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1.
Di J  Yang T 《Talanta》2003,61(2):165-171
A new high sensitive spectrophotometric determination of trace molybdenum was investigated. The sensitivity of the determination of molybdenum, which based on the color charge transfer complex of molybdotungstophosphate-3,3′,5,5′-tetramethylbenzidine, was greatly enhanced by copper(II) ions in the presence of polyvinyl alcohol. The improved method maintained the features of simplicity, rapidity and selectivity, especially eliminating the interference from tungsten. Under the optimum conditions, Beer's law was obeyed over the range from 2 to 32 ng ml−1 molybdenum with molar absorptivity being 4.92×105 l mol−1 cm−1 at 660 nm. The relative standard deviation was 1.2% under nine determinations for 16 ng ml−1 Mo(VI). The present method had been applied to the determination of trace molybdenum in tungsten ores with satisfactory results.  相似文献   

2.
Silica gel-bound amines phase modified with p-dimethylaminobenzaldehyde (p-DMABD) was prepared based on chemical immobilization technique. The product (SG-p-DMABD) was used as an adsorbent for the solid-phase extraction (SPE) Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II) prior to their determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The uptake behaviors of SG-p-DMABD for extracting these metal ions were studied using batch and column procedures. For the batch method, the optimum pH range for Cr(III) and Ni(II) extraction was ≥ 3, for Cu(II), Pb(II) and Zn(II) extraction it was ≥ 4. For simultaneous enrichment and determination of all the metals on the newly designed adsorbent, the pH value if 4.0 was selected. All the metal ions can be desorbed with 2.0 mL of 0.5 mol L− 1 of HCl. The results indicate that SG-p-DMABD has rapid adsorption kinetics using the batch method. The adsorption capacity for these metal ions is in the range of 0.40-1.15 mmol g− 1, with a high enrichment factor of 125. The presence of commonly coexisting ions does not affect the sorption capacities. The detection limits of the method were found to be 1.10, 0.69, 0.99, 1.10 and 6.50 μg L− 1 for Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II), respectively. The relative standard deviation (RSD) of the method under optimum conditions was 5.0% (n = 8) for all metal ions. The method was applied to the preconcentration of Cr(III), Cu(II), Ni(II), Pb(II) and Zn(II) from the certified reference material (GBW 08301, river sediment) and water samples with satisfactory results.  相似文献   

3.
Preparations, crystal structures, electronic and CD spectra are reported for new chiral Schiff base complexes, bis(N-R-1-naphthylethyl-3,5-dichlorosalicydenaminato)nickel(II), copper(II), and zinc(II). Nickel(II) and copper(II) complexes adopt a square planar trans-[MN2O2] coordination geometry with Δ(R,R) configuration. While zinc(II) complex adopts a compressed tetrahedral trans-[MN2O2] one with Δ(R,R) configuration and exhibits an emission band around 21 000 cm−1 (λex = 27 000 cm−1). Absorption and CD spectra were recorded in N,N′-dimethylformamide, acetone, methanol, chloroform, and toluene solutions to discuss relationships between spectral shifts of d–d and π–π bands by structural changes of the complexes and physical properties of the solvents. Moreover, we have attempted to investigate conformational changes of the complexes induced by photoisomerization of azobenzene, 4-hydroxyazobenzene, or 4-aminoazobenzene, in various solutions under different conditions. Weak intermolecular interactions between complexes and azobenzenes are important for the phenomenon by conformational changes of bulky π-conjugated moieties of the ligands.  相似文献   

4.
《Analytical letters》2012,45(6):1209-1226
Abstract

A sensitive method for the simultaneous spectrophotometric determination of Fe(II), Cu(II), Zn(II), and Mn(II) in mixtures has been developed with the aid of multivariate calibration methods, such as classical least squares (CLS), principal component regression (PCR) and partial least squares (PLS). The method is based on the spectral differences of the analytes in their complexation reaction with 4‐(2‐pyridylazo)‐resorcinol (PAR) and the use of full spectra with wavelengths in the range of 300–600 nm. It was found that both the spectral positive and negative bands obtained against the PAR blank, are proportional to the concentration for each metal complex. The obtained linear calibration concentration ranges are 0.025–0.6, 0.05–0.8, 0.025–0.8, and 0.05–0.8 µg ml?1 for Fe(II), Cu(II), Zn(II), and Mn(II), respectively, and the LODs for the four metal ions were found to be approximately 1–3×10?2 µg ml?1. The proposed method was applied to a verification set of synthetic mixtures of these four metal ions, with models built in three different wavelength ranges, i.e., 300–450, 450–600, and 300–600 nm, corresponding to the positive, negative bands and their combinations, respectively. It was shown that the PLS model for the 300–600 nm range gave the best results (RPET=6.9% and average recovery ~100%; cf. PCR: RPET=9.5% and average Recovery ~110%). This method was also successfully applied for the determination of the four metal ions in pharmaceutical preparations, chicken feedstuff, and water samples.  相似文献   

