Furoin thiosemicarbazone as an analytical reagent for nickel(II), palladium(II) and copper(II)

Furoin thiosemicarbazone (FTS) reacts with Ni(II), Pd(II) and Cu(II) in aqueous medium, giving yellow solutions at pH 9, 6 and 3 respectively. The complexes have absorption maxima at 360 nm for Ni(II) and Pd(II) and 355 nm for Cu(II). At these wavelengths the reagent absorbance is negligible. The molar absorptivities are 1.54 x 10(4) [Ni(FTS)(2)], 1.98 x 10(4) [Pd(FTS)(2)] and 1.45 x 10(4) 1.mole(-1).cm(-1) (CuFTS). Beer's law is valid up to 4, 5 and 3 ppm for Ni, Pd and Cu respectively. The apparent instability constant of the Ni-FTS system is found to be 6.5 x 10(-11), of the Cu-FTS system 7.1 x 10(-7) and of the Pd-FTS system 3 x 10(-12) at the recommended pH values. The effect of various ions is reported.     

Speciation of Co(II), Co(III), and Cu(II) in ethylenediamine solutions by capillary electrophoresis

A capillary electrophoretic (CE) method for the speciation of Co(II), Co(III), and Cu(II) in electroless copper-plating baths containing ethylenediamine (En) has been developed. The method is based on the selective pre-capillary derivatization of Co(II) with 1,10-phenanthroline (Phen) followed by CE separation of stable [CoPhen(3)](2+), [CoEn(3)](3+), and [CuEn(2)](2+) chelates. The proposed derivatization procedure protects Co(II) from oxidation by dissolved oxygen and enables rapid determination of all three metal species within a single run. The optimized separations were carried out in a fused silica capillary (57 cmx75-microm I.D.) filled with an ethylenediamine sulfate electrolyte (20 mmol L(-1) H(2)SO(4), pH 7.0 with En, applied voltage +30 kV) using direct UV detection at 214 nm. The detection limits for a signal-to-noise ratio of 3 and 10 s, hydrodynamic injections were 5x10(-6) mol L(-1) for Cu(II), 1x10(-6) mol L(-1) for Co(III), and 4x10(-7) mol L(-1) for Co(II). Application of the method to the speciation of Co(II), Co(III), and Cu(II) in copper-plating bath samples is also demonstrated.     

Spectrofluorimetric determination of copper(II) by its static quenching effect on the fluorescence of 4,5-dihydroxy-1,3-benzenedisulfonic acid

A spectrofluorimetric method has been developed for the determination of trace Cu(II) in real samples with 4,5-dihydroxy-l,3-benzenedisulfonic acid (Tiron) as a fluorimetric reporter. Tiron is very soluble in water and is a good fluorimetric reagent. However, as Tiron was complexed with Cu(II), the fluorescence intensity decreased proportionally to the concentration of Cu(II) by a static quenching effect. The excitation wavelength and the fluorescence wavelength of Tiron were 294 and 350 nm, respectively, as it was caused by a quenching effect from Cu(II) at pH 8.0. The highest sensitivity was shown at Tiron concentration of 5.0x10(-5) M. To enhance the quenching effect, the Cu(II)-Tiron complex solution was heated up to 80 degrees C for 90 min. As for Cu(II), the interference by Co(II) was very serious, which was eliminated by oxalate ion. The linear response to Cu(II) was shown at the concentration range between 5.0x10(-7) and 1.0x10(-5) M. With this proposed method, the detection limit of Cu(II) was 3.83(+/-0.09)x10(-7) M. Recoveries of Cu(II) in the diluted brass samples and the stream water samples were almost 100%. Based on results from the experiment, this proposed technique could be applied to the practical determination of Cu(II) in real samples.     

