Films of supersaturated Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>S solid solutions: Composition prognostication,chemical synthesis,microstructure

Working conditions and the concentration regions of the joint precipitation of PbS and CdS at which substitution solid solutions Cd _x Pb_1–x can be formed were determined by calculation of ionic equilibria in the citrate-ammonia reaction mixture at 298 and 353 K with consideration for the conversion fractions of lead and cadmium sulfides into the corresponding sulfides. The hydrochemical precipitation onto glass-ceramic substrates was used to obtain Cd _x Pb_1–x S (0 < x ≤ 0.149) solid solution films with thicknesses of 0.5 to 1.7 μm and high supersaturation with the substituting component. All the films crystallize to form the B1 structure. The phase and elemental compositions and morphological specific features of the films were studied. It was shown that the thickness of the deposited layers is most strongly affected by the process temperature, ammonium hydroxide concentration, and relative amounts of the metal salts in the reaction mixture. It was found that there are oxygen and chlorine in the Cd _x Pb_1–x S solid solutions, and the distribution of these elements across the layer thickness was determined, with the layer-by-layer distribution of chlorine having a pronounced oscillatory nature. It was shown that, as the chemical precipitation temperature is raised, the content of CdS in the substitution solid solutions grows exponentially. The activation energies Ea.ic of the lead and cadmium interchange in the PbS crystal lattice were found to be, depending on the initial concentration of the lead salt, 75.3, 42.8, and 22.2 kJ mol^–1.     

Synthesis of cadmium complex sulfides nanoparticles by thermal decomposition

Summary The paper presents the conditions of synthesis and results in the characterization (chemical analysis, thermal analysis, kinetic of decomposition) for two complex compounds of cadmium: [Cd(S₂O₃)phen]×H₂O and [Cd(S₂O₃)phen₂]×2H₂O. The obtained complexes were used as precursors for complex sulfides by controlled thermal decomposition. On the basis of transmission electron microscopy (TEM) the complex sulfides may be included in the nanomaterials category.     

Fluorescence properties of nanosized sulfides

The absorption spectra of nanosized sulfides and selenides (ZnS, CdS, CuS, Cu₂S, AgS, In₂S₃, SnS, PbS, Sb₂S₃, FeS, CoS, NiS, CdSe, and Ag₂Se) showed one absorption band with a maximum at wave-lengths shorter than 300 nm. The UV fluorescence spectra of all of these nanosized sulfides in a polyvinyl alcohol film contained maxima at 380–440 nm. Nanosized sulfides are thus characterized by a very large (up to 15000 cm⁻¹) Stokes shift of fluorescence. In a polyvinyl alcohol film, a decrease in the concentration of cadmium sulfide from 0.05 to 0.002 M led to a threefold increase in the fluorescence intensity. The dependence of the degree of fluorescence buildup on the sulfide concentration is nearly linear. An increase in sulfide concentration to more than 5 × 10⁻³ M in solution led to a complete coagulation of particles.     

Combined spectroscopic investigation on the thermal decomposition mechanism of CdHg(SCN)4

The very useful second order nonlinear optical crystal material: cadmium mercury thiocyanate, CdHg(SCN)₄, was synthesized and purified by using a simple and highly-effective method. The thermal decomposition process of CdHg(SCN)₄ was studied by means of thermogravimetric analysis and differential thermal analysis in air. The factual thermal decomposition behavior encountered throughout the heat treatment was investigated by using an electric muffle furnace. The samples calcined at different temperatures were characterized by X-ray powder diffraction and infrared spectroscopy techniques. The intermediates were cadmium mercury thiocyanates and sulfides, cadmium normal and basic sulfates, and the final product was cadmium oxide. A possible chemical decomposition procedure has been put forward and a theoretical explanation has been provided based on the crystal structure.     