5.
Wei Q  Yan L  Chang G  Ou Q 《Talanta》2003,59(2):253-259
A new catalytic kinetic spectrophotometric method has been developed for the determination of trace amount of manganese (II) in nonionic microemulsion medium. The method is based on the catalytic effect of manganese (II) on the oxidation of dahlia violet by potassium periodate with nitrilotriacetic acid as an activitor in the presence of nonionic microemulsion. Under the optimum conditions, the calibration graph is linear in the range of 0.0004-0.0056 μg ml−1 of manganese (II) at 580 nm. The detection limit achieved is 3.75×10−5 μg ml−1. Manganese (II) in foodstuff samples was determined with satisfactory results.  相似文献   

6.
A novel chelating resin (poly-Cd(II)-DAAB-VP) was prepared by metal ion imprinted polymer (MIIP) technique. The resin was obtained by one pot reaction of Cd(II)-diazoaminobenzene-vinylpyridine with cross-linker ethyleneglycoldimethacrylate (EGDMA). Comparing with non-imprinted resin, the poly-Cd(II)-DAAB-VP has higher adsorption capacity and selectivity for Cd(II). The distribution ratio (D) values for the Cd(II)-imprinted resin show increase for Cd(II) with respect to both D values of Zn(II), Cu(II), Hg(II) and non-imprinted resin. The relatively selective factor (αr) values of Cd(II)/Cu(II), Cd(II)/Zn(II) and Cd(II)/Hg(II), are 51.2, 45.6, and 85.4, which are greater than 1. poly-Cd(II)-DAAB-VP can be used at least 20 times without considerable loss of adsorption capacity. Based on poly-Cd(II)-DAAB-VP packed columns, a highly selective solid-phase extraction (SPE) and preconcentration method for Cd(II) from aqueous solution was developed. The MIIP-SPE preconcentration procedure showed a linear calibration curve within concentration range from 0.093 to 30 μg l−1. The detection limit and quantification limit were 0.093 and 0.21 μg l−1 (3σ) for flame atomic absorption spectrometry (FAAS). The relative standard deviation of the eleven replicate determinations was 3.7% for the determination of 10 μg of Cd(II) in 100 ml water sample. Determination of Cd(II) in certified river sediment sample (GBW 08301) demonstrated that the interfering matrix had been almost removed during preconcentration. The column was good enough for Cd(II) determination in matrixes containing components with similar chemical property such as Cu(II), Zn(II) and Hg(II).  相似文献   

7.
《Analytical letters》2012,45(9):1675-1684
Abstract

The reaction between lead(II) and 2-(2-Thiazolylazo)-p-Cresol(TAC) in the presence of TERGITOL NPX (4 mg/ml) at an apparent pH 9.0–10.0 results in an intensely colored complex which is stable for at least 4 hr.

The composition of the complex is 1:2 cation: TAC and the log of the formation constant is 11.92 ± 0. 40. Beer's law is obeyed up to 6.0μg.ml?1 of lead(II) at 650nm.

The apparent molar absorptivity at 650 nm is 2.07 × 104 1. mole?1.cm?1 and the detection limit was obtained as 10.0 ng.ml?1 of lead(II).

The method is applied to determination of lead(II) in copper-base alloy.  相似文献   

8.
The reagent 3,8,13,18-tetramethyl-21H,23H-porphine-2,7,12,17-tetrapropionic acid or coproporphyrin-I (CPI) was used for the spectrophotometric determination of copper(II) and cobalt(II) in the presence of pyridine and imidazole catalysts. Optimum conditions were investigated and the methods were applied to the determination of parts per billion levels of copper(II) and cobalt(II). The Sandell sensitivities of the recommended procedures were 0.568 μm cm−2 and 0.464 μg cm−2 (for A = 0.001) for copper and cobalt, respectively. The relative standard deviations were 2.0% for copper and 1.0% for cobalt. The kinetics of the reaction of CPI with copper(II) and cobalt(II) in the presence of the catalysts and the influence of the temperature were studied, and their kinetic constants determined.The influence of light on the photodecomposition of CPI was also studied.  相似文献   

