Indirect complexometric determination of cadmium(II) using 1,10-phenanthroline as selective masking agent

An indirect complexometric method is described for the determination of cadmium(II), 1,10-phenanthroline being used as masking agent. Cadmium(II) in a given sample solution is initially complexed with an excess of EDTA and the surplus EDTA is titrated with lead nitrate solution at pH 5.0–6.0 (hexamine), using xylenol orange as indicator. An excess of 1,10-phenanthroline is then added and the EDTA released from the Cd-EDTA complex is titrated with standard lead nitrate solution. Results are obtained for 1.5–57 mg of Cd with relative errors 0.90% and standard deviations 0.06 mg. Cu(II), Co(II), Hg(II), Ni(II), Zn(II), Pd(II), Tl(III), Au(III) and Sn(IV) interfere, but can be easily masked. The method is applied for the determination of cadmium in synthetic alloy solutions.     

Indirect complexometric determination of palladium usingl-histidine as masking agent

An indirect complexo-titrimetric method is described for the determination of palladium in the presence of other metal ions, L-histidine being used as the masking agent. Palladium(II) and other metal ions are initially complexed with an excess of EDTA and the surplus EDTA titrated with standard zinc sulfate solution at pH 4.5–5.5 using xylenol orange as indicator. An excess of 1 % L-histidine solution is then added, and the released EDTA is titrated with standard zinc sulfate solution. Accurate and reproducible results were obtained for 2–15 mg of Pd with relative errors 0.4% and standard deviations < 0.02mg. Sn(IV) and Au(III) interfere, but can be easily masked. The method is successfully applied for the determination of palladium(II) in alloy compositions.     

Complexometric determination of cadmium using 2-Mercaptoethanol as masking reagent

A complexometric method for the determination of cadmium(II) in presence of other metal ions is described based on the selective masking ability of 2-mercaptoethanol towards cadmium(II). Cadmium and other ions in a given sample solution are initially complexed with excess of EDTA and the surplus EDTA is titrated with lead nitrate solution at pH 5.0–6.0 (hexamethylentetramine), using xylenol orange as indicator. A known excess of 2-mercaptoethanol solution (10% alcoholic) is then added, the mixture is shaken well and the released EDTA from the Cd-EDTA complex is titrated against standard lead nitrate solution. The interferences of various ions are studied and the method is applied to the determination of cadmium in its complexes. Reproducible and accurate results are obtained for 3.5–25mg of Cd with relative errors 0.65% and standard deviations 0.06 mg.     

Complexometric determination of copper(II) in ores,alloys and complexes using 2-mercaptoethanol as indirect masking reagent

A complexo-titrimetric method for the determination of copper(II) in the presence of other metal ions is described, based on the selective masking ability of 2-mercaptoethanol towards copper(II). Copper and other ions in a given sample solution are initially complexed with an excess of EDTA and the surplus EDTA is titrated with zinc sulfate solution at pH 5.0–6.0 (hexamine), using xylenol orange as indicator. A known excess of 2-mercaptoethanol solution (10%) is then added, the mixture is shaken well and the released EDTA from the Cu-EDTA complex is titrated against standard zinc sulfate solution. The interferences of various ions are studied and the method is applied to the determination of copper in its ores, alloys and complexes. Reproducible and accurate results are obtained for 2.5–40 mg of Cu with relative errors 0.4% and standard deviations 0.04 mg.     

Indirect complexometric determination of palladium(II) using sodium nitrite as a selective masking reagent

A selective complexometric method is described for the determination of palladium, sodium nitrite being used as masking reagent. Palladium(II) in a given sample solution is initially cornplexed with an excess of EDTA and the surplus EDTA is titrated with zinc sulfate solution at pH 4.5–5.5 (acetic acid-sodium acetate buffer), using xylenol orange as indicator. An excess of sodium nitrite is then added, the mixture is shaken well and the EDTA released from the Pd-EDTA complex is titrated with a standard zinc sulfate solution. Results are obtained for 2.5–27.5 mg of Pd with relative errors 0.5% and standard deviations 0.05 mg. The interferences of various ions are studied. The method is applied for the determination of palladium(II) in alloys and complexes.     