Etude photoelectronique de la separation du plomb et du cadmium par echange ionique sur le phosphate de hafnium: X-ray photoelectronic study of the separation of lead and cadmium ions on crystalline hafnium phosphate used as a cation exchanger

X-ray photoelectronic study of the separation of lead and cadmium ions on crystalline hafnium phosphate used as a cation exchanger.Crystalline hafnium monohydrogenphosphate monohydrate [Hf(HPO₄)₂·H₂O] is a useful cationic exchanger for separating lead(II) and cadmium(II) ions. Studies have been carried out at various pH and in the presence of various ligands. X-ray photoelectron spectroscopy has shown that lead diffuses into the deeper layers of the exchanger while cadmium remains near the surface. This property can be used to improve the selectivity of the method by masking cadmium with a large ligand (1,10-phenanthroline), which prevents the metal from adsorbing without any effect on lead fixation.     

Electrochemical Detection of Trace Concentrations of Cadmium and Lead with a Boron‐Doped Diamond Electrode: Effect of KCl and KNO3 Electrolytes,Interferences and Measurement in River Water

Parts‐per‐billion levels of cadmium and lead were detected using square‐wave anodic stripping voltammetry with a boron‐doped diamond electrode. Calibration plots (10‐minute deposition time) in KCl and KNO₃ were non‐linear at low concentrations (1–5 ppb) due to the deposition mechanism of these metals. The preferred electrolyte for cadmium was KCl, while lead could be measured in either electrolyte. The lowest concentrations included in the linear portion of the calibration plot (5 minute deposition time) for cadmium were 10 ppb and 50 ppb in KCl and KNO₃, respectively, and 10 ppb for lead in KNO₃. The presence of either lead or copper suppressed the cadmium stripping peak, but the lead stripping peak was unaffected by cadmium, and enhanced by the addition of copper. A river water sample was analyzed for cadmium and lead, and the cadmium results were confirmed using ICP‐AES spectrometry. It was determined electrochemically that a fraction of lead in the river sample was bound by complexing material in the sample.     

Bestimmung von Mikromengen Schwefel nach Aufspaltung des S8-Ringes in Indium-, Blei-, Antimonund Wismutsulfiden mit Hilfe einer induzierten Reaktion von Natriumazid mit Jod

Zusammenfassung Die Bestimmungsmethode für Mikromengen elementaren, in Sulfiden enthaltenen Schwefels mit Natriumazid und Jod wurde modifiziert. Der Analyse geht die Aufspaltung des S₈-Ringes voraus, die man dank der nukleophilen Wirkung von N₃ ^– in DMF-Lösung erreicht. Diese Methode wurde auf die Bestimmung des Schwefels in Indium-, Blei-, Antimon- und Wismutsulfid angewandt. Sie ist einfach und empfindlich. Ihre Fehlergrenze liegt bei ± 4%.

---

Determination of microamounts of sulfur after cleavage of the S₈ king in indium, lead, antimony and bismuth sulfides by means of an induced reaction of sodium azide with iodine

Summary The determination of microamounts of elemental sulfur contained in sulfides using sodium azide and iodine was modified. The analysis was preceded by cleavage of the S₈ ring, which is achieved by virtue of the nucleophilic action of N₃ ^– in DMF solution. This method was applied to the determination of sulfur in indium, lead, antimony and bismuth sulfides. It is simple and sensitive. Its limit of error is ±4%.

     

New Sensory Materials Based on Chalcogenide Glasses Containing Zinc,Cadmium, and Manganese Sulfides

New chalcogenide glasses of the system 0.5AgI-(0.5 - x)Sb₂S_3-x MS containing cadmium, man- ganese, and zinc sulfides were obtained. The high purity of these materials and their glassy state were proved by X-ray analysis and X-ray fluorescence energy-dispersive spectroscopy. The impedance of the glasses obtained was measured within a wide range of frequencies, and the dependences of the conductivity on the composition of glasses were studied. New potentiometric sensors based the new glasses were developed, and an electrochemical experiment was carried out.     

A Potentiometric Sensing System for Lead

Abstract

A pontentiometric flow system based on a sparingly soluble mixture of lead laurate and lauric acid as the responsive element and a glass electrode as the primary sensor is reported. The response of the system to copper, cadmium, zinc and aluminium is also presented.Although the system is relatively unselective, it has the advantage over commercial (Ag₂S/PbS-based) lead ion-selective electrodes of reversibility of response to copper and cadmium.     

