A sensitive and selective method for determination of gold(III) based on electrothermal atomic absorption spectrometry in combination with dispersive liquid-liquid microextraction using dicyclohexylamine

A combined method with dispersive liquid-liquid microextraction (DLLME) and electrothermal atomic absorption spectrometry (ETAAS) has been developed for determining gold(III). Dicyclohexylamine, a new extractant for gold(III), showed excellent performance in DLLME. Acetone was indispensable to the quantitative extraction of gold(III), contributing to decrease in hydration, decrease in the difference in the dielectric constants between the supernatant phase and the sedimented phase, and dissolution of a part of chloroform as an extraction solvent to the supernatant phase as well as improvement of dipersibility. In DLLME using a mixture of 1.0 mL of acetone and 100 μL of chloroform containing 50 mmol L⁻¹ of dicyclohexylamine, gold(III) could be extracted selectively and effectively from 8 mL of a sample solution in the presence of iron(III), cobalt(II), nickel(II), copper(II), palladium(II), and platinum(IV) at pH 1. The extracted gold(III) was determinable by ETAAS; the detection limit was 0.002 μg L⁻¹ (three times the standard deviation of the blank values, n = 8) as a gold(III) concentration in 8 mL of sample solution. The proposed method was applicable to the determination of gold in platinum metal and its alloy as well as effluent without any interference by the matrices.     

Simultaneous Detection of Copper,Lead and Zinc on Tin Film/Gold Nanoparticles/Gold Microelectrode by Square Wave Stripping Voltammetry

In this work, three heavy metals (Cu(II), Pb(II) and Zn(II)) in wide potential window were simultaneously detected on tin film/gold nanoparticles/gold microelectrode (Sn/GNPs/gold microelectrode) by the method of square wave stripping voltammetry. The Sn/GNPs/gold microelectrode was fabricated by in situ plating of a Sn film on a gold nanoparticles (GNPs) modified gold microelectrode. The influence of hydrogen overflow on stripping of Zn(II) on the gold microelectrode was reduced by modification of GNPs, which made the stripping potential of target metals shift positively. The interference of sulfhydryl groups was reduced and the selectivity of the microelectrode was improved due to the addition of Sn in the detection solution. After accumulation at ?1.4 V for 300 s in acetate buffer solution (0.1 mol L^?1, pH 4.5), the Sn/GNPs/gold microelectrode revealed a good linear behavior in the examined concentration ranges from 5 to 500 µg L^?1 for Cu(II) and Pb(II), and from 10 to 500 µg L^?1 for Zn(II), with a limit of detection of 2 µg L^?1 for Cu(II), 3 µg L^?1 for Pb(II) and 5 µg L^?1 for Zn(II) (S/N=3). When compared with a Sb/GNPs/gold microelectrode and a Bi/GNPs/gold microelectrode, the Sn/GNPs/gold microelectrode showed the best stripping performance to Cu(II), Pb(II) and Zn(II). As a new type of environment‐friendly electrode, the Sn/GNPs/gold microelectrode has potential applications for detection of heavy metals.     

Solvation of Cobalt(II) Ion in N,N-Dimethylformamide–Methanol Mixed Solvent: Calorimetry and VIS Spectroscopy Studies

The enthalpies of solution of Co(II) and Na(I) trifluoromethanesulfonates (triflates) in N,N-dimethylformamide (DMF)–methanol (MeOH) mixtures have been measured over the whole range of solvent composition. From these data the enthalpies of transfer of Co(II) and triflate ions from methanol to the mixed solvent have been determined usingliterature values of the enthalpies of transfer of the Na⁺ ion. The results have been analyzed by means of the theory of preferential solvation. The analysis revealed the preference of DMF for solvating the Co(II) ion in the MeOH-rich region of solvent composition and the lack of preference of any component in the DMF-rich region. Visible absorption spectra of the Co(II) ion in DMF–MeOH mixtures have been also measured in the whole range of solvent composition and analyzed using the partial least-squares method. The mean composition of the solvation sphere of the Co(II) ion versus solvent composition has been determined on the basis of both analyses. The results were found to be consistent with each other and with those obtained previously from FT-IR spectra.     