Triterpene Glycosides of Astragalus and Their Genins. LXI. Occurrence of Cycloartane 6-O-Monodesmosides

Cyclosiversigenin 6-O--L-rhamnopyranoside and 6-O--D-glucopyranoside were isolated fromAstragalus coluteocarpusBoiss. (Leguminosae) andAstragalus dissectusB. Fedtsch. et N. Ivanova, respectively. Cyclosiversigenin 5-O--L-rhamnopyranoside was shown to be an artifact forAstragalus coluteocarpus.Thus, the cyclosiversigenin 6-O--D-glucopyranoside that was isolated from certainAstragalusspecies is hypothesized also to be an artifact. Glycosylation of the 6 -hydroxyl group of cycloartanes by D-glucose and D-xylose, in contrast with other substituents, does not change the low-field position of the PMR signal of the 4-CH ₃ group (1.65 2.01 ppm) that is caused by the influence of deuteropyridine directly on the 6 -hydroxyl. Obviously one of the hydroxyls of the -D-glucopyranoside or -D-xylopyranoside residues has the same effect in this instance.     

Optimizing Instrumental Neutron Activation Analysis of Extraterrestrial Materials: Fragments of Lunar Rocks, Meteorites, Chondrules, and Ultrarefractory Inclusions

A previously developed approach to the optimization of instrumental neutron activation analysis based on the simulation of gamma spectra of samples of the specified composition was extended to the analysis of samples of cosmic origin differing in chemical composition, including samples of small mass (0.01 mg) and dimensions (100 m). The approach was justified by comparing the results obtained with the published data.     

Determination of cadmium, lead, and thallium in materials of the environmental specimen bank using mass spectrometric isotope dilution analysis (MS-IDA)

Summary An analytical procedure for the simultaneous determination of cadmium, lead, and thallium in the mg/kg- and g/kg-range in biological materials and sewage sludge by mass spectrometric isotope dilution analysis (MS-IDA) is described.Cadmium, lead, and thallium were separated by electrolytical deposition after low temperature ashing (LTA) of the samples in oxygen plasma and dissolution of the ashes in HNO₃ or HNO₃/HF. Measurement of the isotopic ratio was carried out with a thermal ionization mass spectrometer using the silica gel technique. Cadmium contents ranging from 1.03 to 4.60 mg/kg with relative standard deviations from 0.3 to 1.3%, lead contents ranging from 75 g/kg to 25 mg/kg with relative standard deviations from 0.6 to 3.5%, and thallium contents ranging from 2.9 to 247.7 g/kg with relative standard deviations from 0.1 to 1.7% were determined in the materials of the environmental specimen bank analyzed.

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Bestimmung von Cadmium, Blei und Thallium in Materialien der Umweltprobenbank mit der massenspektrometrischen Isotopenverdünnungsanalyse

Zusammenfassung Ein Analysenverfahren zur simultanen Bestimmung von Cadmium, Blei und Thallium im mg/kg- und g/kg-Bereich in biologischen Materialien und Klärschlamm mit der massenspektrometrischen Isotopenverdünnungsanalyse (MS-IDA) wird beschrieben.Nach Niedertemperaturveraschung (LTA) der Proben im Sauerstoffplasma und Lösen der Aschen in HNO₃ oder HNO₃/HF-Gemisch werden Cadmium, Blei und Thallium durch elektrolytische Abscheidung abgetrennt. Die Isotopenverhältnismessung erfolgt mit der Silicageltechnik in einem Thermionen-Massenspektrometer. In den analysierten Probenbankmaterialien werden Cadmiumgehalte im Bereich von 1,03 bis 4,60 mg/kg mit relativen Standardabweichungen von 0,3 bis 1,3%, Bleigehalte im Bereich von 75 g/kg bis 25 mg/kg mit relativen Standardabweichungen von 0,6 bis 3,5 % und Thalliumgehalte im Bereich von 2,9 bis 247,7 g/kg mit relativen Standardabweichungen von 0,1 bis 1,7% bestimmt.