Effect of cadmium and lead adatoms on the reduction kinetics of peroxodisulfate anions at platinized platinum in acid solutions

The reduction of peroxodisulfate anions on a rotating Pt/Pt disk electrode in solutions of sulfuric and perchloric acids with or without cadmium and lead salts is studied. At E _r > 0.2V (RHE) the reduction rate in HClO₄ exceeds that in H₂SO₄, but at E _r < 0.2V, the process in HClO₄ is strongly inhibited upon approaching E _r = 0. Lead adatoms catalyze the process, while cadmium adatoms inhibit it in H₂SO₄ and accelerate it at E _r < 0.2V in HClO₄. The results are interpreted by taking account of the specific adsorption of sulfuric-acid anions and their co-adsorption with cadmium cations, as well as the adsorption of peroxodisulfate anions on the Pt surface modified by lead and cadmium ions in perchlorate solutions.Translated from Elektrokhimiya, Vol. 41, No. 2, 2005, pp. 137–141.Original Russian Text Copyright © 2005 by Nikiforova, Petrii.This revised version was published online in April 2005 with corrections to the article note and article title and cover date.     

Rapid Determination of Cadmium and Lead in Maca (Lepidium meyenii) by Magnetic Solid-Phase Extraction and Flame Atomic Absorption Spectrometry

Multiwalled carbon nanotubes were modified by Fe₃O₄ nanoparticles with application for the preconcentration of metals. The modified materials were characterized by infrared spectroscopy, transmission electron microscopy, and X-ray diffraction. The Fe₃O₄ nanoparticle modified multiwalled carbon nanotubes were used as sorbents for the extraction of cadmium and lead from maca prior to analysis by flame atomic absorption spectrometry. The amount of nanoparticles, pH, adsorption time, coexisting ions, eluent solution, and reuse of the material were characterized to optimize the recoveries of the analytes. Under the optimum conditions, the calibration curves were linear from 0.05 to 20 milligrams per liter for cadmium and from 0.05 to 25 milligrams per liter for lead. The limits of detection were 0.32 and 0.57 micrograms per liter while the relative standard deviations were 2.1 and 1.9 percent, respectively. The method was employed for the determination of cadmium and lead in maca and recoveries between 94.8 and 105.6 percent were obtained.     

Structural characterization of dicyanidobis-(N,N′-dimethylthiourea-κS)cadmium(II)

A cadmium(II) complex dicyanidobis(N,N′-dimethylthiourea-S) cadmium(II) [Cd(Dmtu)₂(CN)₂] (1) is prepared and its structure in the solid state is determined by single crystal X-ray structural analysis. The cadmium(II) ion is four-coordinate having a distorted tetrahedral geometry composed of two cyanide C atoms and two thione S atoms of N,N′-dimethylthiourea (dmtu). The molecular structure is stabilized by intermolecular N-H…N(CN) hydrogen bonding interactions that lead to a 3D network structure. The complex was also characterized by IR and NMR spectroscopy.     

Determination of Lead and Cadmium at Silver Electrode by Subtractive Anodic Stripping Voltammetry in Plant Materials Containing Tl

Lead and cadmium have been determined by the subtractive anodic stripping voltammetry using the square‐wave mode at a silver electrode without removal of oxygen. The samples containing large amount of thallium were collected from a highly contaminated region. The presence of thallium strongly affects the peak shape of Cd. The plant material digestion was performed with HNO₃/HClO₄ mixture using pressurised microwave decomposition. The proposed method used for the lead determination was validated by the inter‐method comparison (ICP‐MS). The cadmium determination was validated using certified reference material. The results obtained, supported by statistical tests, demonstrated the usefulness of the method for the lead determination in samples containing large amounts of Cd and Tl. It is important to note that Cd can only be quantified when the thallium concentration is much lower than that of cadmium.     