Colorimetric detection of cadmium in water using L-cysteine Functionalized gold–silver nanoparticles

Abstract

A new simple colorimetric assay was developed for the selective and sensitive detection of cadmium (II) in water samples using L-cysteine functionalized gold–silver nanoparticles. The gold–silver nanoparticles were synthesized by reducing HAuCl₄ and AgNO₃ in aqueous medium and were further functionalized with L-cysteine. The formation of homogeneous gold–silver nanoparticles was characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy, particle size distribution, and ultraviolet–visible absorption methods. In the presence of cadmium (II), the aggregation of functionalized gold–silver nanoparticles caused by the interaction between cadmium (II) and L-cysteine resulted in a naked-eye visible color change of L-cysteine functionalized gold–silver nanoparticles from orange–yellow to green, which can be monitored by a simple ultraviolet–visible spectrophotometer. Under the optimal conditions, the absorbance ratio at 600–435?nm (A₆₀₀/A₄₃₅) was linear to the concentration of cadmium (II) from 0.4 to 38.6?μM, and the limit of detection of cadmium (II) was 44?nM. Interference measurements showed that the method exhibited good selectivity. The proposed method was successfully applied to the determination of cadmium (II) in environmental water samples. The results indicated that this simple, selective, and sensitive sensing system has good potential for practical applications.     

Formation of Oxazoles from Elusive Gold(I) α‐Oxocarbenes: A Mechanistic Study

The gold(I) catalyzed reaction between phenylacetylene, pyridine N‐oxide and acetonitrile leading, via a putative gold‐α‐oxocarbene intermediate, towards an oxazole product has been investigated. A novel mass spectrometric method called “delayed reactant labeling” is used to track consecutive and parallel reactions. It clearly shows that the intramolecular formation of a pyridine adduct of gold‐α‐oxocarbene is in competition with the formation of the oxazole product. The reaction mechanism most probably corresponds to competition between acetonitrile and pyridine in an almost barrierless reaction with putative gold‐α‐oxocarbene within the solvent cage. The detected ionic species have been characterized by helium tagging infrared photodissociation spectroscopy.     

Development of a green effervescence-assisted dispersive liquid–liquid microextraction method using a home-made tablet disperser for trace analysis of Cd(II) and Pb(II)

An analytical approach for the determination of trace amounts of Cd(II) and Pb(II) has been developed using a home-made tablet-based effervescence-assisted dispersive liquid–liquid microextraction (DLLME) method which was performed in a narrow-bore tube, followed by flame atomic absorption spectrometry. In this method, a mixture of tartaric acid, sodium bicarbonate and NaCl was used to make the disperser tablet. Then, microlitre level of an extraction solvent was added in the tablet, and then, it was released into a narrow-bore tube containing sample solution and a complexing agent. An acid–base reaction immediately occurred between tartaric acid and sodium bicarbonate, and the produced CO₂ led to the dispersion of the extraction solvent into the solution as tiny droplets and subsequent extraction of the analytes. The method made possible the determination of Cd(II) and Pb(II) in the ranges of 0.1–10 and 1.0–20 µg L^?1, respectively. The limits of detection were obtained 0.43 and 0.05 µg L^?1 for Pb(II) and Cd(II), respectively. The limits of quantifications were 0.80 and 0.09 µg L^?1 for Pb(II) and Cd(II), respectively. Repeatability of the method, which is expressed as relative standard deviation, was obtained 3.1% (n = 6, C = 2 µg L^?1) and 1.3% (n = 6, C = 0.2 µg L^?1) for Pb(II) and Cd(II), respectively. The accuracy of the developed method was verified by analysing a certified reference material, namely SPS-WW2 Batch 108. Relative recoveries (84–107%, obtained at three fortification levels) confirmed the usefulness of the method for analysis of the analytes in the environmental water samples and fruit juices. The method was shown to be fast, reliable and environmentally friendly with low organic solvent consumption.     

Pyrimidinethiol as a reagent for extraction separation of platinum metals and gold Determination of Pd(II), Os(VIII) and Ru(III)

The solvent extraction separation of Pt(IV), Pd(II), Os(VIII), Ru(III) and Au(III) from one another and also from Rh(III) and Ir(III) with 1-(2'-nitro-4'-tolyl)-4,4,6-trimethyl-(1H, 4H)-2-pyrimidinethiol has been investigated. Photometric procedures have been developed for the determination of Pd(II), Os(VIII) and Ru(III) with the same reagent. The reagent allows the enrichment of Pd(II) and Au(III) at the trace level from a large volume of aqueous medium even in the presence of base metals. The method can be used for the determination of platinum metals and gold in alloys.     