9.
Xi J  Ai X  He Z 《Talanta》2003,59(5):1045-1051
A chemiluminescence (CL) method for the determination of barbituric acid (BA) was proposed, which is based on the enhancement of BA to the CL intensity of Tris-(1,10-phenanthroline)ruthenium(II) (Ru(phen)32+)-cerium(IV) (Ce(IV)) system. The concentration of BA is proportional to the CL intensity in the range of 5.0×10−3-2.0 μg ml−1. The detection limit is 6.9×10−4 μg ml−1. The relative standard deviation (R.S.D.) of determining 11 samples containing 0.20 μg ml−1 BA is 3.2%. This CL method has been successfully applied to the determination of BA in the synthetic samples. The mechanism of CL reaction was studied.  相似文献   

10.
This paper describes a highly sensitive, selective catalytic-kinetic-spectrophotometric method for the determination of copper(II) concentration as low as 6 ng ml−1. The method is based on the catalytic effect of copper(II) on the oxidation of citric acid by alkaline hexacyanoferrate(III). The reaction was followed by measuring the decrease in absorbance of hexacyanoferrate(III) at 420 nm (λmax of [Fe(CN)6]3−,  = 1020 dm3 mol−1 cm−1). The dependence of rate of the indicator reaction on the reaction variables has been studied and discussed to propose a suitable mechanism to get a relation between the reaction rate and [Cu2+]. A fixed time procedure has been used to obtain a linear calibration curve between the initial rate and lower [Cu2+] or log[Cu2+] in the range 1 × 10−7 to 4 × 10−4 mol l−1 (6.35-25,400 ng ml−1). The detection limit has been calculated to be 4 ng ml−1. The maximum average error is 3.5%. The effect of the presence of various cations, commonly associated with copper(II) and some anions has also been investigated and discussed. The proposed method is sensitive, accurate, rapid and inexpensive compared to other techniques available for determination of copper(II) in such a large range of concentration. The new method has been successfully applied for the determination of copper(II) in various samples.  相似文献   

11.
A cloud-point extraction (CPE) process using the nonionic surfactant Triton X-114 to simultaneous extraction and spectrophotometric determination of Zn(II), Co(II) and Ni(II) from aqueous solution using partial least squares (PLS) regression is investigated. The method is based on the color reaction of these cations with 1-(2-pyridylazo)2-naphthol and subsequent micelle-mediated extraction of products. The optimum extraction and reaction conditions such as pH, reagents concentration and effect of time have been studied. Linearity was obeyed in the range 2–150, 5–250 and 2–150 ng mL−1 of Zn(II), Co(II) and Ni(II) respectively. The relative standard error (RSE) for the simultaneous determination of 15 test samples of different concentrations of Zn(II), Co(II) and Ni(II) was 4.38%;, 1.18% and 2.42%, respectively. The total relative standard error (RSEt) for applying the PLS method to 15 synthetic samples in the linear ranges of these metals was 2.36%. The interference effect of some anions and cations was also tested. The method was applied to the simultaneous determination of Zn(II), Co(II) and Ni(II) in water and human urine samples.  相似文献   

12.
Ensafi AA  Khayamian T  Atabati M 《Talanta》2003,59(4):727-733
A sensitive cathodic stripping voltammetric method is developed for determination of lead(II), with adsorptive collection of complexes with Pyrogallol red (PGR) on to a hanging mercury drop electrode. After accumulation of the complex at −0.80 V vs. Ag/AgCl reference electrode, the potential is scanned in a negative direction from −0.20 to −0.50 V with differential pulse method. Then the reduction peak current for the lead(II)-PGR complex is measured at −0.39 V. The influence of reagent and instrumental variables was completely studied by factorial design analysis. The optimum analytical conditions for the determination of lead(II) were established. Under optimum conditions, lead(II) determined in the range of 0.1-30.0 ng ml−1 with a limit of detection of 0.06 ng ml−1. The method is successfully applied to determination of lead(II) in water sample.  相似文献   

13.
A simple and sensitive kinetic method for the determination of traces of mercury (70-760 ng ml−1) based on its inhibitory effect on the addition reaction between methyl green and sulfite ion is proposed. The reaction was monitored spectrophotometrically by measuring the decrease in absorbance of methyl green at 596 nm between 2 and 4 min using a fixed time method. Artificial neural networks with back propagation algorithm coupled with an orthogonal array design were applied to the modeling of the proposed kinetic system and optimization of experimental conditions. An orthogonal design was utilized to design the experimental protocol, in which pH, concentration of sulfite, temperature, and concentration of methyl green were varied simultaneously. Optimum experimental conditions in term of sensitivity were generated by using ANNs. The rate of decrease in absorbance is inversely proportional to the concentration of Hg(II) over entire concentration range tested (100-550 ng ml−1) with a detection limit of 45 ng ml−1 and a relative standard deviation at 200-400 ng ml−1 Hg(II) of 3.2% (n=5). A simple preconcentration step improved the limit of detection and linear dynamic range of the method to about 8 and 12-760 ng ml−1, respectively, by about 10 times enrichment of mercury between 12 and 75 ng ml−1. The method was based on enrichment of Hg(II) from dilute samples on an anionic ion exchanger fixed on a plastic strip and was applied to the determination of Hg(II) in environmental samples with satisfactory results.  相似文献   