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Dedicated to Prof. Dr. W. Fresenius on the occasion of his 70th birthday     

Hydrophile-lipophile balance of alkyl ethoxylated surfactants as a function of intermolecular energies

Summary The semiempirical MNDO method has been used in order to examine the variation of the molecular properties of hydrocarbons C_nH_2n+2 (with 1n19) and ethylene oxide chains CH₃(CH₂CH₂O)_mCH₃ (with 1m19) as a function of their molecular length. Least-square fits of those properties have been calculated, along with two mathematical relations between the hydrophile-lipophile balance of alkyl-phenol ethoxylated surfactants and (1) the ratio of molecular lengths between their lipophilic and hydrophilic branches; (2) the intermolecular energies between the molecules of surfactant, water and hexane.     

Liquid Chromatographic Determination of Sulfamonomethoxine, Sulfadimethoxine, and their N 4-Acetyl Metabolites in Chicken Plasma

An environmentally-friendly method has been established for simultaneous determination of sulfamonomethoxine, sulfadimethoxine, and their N⁴-acetyl metabolites in chicken plasma. The sample is prepared by mixing with 4 mol L^–1 ammonium sulfate solution then centrifugation, and analysis is performed by high-performance liquid chromatography (HPLC) on a polyethylene glycol reversed-phase column with 0.001 mol L^–1 sodium acetate solution as mobile phase and photodiode-array detection. Average recoveries from samples spiked with 0.1, 0.5, and 1.0 g mL^–1 of each drug were >78% and relative standard deviations were within 4%. The practical quantitation limits were 0.09 g mL^–1. No organic solvents or hazardous reagents were used at any stage of the analysis.     

Nachweisstarke,hochselektive extraktions-spektral-photometrische Thalliumbestimmung mit Rhodamin B

Zusammenfassung Zur zuverlässigen Erfassung von Thalliumspuren (20 ng Tl absolut) in wäßrigen, silikatischen und biologischen Proben wurden die herkömmlichen spektralphotometrischen Bestimmungsmethoden kritisch diskutiert und die besonders nachweisstarke und selektive, extraktionsphotometrische Methode über den Tl(III)-Bromo-Rhod-amin-B-Komplex eingehend auf Fehler untersucht. Durch Schütteln der thalliumhaltigen organischen Phase mit 0,5 M HBr-Lösung, die 0,2% Hydroxylamin enthält, konnten Störungen von Elementen (Au, Hg, J), die ebenfalls mit Rhodamin B intensive Farbkomplexe bilden, wesentlich vermindert werden. Die zulässigen Höchstkonzentrationen für Störelemente wurden tabelliert.Die ausgearbeitete Vorschrift erlaubt es, Thalliumgehalte 20 ng neben praktisch allen in umweltrelevanten Proben vorkommenden Elementen mit hoher Genauigkeit zu bestimmen. Die Standardabweichung beträgt bei der Bestimmung von 100 ng Tl/ml±2,5% (20 Bestimmungen).

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Powerful, highly selective extraction-spectrophotometrical determination of thallium with khodamine B

Summary Common spectrophotometric methods for the reliable determination of traces of thallium (20 ng) in aqueous and biological samples and in silicates have been discussed critically; the sources of error in the extraction-photometric method of using the thallium-bromo-rhodamine B complex, which is highly selective and sensitive, have been examined.Shaking of the thallium-containing organic layer with 0,5M HBr-solution containing 0.2% of hydroxylarnine is able to diminish the interference of elements (Au, J, Hg), which give intensively coloured complexes with rhodamine B, too. The permissible limits of concentration of foreign ions are tabulated.The elaborated procedure permits the determination of more than 20 ng thallium in presence of practically all elements occurring in environmental samples with high accuracy. The standard deviation at the 100 ng Tl/ml level is ±2.5% (20 determinations).

