resin is described. The functionality of the polymer is 1.76 mmolg^–1. The hydrogen capacity, water regain and adsorption capacities for iron(III), cadmium(II), cobalt(II), copper(II), nickel(II) and zinc(II) were measured at various pH values; uptake of the metal ions increased with pH and was quantitative above pH 3 for most of the metal ions. All cations studied showed high exchange rates towards the resin. The half saturation times for iron(III), cadmium(II), copper(II) and zinc(II) were all less than 1 min. The coordination behaviour of the resin was studied with the help of e.p.r., i.r., u.v. and potentiometry. The pK _a of the resin is 10.70 and the log value of the stability constants for iron(III), copper(II), lead(II), zinc(II), cobalt(II), manganese(II), cadmium(II) and nickel(II) were measured as 21.81, 19.50, 19.20, 18.59, 18.51, 18.46, 18.37 and 18.36, respectively, at 25 ° C and I = 0.2M KCl.