Rare earth transition metal sulfides,LnMS3

Ternary rare earth transition metal sulfides LnMS₃ with Ln = La, Nd, and Gd, and M = V and Cr; as well as Ln = La and M = Mn, Fe, Co, and Ni have been prepared and characterized. The vanadium and chromium sulfides crystallize in a monoclinic layer structure isotypic with LaCrS₃, while the other LnMS₃ sulfides crystallize in a hexagonal structure. Chemical shifts of the metal K-absorption edge and XPS binding energies of core levels indicate that the transition metal is trivalent in the V and Cr sulfides, while it is divalent in the Mn, Fe, Co, and Ni sulfides. Electrical and magnetic properties of the sulfides are discussed in terms of their structures and the electronic configurations of the transition metal ions.     

Simultaneous Determination of Cadmium,Copper, Lead and Zinc in Amino Acid Parenteral Nutrition Solutions by Anodic Stripping Voltammetry and Sample Digestion by UV Irradiation

Abstract

Irradiation with ultraviolet (UV) energy was investigated to assay cadmium, copper, lead, and zinc by anodic stripping voltammetry (ASV) in amino acid parenteral nutrition (PN) solutions. Sample digestion by UV irradiation showed the best performances to liberate the metals from the samples (metal recoveries between 90% and 102%) in comparison with classical oxidative wet digestion methods. The best UV digestion condition was obtained with 1:10 diluted PN samples irradiated during 10 h at 90±3°C with the addition of one aliquot of 50 µL concentrated H₂SO₄ and repeated additions of 50 µL 30% (v/v) H₂O₂ at each 60 min irradiation interval. By using the UV digestion procedure cadmium, copper, lead, and zinc were simultaneously assayed in commercial amino acid PN solutions by ASV. The metal concentrations ranged between 1.3 to 4.4 for cadmium, 2.9 to 40.8 for copper, 4.4 to 16.8 for lead, and 1.4 to 208.5 for zinc. The ASV method correlated well with atomic absorption spectrometry measurements to assay the investigated analytes in amino acid PN samples after the UV digestion.     

In-Situ Investigation of Discolouration Processes Between Historic Oil Paint Pigments

Discolouring interactions between paint pigments have been observed since the mid 19^th century. The source of some of these discolourations is the production of copper sulfides from an interaction between cadmium sulfide pigments and copper containing pigments. In this work, the discolouring interaction between cadmium yellow and malachite pigments was observed dynamically using the environmental scanning electron microscope (ESEM).     

Determination of nanomolar concentrations of lead and cadmium by anodic-stripping voltammetry at the silver electrode

Lead and cadmium have been determined by subtractive anodic-stripping voltammetry (SASV) in the square-wave mode at a silver electrode without removal of oxygen. The sensitivities and detection limits for the two metals differ considerably. Detection limits of 0.05 nM for lead and 1 nM for cadmium have been achieved following 90 s electrodeposition. The repeatability of consecutive SASV runs is good (for lead 0.5% at 20 nM for 30 s electrolysis, 5% at 0.3 nM for 60 s electrolysis; for cadmium 2.5% at 20 nM for 30 s electrolysis, 5% at 5 nM for 60 s). Hundreds of runs can be carried out without any pretreatment of the electrode. The high stability is attributed to renewal of the electrode surface that takes place during the electrodeposition step in a two-electrode cell: the silver counter/quasi-reference electrode generates silver ions that codeposit with lead and cadmium at the Ag-RDE, thus ensuring a continuity of the latter. Underpotential deposition (UPD) plays a central role in anodic-stripping voltammetry (ASV). During the deposition step, the adatom coverage of trace elements is in the range of 0.01-1% and no bulk deposition is invoked for metals that exhibit UPD. The UPD properties and, as a result, the ASV signals are strongly affected by the type and concentration of the supporting electrolyte. The effects of Cl⁻, Br⁻, SO₄²⁻ and NO₃⁻ are shown. The analysis of lead and cadmium in natural waters has been performed. Surfactants distort the SASV signal. In order to ensure surfactant-free solutions, the samples were pretreated by wet ashing.     