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.     

Reversed phase partition chromatographic separation of divalent copper with N-n-octylaniline on silica gel

A novel separation method was developed for the extraction and chromatographic separation of copper(II). The quantative extraction of 25.0–125.0 μg copper(II) has been observed from 0.05 to 0.25 mol/L of ascorbic acid at pH 9.0–12.0 with 0.087 mol/L N-n-octylaniline (liquid anion exchanger) coated on silica gel at a flow rate of 1.0 ml/min. The extracted metal ion has been recovered by eluting with 25.0 ml of 1.0 mol/L hydrochloric acid and determined spectrophotometrically by rubeanic acid method. The various influencing parameters viz. acid concentrations, reagent concentration, eluates effect of pH, and effect of flow rate on extraction were studied. The method is free from large number of interferences from cations and anions. A scheme for mutual separation of copper(II), gold(III) and bismuth(III) has been developed. Copper(II) has been separated from ayurvedic (Herbal) medicine and synthetic mixtures corresponding to alloy. The log–log plot of N-n-octylaniline concentration versus the distribution coefficient indicates that the probable extracted species is [.     

Separation of gold from Cu, Pt, Pd, Ni, Zn, Cd and Hg using triphenylarsine oxide as an extractant

A method is developed for extraction of gold(III) (75–300 g) from hydrochloric acid solution with triphenylarsine oxide dissolved in toluene as extradant. Gold(III) is determined spectrophotometrically with stannous chloride. The extraction is quantitative from 1.5–1.9M hydrochloric acid with 0.25% triphenylarsine oxide and an equilibration period of 30s. The method permits separation of gold(III) from Cu(II), Pt(IV), Pd(II), Ni(II), Zn(II), Cd(II) and Hg(II) and its spectrophotometric determination in ayurvedic medicines. The recovery and relative standard deviation obtained are >99.0% and <1.0%.     

金矿石化学物相分析选择性溶剂实验探索

运用碘-碘化钾氨性溶液作为裸露及半裸露包裹金的选择性溶剂,硫代硫酸钠-亚硫酸钠溶液作碳酸盐包裹金的选择性溶剂,以及溴素-氯化钠溶液作硫化矿包裹金的选择性溶剂进行实验探索.使用国家标准物质GBW07190对方法进行评价,并对该标准物质中其他矿物中金(AAu)的这一相态做了更详细的分离,测定了其中的碳酸盐包裹金、褐铁矿包裹金、黄铁矿包裹金,石英和硅酸盐包裹金的含量.火焰原子吸收法测定金的检出限是0.05×10-6;石墨炉原子吸收法测定金的检出限是0.30×10-9.RSD为0.29%~11.6%,RE为0.11%~8.40%.方法适用于各种金矿物的相态分离,进一步细化了金的各种赋存状态,所得结果令人满意.完全满足矿床划带、选矿试验和成矿规律研究的实际需要.     

Dispersive liquid-liquid microextraction of Fe(II) and Cu(II) with diethyldithiocarbamate and their simultaneous spectrophotometric determination using mean centering of ratio spectra

A new dispersive liquid-liquid microextraction (DLLME) method for preconcentration of trace quantities of Fe(II) and Cu(II) followed by their spectrophotometric determination has been developed. For the extraction, an appropriate mixture of ethanol (the disperser solvent) and carbon tetrachloride (the extraction solvent) was injected rapidly into the water sample containing Fe(II) and Cu(II) after formation of complexes with diethyldithiocarbamate. Mean centering (MC) of ratio spectra has been used for simultaneous determination of Fe(II) and Cu(II). Linear range of the method is 1.0–100 ng/mL for Fe(II) and 0.3–100 ng/mL for Cu(II), the detection limit is 0.53 ng/mL and 0.14 ng/mL Cu(II), resp. The interference effect of some anions and cations is reported. The method was applied to the determination of Fe(II) and Cu(II) in well water samples.     