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Dankt der Max-Planck-Gesellschaft für ein Gastwissenschafter-Stipendium.     

Sol-Gel Preparation of Silica Films with Controlled Surface Morphology and Their Application to a Low Reflective Glass

Silica coating films with various surface morphologies, such as flat, porous (with deep pores), concave-convex (with hills and valleys), and convex (with hills on flat plane) structure were prepared from a mixture of two kinds of sols derived from polymerized tetraethoxy-silane (TEOS) and methyltriethoxysilane (MTES). Different surface morphologies were obtained by varying the molar ratio r = MTES/TEOS of the coating solution. The surface was flat for r less than 2.5, porous for 2.5 r < 5, concave-convex for 5 r < 7.5, convex for 7.5 r < 13, and again flat for r larger than 13. For 2.5 r < 5, the apparent refractive index of the silica film with porous morphology was decreased to 1.23 by selecting the solvent and by controlling the relative humidity of the coating atmosphere and the heat treatment temperature. Coating of glass with silica films of low refractive index of 1.23 led to the low reflective glasses with visible light reflectance Rvis of less than 0.2%.     

Radiation induced electron exchange reaction of thallium/I/-thallium/III/ at low sulfate ion concentration in perchloric acid solution

To understand the behaviour of Tl/II/ and the bridging group SO ₄ ^2– in radiation induced electron exchange reactions we have investigated the rate constants and mechanisms of reaction of Tl/II/ with Tl/I/ and Tl/III/ in perchloric acid solutions. The results indicated that Tl/II/ is an intermediate in the -ray induced electron exchange process of T1/I/–T1/III/. Sulfate ions at [SO ₄ ^2– ]>-0.02M serve as bridging groups and play an important role in accelerating the T1/II/–T1/I/ reaction. A cooperative effect was found between hydrogen peroxide and sulfate ion at low sulfate ion concentration, [SO ₄ ^2– ]0.02M in perchloric acid solution.     

Thermodynamic Analysis of Phase Equilibria in the System Cyclohexane—Methanol

The phase diagram of cyclohexane-methanol was thermodynamically modeledin the range of 150 T/K 360 and at a pressure of 1 bar on the basis ofavailable experimental data. The Gibbs energy functions of four pure solid andtwo mixture phases were taken into consideration. The liquid phase was describedby a model based on mole fraction statistics and the simplified assumption ofmethanol tetramers mixed with cyclohexane monomers. The gas phase was treatedas a nonideal mixture with a Gibbs energy modeled on the basis of the virialcoefficient formalism considering only monomers. The Gibbs energies of the twosolid modifications of pure methanol, as well as pure cyclohexane, were fixedusing literature data. The pressure dependence of the Gibbs energies of the liquidand solid phases were neglected. The complete T-x phase diagram includinggas/liquid equilibria as well as p-x phase diagrams in the range of 20 and 55°C werecalculated. Experimental and calculated data were found to agree reasonably well.     

Air Pollution Investigation in Vitória Metropolitan Region, ES, Brazil

The application of Mössbauer spectroscopy, X-ray diffractometry, thermogravimetric analysis and PIXE in the characterization of the particulate matter in atmospheric aerosols in Metropolitan Region of Vitória (MRV), Brazil have been investigated. The main sources of particulate matter, natural, industrial and antropogenic from human activities, have been studied to identify its contribution in the atmospheric particles. During the years 1995 to 1999 samples of total suspended particles (TSP, Ø 100 m) were collected from four points within MRV. The inhalable particles (PM₁₀ Ø 10 m) and sedimented particles (SP) were also collected from the same region. A receptor modeling was used for the identification of the source of particulate matter in the collected urban aerosol.     