Simultaneous Determination of Tin,Nickel, Lead,Cadmium and Mercury in Tobacco and Tobacco Additives by Microwave Digestion and RP‐HPLC Followed by On‐Line Column Enrichment

A new method for the simultaneous determination of five heavy metal ions, tin, nickel, lead, cadmium and mercury ions as metal‐tetra‐(2‐aminophenyl)‐porphyrin (T₂APP) chelates was developed using reversed‐phase high performance liquid chromatography (RP‐HPLC) equipped with a photodiode array detector and combined with an on‐line enrichment technique. The tin, nickel, lead, cadmium and mercury ions were pre‐column derivatized with T₂APP to form color chelates. The Sn‐T₂APP, Ni‐T₂APP, Hg‐T₂APP, Cd‐T₂‐APP and Pb‐T₂APP chelates can be absorbed onto the front of the enrichment column when they are injected into the injector and sent to the enrichment column [Waters Xterra? RP₁₈(5μ, 3.9 × 20 mm)] with a buffer solution of 0.05 mol/L pyrrolidine‐acetic acid (pH = 10.0) as mobile phase. After the enrichment had finished, by switching the six‐port switching valves, the retained chelates were back‐flushed by mobile phase and traveling towards the analytical column. These chelates separation on the analytical column [Waters Xterra? RP₁₈ (5μ, 3.9 × 150 mm)] was satisfactory by gradient elution with methanol (containing 0.05 mol/L pyrrolidine‐acetic acid buffer salt, pH = 10.0) and acetone (containing 0.05 mol/L pyrrolidine‐acetic acid buffer salt, pH = 10.0) as mobile phase. The linearity range is 0.01?120 μg/L for each metal ion. The detection limits (S/N = 3) of tin, nickel, lead, cadmium and mercury are 4.0 ng/L, 3.5 ng/L, 2.5 ng/L, 3.0 ng/L and 3.0 ng/L, respectively. This method was applied to the determination of tin, nickel, lead, cadmium and mercury ions in tobacco and tobacco additives with good results.     

Synthesis of 2-mercaptobenzothiazole/magnetic nanoparticles modified multi-walled carbon nanotubes for simultaneous solid-phase microextraction of cadmium and lead

This study describes the successful sequential modification of multi-walled carbon nanotube (MWCNT) by Fe₃O₄ magnetic nanoparticles and 2-mercaptobenzothiazole (MBT) followed by its application as a novel sorbent for simultaneous magnetic solid phase microextraction of lead and cadmium. Fourier transform infrared spectroscopy and scanning electron microscopy were employed to confirm the chemical surface modification of the MWCNT. The ions retained on the 2-MBT/magnetic nanoparticles modified MWCNTs were eluted with 1.0 mL of nitric acid (0.8 mol L^?1) in methanol solution and determined by the flame atomic absorption spectrometry. All parameters affecting the extraction condition were thoroughly investigated and optimised. Under the optimised condition preconcentration factor of 150.0, enhancement factors of 149.0 and 149.2 and limits of detection of 0.21 and 0.01 µg L^?1 were achieved for lead and cadmium, respectively. Using the prepared magnetic nanocomposite, the possible interference of other common ions associated with lead and cadmium determination was effectively avoided and the method was successfully applied to the simultaneous determination of the target ions in various environmental water samples.     

Rapid determination of mono and dinitrophenols by DPP, in the presence of lead and cadmium and using concentrated CaCl2 electrolyte

The contamination of drinking water and industrial wastewaters is a critical environmental problem. The nitrophenol, dinitrophenol, cadmium, and lead contaminants are classified as hazardous compounds. Their rapid determination may be obtained using differential pulse polarography with concentrated electrolyte. CaCl₂, which is very soluble to levels exceeding 5 mol l^–1, allows separation of coalescent peaks at 0.1 mol l^–1. A systematic study undertaken from 0.1 to 5 mol l^–1 shows good separation of lead and cadmium from the organic compounds, and optimization of the electrolyte concentration according to the objective is described. Preconcentration of real samples is necessary because pollution levels are usually very low.