Ligandless-ultrasound-assisted emulsification microextraction followed by inductively coupled plasma-optical emission spectrometry for simultaneous determination of heavy metals in water samples

In this study, a simple and efficient method of ligandless-ultrasound-assisted emulsification microextraction (LL-USAEME) followed by inductively coupled plasma-optical emission spectrometry (ICP-OES) has been developed for simultaneous extraction, preconcentration and determination of manganese, cadmium, cobalt and nickel in water samples. In the proposed approach, tetrachloroethylene was selected as extraction solvent. The effect of important experimental factors such as volume of extraction solvent, pH, sonication time, salt concentration, and temperature was investigated by using a fractional factorial design (2^5?1) to identify important factors and their interactions. In the next step, a Box-Behnken design (BBD) was applied for optimisation of significant factors. The obtained optimal conditions were: 30?µL for extraction solvent, 12 for pH, 5?min for sonication time, and 5% w/v for salt concentration. The limits of detections (LODs) for Cd(II), Co(II), Mn(II) and Ni(II) were 0.20, 0.13, 0.21 and 0.28?µg?L^?1, respectively. Relative standard deviations (RSD, C?=?200.0?µg?L^?1, n?=?9) were between 3.4–7.5% and the calibration graphs were linear in the range of 0.25 to 1000.0?µg?L^?1 for Mn, 0.5–1000.0?µg?L^?1 for Co and Ni and 1.0–250.0?µg?L^?1 for Cd. The determination coefficients (R ²) of the calibration curves for the analytes were in the range of 0.993 to 0.999. The proposed method was validated by using two certified reference materials, and also the method was applied successfully for the determination of heavy metals in different real water samples.     

Chromatography of inorganic ions on cellulose phosphate layer in hydrochlorid acid and in acid ammonium thiocyanate media

Summary Thin-layers of an intermediately acidic cation exchanger, cellulose phosphate (P-cellulose), have systematically been used to study the chromatographic behavior of 58 inorganic ions in both hydrochloric acid and acid ammonium thiocyanate media (0.01–2.0 mol dm⁻³). In both solvent systems, the R _f values of many bivalent cations increase with increasing concentration of the acid and thiocyanate. Polyvalent metal ions including beryllium (II) and the others are strongly retained on the P-cellulose in the acid and thiocyanate systems tested. Palladium(II), mercury(II), ruthenium(III), rhenium(VII), arsenic(III), selenium(IV) and tellurium(IV) are not adsorbed on P-cellulose to any great extent. For silver(I), indium(III), gold(III), and platinum(IV), there are marked differences in the chromatographic behavior between hydrochloric acid and acid ammonium thiocyanate systems. Multicomponent separations conducted on P-cellulose plates with these eluents are presented.     

Synthesis,spectral characterization,and antimicrobial activity of copper(II), cobalt(II), and nickel(II) complexes of 3-formylchromoniminopropylsilatrane

A new series of Cu(II), Ni(II), and Co(II) complexes have been synthesized from 3-formylchromoniminopropylsilatrane (C₁₉H₂₄O₅N₂Si) (2) and 3-formylchromoniminopropyltriethoxysilane (1). Silatrane ligand (C₁₉H₂₄O₅N₂Si) (2) has been synthesized by the reaction between 3-aminopropyltriethoxysilane and 3-formylchromone followed by a treatment with triethanolamine. The nature of bonding and the geometry of the complexes have been deduced from elemental analyses, magnetic susceptibility, infrared, electronic, ¹H NMR, ¹³C NMR, and ESR spectral studies. The electronic absorption spectra and magnetic susceptibility measurements of the complexes indicate square planar geometry for Cu(II) and Ni(II) and tetrahedral geometry for Co(II). The redox behavior of copper complexes was studied by cyclic voltammetry. The biological activity of the ligand and metal complexes has been studied on Klebsiella pneumoniae, Staphylococcus aureus, Escherichia Coli, and Bacillus subtilis by the well diffusion method using acetonitrile as solvent. The zone of inhibition values were measured at 37°C for 24 h. Antimicrobial screening tests show better results for the metal complexes than the ligand.     