Simultaneous kinetic spectrophotometric determination of Cu(II), Co(II) and Ni(II) using partial least squares (PLS) regression

A partial least squares (PLS-1) calibration model based on kinetic—spectrophotometric measurement, for the simultaneous determination of Cu(II), Ni(II) and Co(II) ions is described. The method was based on the difference in the rate of the reaction between Co(II), Ni(II) and Cu(II) ions with 1-(2-pyridylazo)2-naphthol in a pH 5.8 buffer solution and in micellar media at 25°C. The absorption kinetic profiles of the solutions were monitored by measuring the absorbance at 570 nm at 2 s intervals during the time range of 0–10 min after initiation of the reaction. The experimental calibration matrix for the partial least squares (PLS-1) model was designed with 30 samples. The cross-validation method was used for selecting the number of factors. The results showed that simultaneous determination could be performed in the range 0.1-2 μg mL⁻¹ for each cation. The proposed method was successfully applied to the simultaneous determination of Cu(II), Ni(II) and Co(II) ions in water and in synthetic alloy samples.      

Separation and determination of trace amounts of beryllium(II), aluminium(III) and chromium(III) with chromotrope 2C chelates by RP-HPLC

A reversed-phase high-performance liquid chromatographic separation and determination of beryllium(II), aluminium(III) and chromium(III) with chromotrope 2C chelates on a C18-bonded stationary phase is reported. Methanol-water (45:55 v/v) containing 6 x 10(-3)M tetra-n-butylammonium bromide (TBAB) and 2 x 10(-2)M acetate buffer solution (pH 6.0) as mobile phase and with spectrophotometric detection at 530 nm was applied. The method has high sensitivity, the detection limits being 0.2 ppb for beryllium(I), 1 ppb for aluminium(III) and 2 ppb for chromium(III). Under the optimum conditions, most other metal ions did not interfere, e.g. up to 2 mg of Hg(II), Sn(II, IV), Pb(II), Bi(III), Ag(I), Zn(II), Cd(II), Cu(II), 1.5 mg of Fe(II), Co(II), Ni(II), 1.2 mg of Ca(II), Mg(II), Sr(II), Ba(II), 1 mg of Ga(III), In(III), 0.5 mg of Fe(III), 1 mg of Ga(III), In(III), 0.5 mg of Fe(III), 0.4 mg of Th(IV), Zr(IV). The method can be applied to the simultaneous determination of trace amounts of beryllium(II), aluminium(III) and chromium(III), in water, rice, flour and human hair samples.     

A rapid and sensitive extractive spectrophotometric determination of copper(II) in pharmaceutical and environmental samples using benzildithiosemicarbazone.

Benzildithiosemicarbazone (BDTSC) is proposed as a sensitive and selective analytical reagent for the extractive spectrophotometric determination of copper(II). BDTSC reacts with copper(II) in the pH range 1.0-7.0 to form a yellowish complex. Beer's law is obeyed in the concentration range 0.5-0.4 microg cm(-3). The yellowish Cu(II)-BDTSC complex in chloroform shows a maximum absorbance at 380 nm, with molar absorptivity and Sandell's sensitivity values of 1.63 x 10(4) dm3 mol(-1) cm(-1) and 0.00389 microg cm(-2), respectively. A repetition of the method is checked by finding the relative standard deviation (RSD) (n = 10), which is 0.6%. The composition of the Cu(II)-BDTSC complex is established as 1:1 by slope analysis, molar ratio and Asmus' methods. An excellent linearity with a correlation coefficient value of 0.98 is obtained for the Cu(II)-BDTSC complex. The instability constant of the complex calculated from Edmond and Birnbaum's method is 7.70 x 10(-4) and that of Asmus' method is 7.66 x 10(-4), at room temperature. The method is successfully employed for the determination copper(II) in pharmaceutical and environmental samples. The reliability of the method is assured by analyzing the standard alloys (BCS 5g, 10g, 19e, 78, 32a, 207 and 179) and by inter-comparison of experimental values, using an atomic absorption spectrometer.     

A liquid-state copper(II) ion-selective electrode containing a complex of Cu(II) with salicylaniline

A new liquid-state ion-selective electrode based on a complex of Cu(II) with salicylaniline is described. The electrode shows linear dependence of potential on the activity of Cu(2+) in the range from 5 x 10(-6) to 0.1M, with a slope of 28.3 mV/pCu at 18 degrees . The electrode shows a better selectivity relative to Ag(I) and Hg(II) than other copper(II) ion-selective electrodes. The possibilities for using the electrode for determination of copper in the presence of interfering cations are described.     