14.
Hu C  Wu K  Dai X  Hu S 《Talanta》2003,60(1):17-24
A simple and effective chemically modified carbon paste electrode (CMCPE) for the simultaneous determination of lead(II) and cadmium(II) was developed in this work. The electrode was prepared by the addition of diacetyldioxime into a carbon paste mixture. Pb2+ and Cd2+ were preconcentrated on the surface of the modified electrode by complexing with diacetyldioxime and reduced at a negative potential (−1.10 V). Then the reduced products were oxidized by differential pulse stripping. The fact that two stripping peaks appeared on the voltammograms at the potentials of −0.65 V (Cd2+) and −0.91 V (Pb2+) demonstrates the possibility of simultaneous determination of Pb2+ and Cd2+. Under the optimized working conditions, calibration graphs were linear in the concentration ranges of 1.0×10−7-1.5×10−5 mol l−1 (Pb2+) and 2.5×10−7-2.5×10−5 mol l−1 (Cd2+), respectively. For 5 min preconcentration, detection limits of 1×10−8 mol l−1 (Pb2+) and 4×10−8 mol l−1 (Cd2+) were obtained at the signal noise ratio (SNR) of 3. To evaluate the reproducibility of the newly developed electrode, the measurements of 5×10−7 mol l−1 Pb2+ and Cd2+ were parallel carried out for six times at different electrodes and the relative standard deviations were 2.9% (Pb2+) and 3.2% (Cd2+), respectively. Interferences by some metals were investigated. Only Ni2+ and Hg2+ apparently affected the peak currents of Pb2+ and Cd2+. The diacetyldioxime modified carbon paste electrode was applied to the determination of Pb2+ and Cd2+ in water samples. The results indicate that this electrode is sensitive and effective for the simultaneous determination of Pb2+ and Cd2+.  相似文献   

15.
New complexes of Cd(II), Zn(II) and Ni(II) with 2-quinolinecarboxaldehyde selenosemicarbazone (Hqasesc) were synthesized and structurally characterized. The structure of the ligand, Cd(II) and Zn(II) complexes was determined by NMR and IR spectroscopy, elemental microanalysis and molar conductivity measurements. Both complexes occur in solution in two forms, the major tetrahedral and minor octahedral. In the major Cd(II) complex one qasesc ligand is coordinated as a tridentate, the fourth coordination site being occupied by acetate, while in the major Zn(II) complex two qasesc ligands are coordinated as bidentates. In both minor complexes two qasesc ligands are coordinated as tridentates forming the octahedral geometry around the central metal ion. The only paramagnetic complex in the series is Ni(II) complex for which X-ray structure analysis was performed. The complex has the angularly distorted octahedral geometry with two qasesc ligands coordinated as tridentates, in a similar way as in the minor complexes of Cd(II) and Zn(II).  相似文献   

16.
A new chelating matrix has been prepared by immobilising sulfanilamide (SA) on silica gel (SG) surface modified with 3-chloropropyltrimethoxysilane as a sorbent for the solid-phase extraction (SPE) Cu(II), Zn(II) and Ni(II). The determination of metal ions in aqueous solutions was carried out by inductively coupled plasma optical emission spectrometry (ICP-OES). Experimental conditions for effective sorption of trace levels of Cu(II), Zn(II) and Ni(II) were optimised with respect to different experimental parameters using the batch and column procedures. The presence of common coexisting ions does not affect the sorption capacities. The maximum sorption capacity of the sorbent at optimum conditions was found to be 34.91, 19.07 and 23.62 mg g?1 for Cu(II), Zn(II) and Ni(II), respectively. The detection limit of the method defined by IUPAC was found to be 1.60, 0.50 and 0.61 µg L?1 for Cu(II), Zn(II) and Ni(II), respectively. The relative standard deviation (RSD) of the method under optimum conditions was 4.0% (n = 8). The method was applied to the recovery of Cu(II), Zn(II) and Ni(II) from the certified reference material (GBW 08301, river sediment) and to the simultaneous determination of these cations in different water samples with satisfactory results.  相似文献   

17.