Ligandless,deep eutectic solvent‐based ultrasound‐assisted dispersive liquid‐liquid microextraction with solidification of the aqueous phase for preconcentration of lead,cadmium, cobalt and nickel in water samples

A green and efficient sample preparation method using a deep eutectic solvent‐based ultrasounds‐assisted dispersive liquid–liquid microextraction with solidification of the aqueous phase followed by high performance liquid chromatography analysis was developed for preconcentration and determination of heavy metals in environmental samples. In the proposed method, a novel, low density deep eutectic solvent was prepared by mixing trihexyl(tetradecyl)phosphonium chloride and thiosalicylic acid at a molar ratio of 1:2 and used both as an extractant and complexing agent. Ultrasound was used to disperse the extractant in the aqueous phase of the sample. Then, the phases were separated by centrifugation, after which the aqueous phase was frozen and the surface extractant phase was dissolved in a small volume of acetonitrile and subjected to liquid chromatographic analysis. The proposed method provided precisions (relative standard deviation, n = 5) in the range of 2.6–4.7%. The limit of detection were 0.05, 0.13, 0.06, and 0.11 µg/L for Pb(II), Cd(II), Co(II), Ni(II), respectively. The enhancement factors were equal to 154, 159, 162, and 158 for lead(II), cadmium(II), cobalt(II), and nickel(II), respectively. The accuracy of the proposed method was evaluated using certified reference materials (CA011b – hard drinking water, NIST 1643e – trace elements in water, TMRAIN‐04 – simulated rain sample).     

Recycling of Palladium and Selected Metal Ions from Simulated Spent Catalysis Waste Solution Using Novel Dithiodiglycolamides Derivatives

The present study focusing on design and evaluation of series of eight new structurally related dithiodiglycolamides (DTDGA) as a novel promising solvent extraction reagents. The influence of the nature of the alkyl chain on the distribution ratio of Pd(II) was investigated. Both N, N-di-hexyl-N′, N′-di-octyldithiodiglycolamide (DHDODTDGA) and N, N-di(2-ethylhexyl)-N′, N′-dioctyldithiodiglycolamide (DEHDODTDGA) were chosen and applied to perform the selective recovery and separation of Pd(II) from certain commonly associated elements such as Pt(IV), Rh(III), Fe(III), Cr(II), Mn(II), Zr(II), and Ni(II) contained in hydrochloric acid solutions using n-dodecane as diluent. A systematic investigation has been carried to understand the extraction behavior of Pd(II) using the synthesized extradant. The extraction equilibrium of Pd(II) was obtained within 3–4 min. The investigated extractants showed quantitative extraction of Pd(II) at ～ 4 M HCl. The main extracted species of Pd(II) at 3.5 M HCl is Pd.DTDGA and IR spectra of the extracted species have been also studied. The other investigated metals ions were found poorly extracted under the same extraction contortions. Quantitative back-extraction of Pd(II) in the organic phase was obtained in single contact using thiourea solution. The obtained results make the novel synthesized ligands a promising candidates for selective recovery and separation of Pd(II) from spent catalyst dissolver (SSCD) solution.

     

Extraction of some transition metals with N,N-dibutyl-N'-benzoylthiourea into molten paraffin at 65 degrees C

The solid-liquid extraction behaviour of some transition metals (Cu(II), Co(II), Ni(II), Cd(II) and Pb(II)) by the use of N,N-dibutyl-N'-benzoylthiourea as an extractant in paraffin (58-60 degrees C) has been investigated at 65.0+/-0.5 degrees C. The effect of equilibration time, pH of the aqueous phase, concentration of extractant and solid solvent used on the extraction efficiency of these metals have been discussed. The interferences of various ions are examined. The method has been applied to the determination of these metals in synthetic samples, mushrooms and sediment.     

Thermodynamic Complexation of Dopamine with Zinc(II) in Media with Different Dielectric Constants

The complexation of zinc(II) with dopamine has been investigated by spectrophotometric measurements in mixed solvent system at an ionic strength of 0.2 mol•dm－3 sodium chloride, employed at at (15±0.1), (25±0.1), (35±0.1) ℃ at inin a pH range of ca. 6 to ca. 7 with a high ratio of ligand to metal. The effect of solvent systems on protonation and complexation are was was discussed. Linear relationships are werewere observed by plotting lg K versus 1/D, where K and D show stability and dielectric constants, respectively.     

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.