Simultaneous determination of Cu(II) and Ag(I) on SP Sephadex C25 as complexes with 1-phenyl-1,2-propanedione-2-oximethiosemicarbazone by derivative spectrophotometry

A simple, rapid, and sensitive method has been developed for the simultaneous determination of trace amounts of copper and silver using 1-phenyl-1,2-propanedione-2-oximethiosemicarbazone (PPDOT) as a chromogenic reagent. The proposed method was based on retention and preconcentration of the complexes Cu(III)-PPDOT and Ag(I)-PPDOT on a solid phase in acid medium. The complexes were quantitatively retained in the cation exchanger SP Sephadex C25, and the analytical measurements were executed directly in the solid phase by derivative spectrophotometry. In this simultaneous determination, the second derivative and the zero crossing method were used. The determination of copper and silver was carried out to 321.0 and 427.0 nm, respectively. In order to obtain quantitative recoveries of the metal ions, various experimental analytical parameters, such as pH, stirring time, volume, and amount of solid phase, were optimized. The effect of interfering ions on the determination was described. The recovery values for Cu(II) and Ag(I) were found to be > 98%, and the relative standard deviation was < or = 2%. The detection limits (3sigma criterion) for Cu(II) and Ag(I) were found to be 0.9 x 10(-8) and 13 x 10(-8) M, respectively. The developed method was utilized for preconcentration and determination of Cu(II) and Ag(I) in industrial effluents and natural water samples. The results were consistent with those provided by inductively coupled plasma/mass spectrometry.     

Copper (II) adsorption from aqueous solution by herbaceous peat

In this research, the herbaceous peat collected from Gavurgolu peatlands, one of the biggest Turkish peatlands, was utilized as an adsorbent for the removal of copper (II) ions from aqueous solution. Adsorption experiments were conducted under various conditions, i.e., initial concentration, temperature, and pH. While the amount of Cu (II) adsorbed on the peat increased with increasing concentration of Cu (II) ions, it was not markedly affected by temperature and pH. Percentage removal was higher at lower concentration. For example, the maximum percentage removal of Cu (II) ions for initial concentration of 3 x 10(-4) M was 97.04% at 21 degrees C and pH 5.5. The adsorption capacity (Q(0)) of the peat was 4.84 mgg(-1) from Langmuir adsorption isotherm for the concentration range of 3 x 10(-4)-6 x 10(-4) M at 21 degrees C and pH 5.5. The equilibrium time of adsorption of Cu (II) ions was 150 min and independent of concentration and temperature. The amount of Cu (II) adsorbed at equilibrium time did not considerably change with temperature and pH. It was also determined that adsorption isotherm followed both Freundlich and Langmuir. Uptake mechanism of Cu (II) ions by the peat occurs via cation exchange (especially by means of Ca(2+) and Mg(2+)) as well as copper/peat complexation. Adsorption kinetic was consistent with the pseudo-second-order model.     

Preconcentration of iron (III), cobalt (II) and copper (II) nitroso-R complexes on tetradecyldimethylbenzylammonium iodide-naphthalene adsorbent