In this study, 1,2-dihydroxyimino-3,7-di-aza-9,10-O-α-methyl benzal decane (LH2) was synthesized starting from 1,2-O-α-methyl benzal-4-aza-7-amino heptane (RNH2) and antichloroglyoxime. With this ligand, complexes were synthesized using Ni(II) and Cu(II) salts with a metal:ligand ratio of 1:2. However, the reaction of the ligand with salts of Zn(II) and Cd(II) gave products with metal:ligand ratio of 1:1. Structures of the ligand and its complexes are proposed based on elemental analyses, IR, 13C- and 1H-NMR spectra, magnetic susceptibility measurements and thermogravimetric analyses (TGA).  相似文献   

18.
A highly selective β-cyclodextrin polymer solid-phase spectrophotometric (β-CDPSPS) method is described for the determination of total mercury(II) sub microgram per liter. The methods are based on the chromogenic reaction of mercury(II) with 1,3-di-(4-nitrodiazoamino)-benzene (DNAAB) loaded on β-cyclodextrin polymer (β-CDP). In pH 10.0 borax buffer, Hg(II)-DNAAB complex on β-CDP gives a positive peak at 445 nm and a negative one at 545 nm. The absorbance was measured at two peaks and the net absorbance (As) was calculated between the difference of positive and negative peaks. The apparent molar absorptivity is 1.1 × 107 l mol−1 cm−1 (82-fold of it in solution) for 100 ml sample and the linear range of the determination is 0.062-250 μg l−1. The selectivity for coexistent ions was greatly improved, only silver(I) interfered with the mercury determination and the amount of the others was reduced 25-1000 times compared to previous solution method. The interference caused by silver(I) can be eliminated using tri-n-octylmethylammonium bromide as masking agent. The detection limit and the quantification limit were found to be 0.024 and 0.062 μg l−1, respectively. The relative standard deviation of ten replicate determinations of 5.0 μg mercury(II) in 100 ml sample was of 2.4%. The method was validated by analyzing the water and soil reference materials and successfully applied to the determination of mercury(II) in locally collected water and dust samples.  相似文献   

19.
A simultaneous preconcentration procedure for the determination of Cd(II), Ni(II), Co(II) and Cu(II) by atomic absorption spectrometry is described. The method is based on solid phase extraction of the metal ions on dithizone loaded on naphthalene in a mini-column, elution with nitric acid and determination by flame atomic absorption spectrometry. The sorption conditions including NaOH concentration, sample volume and the amount of dithizone were optimized in order to attain the highest sensitivity. The calibration graph was linear in the range of 0.5–75.0 ng ml?1 for Cd(II), 1.0–150.0 ng ml?1 for Ni(II), 1.0–150.0 ng ml?1 for Co(II) and 1.0–125.0 ng ml?1 for Cu(II) in the initial solution. The limit of detection based on 3Sb was 0.13, 0.32, 0.33 and 0.43 ng ml?1 for Cd(II), Ni(II), Co(II) and Cu(II), respectively. The relative standard deviations (R.S.D) for ten replicate measurements of 20 ng ml?1of Cd(II), 100 ng ml?1 of Ni(II), Co(II) and 75 ng ml?1 of Cu(II) were 3.46, 2.43, 2.45 and 3.26%, respectively. The method was applied to the determination of Cd(II), Ni(II), Co(II) and Cu(II) in black tea, tap and river water samples.  相似文献   

20.
 In this work it was established that, in the presence of ammonium carbonate, traces of manganese(II) catalyse the oxidation of Nile Blue A by hydrogen peroxide, which enables its kinetic determination in the concentration range from 6.6 to 65.9 ng cm−3, the detection limit being 8.0 × 10−2 ng cm−3. Antiviral/antitumour substances modify the catalytic activity of manganese(II): 1-β-D-ribofuranosyl-1,2,4-triazole-3-carboxamide, ribavirin, increases the catalytic effect of manganese(II), while 2-β-D-ribofuranosyl-thiazole-4-carboxamide, tiazofurin, acts as an inhibitor. On the basis of these effects, a kinetic method for determining ribavirin concentrations from 0.5 × 10−1 to 4.0 × 10−1 μg cm−3 and tiazofurin concentrations from 0.3 to 2.6 μg cm−3 is proposed. The kinetics of the indicator reaction were studied in the presence of the substances examined, the kinetic equations established, and the constants of the corresponding reaction rates calculated. The effect of temperature on these reactions was also investigated. The method was applied to the determination of manganese(II) in mineral water and ribavirin in pharmaceutical preparations. Received December 16, 1999. Revision June 6, 2000.  相似文献   

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