Reaction of ammonia with β,β′-dithioalkyl-α,α′-divinyl ketones

Conclusions Syntheses are reported for ,-dithioalkyldivinyl ketones, which react with ammonia to give -amino--thioalkyldivinyl ketones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2414–2415, October, 1988.The authors thank A. M. Kachurin for assistance in taking the spectra.     

Indirect Complexometric Determination of Mercury(II) Using Potassium Bromide as Selective Masking Agent

 A complexometric method for the determination of mercury in presence of other metal ions based on the selective masking ability of potassium bromide towards mercury is described. Mercury(II) present in a given sample solution is first complexed with a known excess of EDTA and the surplus EDTA is titrated against zinc sulfate solution at pH 5–6 using xylenol orange as the indicator. A known excess of 10% solution of potassium bromide is then added and the EDTA released from Hg-EDTA complex is titrated against standard zinc sulfate solution. Reproducible and accurate results are obtained for 8 mg to 250 mg of mercury(II) with a relative error ± 0.28% and standard deviations ≤0.5 mg. The interference of various ions is studied. This method was applied to the determination of mercury(II) in its alloys. Received April 18, 2001 Revision October 10, 2001     

Polydentate coordination of the thallium atom in complexes with chiral amidinylcyclopentadienyl ligands

The chiral thallium amidinium cyclopentadiene-N-ylide complexes [C₅(CO₂Me)₄{ArNC(Ar")NAr}]Tl were synthesized and structurally characterized by X-ray diffraction analysis and NMR spectroscopy. In these complexes, an unusual mode of coordination of the thallium atom was found, viz., the thallium atom is coordinated by both the side-chain nitrogen atom (N—Tl, 2.833(6) ) and the system of the cyclopentadienyl ring (Tl—Cp, 2.887(4) ⁵-bonding).     

Luminescence properties of acridine dyes in micellar sodium dodecyl sulfate solutions containing thallium ions

The effect of external heavy Tl^I ion on the luminescence properties of Trypaflavine, Acridine Yellow, and Acridine Orange solubilized in sodium dodecyl sulfate micelles was studied. An increase in the concentration of thallium ions results in a decrease in the intensity of prompt fluorescence, an increase in the intensity of delayed fluorescence, the appearance of phosphorescence at 20 °C, and a shortening of the triplet state lifetime of the dyes. The effective and micellar Stern—Volmer constants of fluorescence quenching of the dyes by thallium ions were determined. The effective and micellar quenching rate constants of triplet states of the dyes by Tl(i) ions and lifetimes of the triplet states of the dyes in the absence of thallium ions were calculated on the basis of kinetic measurements.     

Solution equilibria in l-glutamic acid and l-serine + iron(III) systems

Complex formation equilibria in l-glutamic acid (H2Glu) and l-serine (HSer) +iron(III) ion systems have been studied by a combination of glass electrode potentiometric and visible spectrophotometric measurements in 0.5 mol dm–3 (Na)NO3 ionic medium at 25°C. In the concentration range 1.0[Fe3+]5.0; 3.0[Glu2–]30.0 mmol dm–3 ([Glu]/[Fe]=3:1 to 30:1) and pH between 1.5 and 4.5, iron(III) and glutamic acid form the Fe(Glu)–2, Fe(Glu)+, Fe(HGlu)2+, Fe(OH)Glu, Fe2(OH)2Glu2+, Fe(OH)Glu22– complexes: and several pure hydrolytic products. Iron(III) and l-serine, beside pure hydrolytic complexes of iron(III), form the Fe(HSer)3+, Fe(Ser)2+, Fe(OH)Ser+, Fe(OH)2- Ser0, Fe(OH)Ser2 and Fe2(OH)2(Ser)2+2 complexes, over a broad concentration range of serine to iron ([Ser]/[Fe]=5:1 to 500:1), from pH 1.5 to 4.0. The stability constants of the complexes are given and their formation mechanism is suggested. The possible structure of the complexes, in solution, is discussed.