Iron, cobalt and copper form coloured water soluble anionic complexes with disodium 1-nitroso-2-naphthol-3-6-disulphonate (nitroso R-salt). The anionic complex is retained quantitatively as a water insoluble neutral ion associated complex (M-nitroso R-TDBA) on tetradecyldimethylbenzylammonium iodide on naphthalene (TDBA(+)I(-)-naphthalene) packed column in the pH range of: Fe(III): 3.1-6.5, Co: 3.4-8.5 and Cu 5.9-8.0 when their solutions are passed individually over this adsorbent at a flow rate of 0.5-5.0 ml/min. The solid mass consisting of an ion associated metal complex along with naphthalene is dissolved out of the column with 5 ml dimethylformamide/chloroform and metals are determined spectrophotometrically. The absorbance is measured at 710 nm for iron, 425 nm for cobalt and 480 nm for copper. Beers law is obeyed in the concentration range 9.2-82 mug of iron, 425 nm for cobalt cobalt and 3.0-62 mug of copper in 5 ml of final DMF/CHCl(3) solution. The molar absorptivities are calculated to be Fe: 7.58 x 10(3), Co: 1.33 x 10(4) and Cu: 4.92 x 10(4)M(-1)cm(-1). Ten replicate determinations containing 25 mug of iron, 9.96 mug of cobalt and 3.17 mug of copper gave mean absorbances 0.677, 0.450 and 0.490 with relative standard deviations of 0.88, 0.98 and 0.92%, respectively. The interference of large number of metals and anions on the estimations of these metals has been studied. The optimized conditions so developed have been employed for the trace determination of these metals in standard alloys, waste water and fly ash samples.     

Synergistic effect of Ni(II) and Co(II) ions on the sulfite induced autoxidation of Cu(II)/tetraglycine complex

The synergistic effect of Ni(II) and Co(II) on the sulfite induced autoxidation of Cu(II)/tetraglycine was investigated spectrophotometrically at 25.0 degrees C, pH = 9.0, 1 x 10(-5) mol dm(-3) < or = [S(IV)] < or = 8 x 10(-5) mol dm(-3), [Cu(II)]= 1 x 10(-3) mol dm(-3), 1 x 10(-6) mol dm(-3) < or = [Ni(II)] or [Co(II)] < or = 1 x 10(-4) mol dm(-3), [O2] approximately 2.5 x 10(-4) mol dm(-3), and 0.1 mol dm(-3) ionic strength. In the absence of added nickel(II) or cobalt(II), the kinetic traces of Cu(III)G4 formation show a large induction period (about 3 h). The addition of trace amounts of Ni(II) or Co(II) increases the reaction rate significantly and the induction period drastically decreases (less than 0.5 s). The effectiveness of Cu(III)G4 formation becomes much higher. The metal ion in the trivalent oxidation state rapidly oxidizes SO3(2-) to SO3*-, which reacts with oxygen to produce SO5*-. The strongly generated oxidants oxidize Cu(II)G4 to Cu(III).     

EPR of Cu(II)-doped seven-coordinate inclusion compounds, M(stpy)3(NO3)2 x 1/2stpy (M = Cd(II) and Zn(II), stpy = trans-4-styrylpyridine): low symmetry effects in admixture of ground states

Single crystal EPR of Cu(II)-doped low symmetry pentagonal bipyramidal Werner-type clathrate inclusion complexes of Cd(stpy)3(NO3)2 x 1/2stpy(1) and Zn(stpy)3(NO3)2 x 1/2stpy(2) (stpy = trans-4-styrylpyridine) is reported. The spin Hamiltonian parameters are found to be orthorhombic with g33 = 2.298, g22 = 2.108, g11 = 2.066, A33 = 107.3, A22 = 54.4 and A11 = 23.1 x 10(-4) cm(-1) for 1 and g33 = 2.292, g22 = 2.111, g11 = 2.067, A33 = 107.5, A22 = 54.7 and A11 = 22.9 x 10(-4) cm(-1) for 2. Angular variation studies for both 1 and 2 suggest that the Cu(II) ions are substitutionally incorporated in the host lattices. The magnitude of Cu(II) hyperfine coupling constant (A33) in both 1 and 2 are found to be low, in comparison to those of the pure Cu(II) complex, indicative of low symmetry for the substitutional sites in accordance with the crystal data. Such large reductions in Cu(II) hyperfine coupling are explicable in terms of a mixed d(x2 - y2)/dz2 ground state and delocalization of unpaired spin density onto the ligands.     

Detection and spectrophotometric determination of EDTA with cobalt(II) and phosphomolybdic acid in urine and detergents

A simple, rapid, sensitive and selective method for the microgram detection and spectrophotometric determination of EDTA in water, human urine and detergents, based on its reaction with Co(II) and phosphomolybdic acid at pH 0.5–2.0 is reported. Absorbance is measured against Co(II)–phosphomolybdic acid reference solution at 750 nm. The effect of time, temperature, pH and Co(II) or phosphomolybdic acid concentration is studied, and optimum operating conditions are established. Beer's law is applicable in the concentration range 0.3–1.9 μg ml⁻¹ of 10⁻⁵M EDTA. Its detection limit is 0.14 μg in the solution phase and 0.03 μg in the resin phase. The relative standard deviation is ±0.13 μg. Ag(I), Zn(II), Cu(II), Ni(II), Pb(II), Cd(II), Ca(II), Mg(II), Fe(III), Cr(III), U(VI), chloride, nitrite, phosphate, oxalate, borate and amino acids do not interfere.     

Spectrophotometric investigation of the reaction of CU(II) and Cu(I) with 1-isonitroso-(1,2,3,4)-tetrahydrophenazine

The reactions of Cu(II) and Cu(I) with 1-isonitroso-(1,2,3,4)-tetrahydrophenazine (HITF) have been studied spectrophotometrically. Both ions form complexes with metal/ligand ratio 1:2. The complex of Cu(I) and ITF can be used for copper determination in the range 2-50 x 10(-6)M, and has been separated as the perchlorate in crystalline form. The spectrophotometric characteristics and the equilibrium constants for the ligand and for the complexes are reported.     

Chemically modified carbon paste electrode for determination of copper(II) by potentiometric method

The utility of carbon paste electrode modified with DTPT (3,4-dihydro-4,4,6-trimethyl-2(1H)-pyrimidine thione) for the potentiometric determination of Cu(II) in aqueous medium is demonstrated. The electrode exhibits linear response to Cu(II) over a wide concentration range (9.77x10(-7)-7.6x10(-2)) with Nernstian slope of 30+/-2 mV per decade. It has a response time of about 45 s and can be used for a period of two months with good reproducibility. The detection limit of this electrode was 7.0x10(-7) M. The proposed electrode shows a very good selectivity for Cu(II) over a wide variety of metal ions. This chemically modified carbon paste electrode was successfully used for the determination of Cu(II) in electronics waste sample solution.     

Photometric determination of aqueous cobalt (II), nickel (II), copper (II) and iron (III) with 1-nitroso-2-naphthol-3,6-disulfonic acid disodium salt in gelatin films

Photometric determination of aqueous Co(II), Cu(II), Ni(II) and Fe(III) was performed using indicator films prepared by immobilization of 1-nitroso-2-naphthol-3,6-disulfonic acid disodium salt (NRS) into hardened photographic film. Immobilization was based on electrostatic interaction of reagent and metal complexes with the gelatin. The isoelectric point pH of hardened gelatin (4.46±0.04) was evaluated by viscometry. Co(II), Fe(III), Ni(II) form 1:3 complexes with NRS in gelatin at pH 2 and Cu(II) forms 1:2 complexes. Their log β′ values were: Co-6.7, Fe-8.6, Cu-8.0, and Ni-6.4. The absorption maxima were: 370nm for NRS, and 430nm, 470nm, 495nm and 720nm for complexes of Co(II), Ni(II), Cu(II) and Fe(III). An algorithm for their simultaneous determination using the indicator films was developed. The detection limits were: c_lim(Co²⁺) = 0.45×10⁻⁵ M, c_lim(Fe³⁺) = 0.50×10⁻⁵ M, c_lim(Cu²⁺) = 0.67×10⁻⁵ M, c_lim(Ni²⁺) = 0.75×10⁻⁵ M,; and their sum c_lim(ΣMn⁺) = 0.82×10⁻⁵ M.      

Determination of components of the Cd(II)-Pb(II)-Cu(II) system in aqueous solutions of (polyethylene imine)methylthiourea by stripping voltammetry

Conditions were studied for the stripping voltammetric determination of components of the Cd(II)-Pb(II)-Cu(II) system in aqueous solutions of (polyethylene imine)methylthiourea (PMT), the most efficient polymer complexant for the membrane preconcentration of heavy metal ions. It was shown that PMT significantly enhances the selectivity of determining Pb(II) and Cd(II) in solutions of Cu(II) by stripping voltammetry. Pb(II) and Cd(II) can be determined in the presence of up to 200- and 50-fold amounts of Cu(II), respectively. The limits of detection for Pb(II) and Cd(II) after a 40-s accumulation were 6.9 x 10^-8 and 6.8 x 10^-7 M, respectively.     

Reaction of copper(II) with ferrocene and 1,1'-dimethylferrocene in aqueous acetonitrile: the copper(II/I) self-exchange rate

The kinetics of the reactions of copper(II) with ferrocene (Fc) and 1,1'-dimethylferrocene (Dmfc) have been studied at 25 degrees C in aqueous acetonitrile (AN) containing 50-97.5 vol % AN. With increasing % AN, the rate constant increases along with the driving-force for the reaction. The results are analyzed in terms of Marcus theory to estimate the Cu(II/I) electron self-exchange rate constant (k11) for the system. Over the solvent range studied, the calculated k11)changes from 1.1 x 10(-9) to 17 x 10(-9) M(-1) s(-1), with an average value of 5 x 10(-9). In addition, the structures of the trifluoromethanesulfonate salts of [Cu(AN)4]+, [Cu(OH2)2(AN)2]2+, and [Cu(AN)4]2+ are reported. It is found that the Cu-NCCH3 bond-length difference between the Cu(I) and Cu(II) oxidation states is only approximately 0.02 A.     

Spectrophotometric determination of a nanomolar amount of ascorbic acid using its catalytic effect on copper(II) porphyrin formation

A simple, fast and sensitive flow-injection method is proposed for the determination of nanomolar amounts of ascorbic acid in tea, urine and blood. The procedure is based on the accelerating effect of a nanomolar level of ascorbic acid on the reaction of cooper(II) with 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin, H(2)tmpyp(4+). Ascorbic acid reduces Cu(II) to Cu(I) which catalyzes the incorporation of Cu(II) into H(2)tmpyp(4+) to form Cu(II)(tmpyp)(4+). In this method two solutions, one containing ascorbic acid and H(2)tmpyp(4+) and the other containing copper(II) and acetate buffer (pH 5.0), were injected into two flowing streams of water through two sample injectors of 120 mu1 sample volume. The mixture was allowed to react in a 2 m reaction coil and the colored solution of Cu(II)(tmpyp)(4+) was monitored at 550 nm (epsilon = 2.01 x 10(4)M(-1)cm(-1)). The present method was applied to the determination of ascorbic acid in tea, urea and blood. Reducing agents such as sugars and vitamins B(1), B(2), B(6) and B(12) did not give serious errors at a concentration of 10(-6) M for the determination of 1.0 x 10(-8)M ascrobic acid. The relative standard deviation of the present method was 2.8% for the determination of 1.0 x 10(-8)M ascorbic acid. The reaction mechanism was clarified from the kinetic results of the formation of Cu(II)(tmpyp)(4+) in the presence of various concentrations of ascorbic acid, copper(II) and hydrogen ion.     

A fluorescent chemosensor for copper(II) based on a carboxylic acid-functionalized tris(2,2'-bipyridine)-ruthenium(II) complex.

In this research, bis(2,2'-bipyridine)(4-methyl-2,2'-bipyridine-4'-carboxylic acid)ruthenium(II).2PF(6)- complex (1), was first used as a fluorescent chemosensor to recognize Cu(II) in EtOH/H(2)O (1:1, v/v) solution. The response of the sensor is based on the fluorescence quenching of complex 1 by binding with Cu(II). The analytical performance characteristics of the proposed Cu(II)-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Cu(II) with a linear range covering from 5.0 x 10(-8) to 1.0 x 10(-4) M and a detection limit of 4.2 x 10(-8) M. The experiment results show that the response behavior of 1 to Cu(II) is pH independent in medium condition (pH 4.0 - 8.0), and show excellent selectivity for Cu(II) over other transition metal cations.