Anwendung von ionenaustauschverfahren zur bestimmung von spurenelementen in natürlichen wässern—IV: Uran,kobalt und kadmium

A method is described for separating and determining. by spectrofluorimetric or spectrophotometric measurement, traces of uranium. cobalt and cadmium at ppM levels in natural waters. The sample is acidified with HCl. filtered. and after addition of ascorbic acid and potassium thiocyanate, passed through a column of Dowex 1.- × 8 anion-exchange resin in the thiocyanate form. The three ions are concentrated on the resin as thiocyanate complexes, being at the same time separated from most of the other ions present in the sample. Elution with a tetrahydrofuranmethylglycol-HCl mixture removes other interfering ions. then 6M HCl strips the cobalt. 1M HCl the uranium, and 2M HNO₃ the cadmium. Data are presented for concentrations of uranium (0·01–5 ppM) cobalt (0·04–1·9 ppM) and cadmium (0·04–0·6 ppM) in a large number of water sources in Austria.     

Anwendung von ionenaustauschverfahren zur bestimmung von spurenelementen in natürlichen wässern—V: Blei

A method is described which makes possible the separation of lead from natural waters at the ppM level, and its final determination by spectrophotometry or atomic absorption. The sample is made 0.15M in hydrobromic acid, filtered, and passed through Dowex 1 X8 (bromide form). The lead is sorbed on the resin and most of the other elements present are separated from it. The lead is eluted with 6M hydrochloric acid and determined by the dithizone method or by atomic-absorption. The method was used to determine lead in drinking water and water from the Danube, lead concentrations in the range 2–14 ppM being found.     

Dissociation constants of carboxymethyloxysuccinic acid

The dissociation constants of carboxymethyloxysuccinic acid (CMOS) have been measured at 25° and an ionic strength of 0·1M in sodium perchlorate. The values found were: pK₁ = 2·52, pK₂ = 3·77 and pK₃ = 5·00. CMOS is thus seen to be rather stronger than its isomer citric acid.     

Kinetics of the R + HBr RH + Br (CH3CHBr, CHBr2 or CDBr2) equilibrium. Thermochemistry of the CH3CHBr and CHBr2 radicals

The kinetics of the reaction of the CH₃CHBr, CHBr₂ or CDBr₂ radicals, R, with HBr have been investigated in a temperature-controlled tubular reactor coupled to a photoionization mass spectrometer. The CH₃CHBr (or CHBr₂ or CDBr₂) radical was produced homogeneously in the reactor by a pulsed 248 nm exciplex laser photolysis of CH₃CHBr₂ (or CHBr₃ or CDBr₃). The decay of R was monitored as a function of HBr concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature. The reactions were studied separately from 253 to 344 K (CH₃CHBr + HBr) and from 288 to 477 K (CHBr₂ + HBr) and in these temperature ranges the rate constants determined were fitted to an Arrhenius expression (error limits stated are 1σ + Student’s t values, units in cm³ molecule⁻¹ s⁻¹, no error limits for the third reaction): k(CH₃CHBr + HBr) = (1.7 ± 1.2) × 10⁻¹³ exp[+ (5.1 ± 1.9) kJ mol⁻¹/RT], k(CHBr₂ + HBr) = (2.5 ± 1.2) × 10⁻¹³ exp[−(4.04 ± 1.14) kJ mol⁻¹/RT] and k(CDBr₂ + HBr) = 1.6 × 10⁻¹³ exp(−2.1 kJ mol⁻¹/RT). The energy barriers of the reverse reactions were taken from the literature. The enthalpy of formation values of the CH₃CHBr and CHBr₂ radicals and an experimental entropy value at 298 K for the CH₃CHBr radical were obtained using a second-law method. The result for the entropy value for the CH₃CHBr radical is 305 ± 9 J K⁻¹ mol⁻¹. The results for the enthalpy of formation values at 298 K are (in kJ mol⁻¹): 133.4 ± 3.4 (CH₃CHBr) and 199.1 ± 2.7 (CHBr₂), and for α-C–H bond dissociation energies of analogous compounds are (in kJ mol⁻¹): 415.0 ± 2.7 (CH₃CH₂Br) and 412.6 ± 2.7 (CH₂Br₂), respectively.     

Self-assembly of the pre-formed inclusion complexes between cyclodextrins and alkanethiols on gold electrodes

A new kind of self-assembled monolayer (SAM) formed in aqueous solution through the pre-formed inclusion complexes (abbreviated CD · C_n) between α, β-cyclodextrins (CDs) and alkanethiols (CH₃(CH₂)_n−1)SH, n = 10, 14 and 18) was prepared successfully on gold electrodes. High-resolution ¹H NMR was used to confirm the formation of CD · C_n. X-ray photoelectron spectroscopy, cyclic voltammetry and chronoamperometry were used to characterize the resulting SAMs (denoted as M_CD·Cn). It was found that M_CD·Cn were more stable against repeated potential cycling in 0.5 M H₂SO₄ than SAMs of CH₃(CH₂)_n−1SH (denoted as M_Cn), with a relative sequence of M_β−CD·Cn > M_α−CD·Cn > M_Cn. In addition, an order of blocking the electron transfer between gold electrodes and redox couples (both Fe(CN)³₆ and Ru(NH₃)³⁴₆) in solution, M_CD·C10 > M_CD·C14 > M_CD·C18, was observed. A plausible explanation is provided to elucidate some of the observations.     

Anwendung von ionenaustauschverfahren zur bestimmung von spurenelementen in natürlichen wässern—VII: Kupfer

A method is described which makes it possible to separate ppM levels of copper from natural waters and complete the determination by atomic-absorption. The sample is made 0.1M in hydrochloric acid, filtered, treated with ascorbic acid and passed through Dowex 1 X8 (chloride form). The anionic copper(I) chloro-complex is sorbed and the copper separated from most other elements present. After elution with 1M nitric acid, the copper is determined by atomic absorption. The method has been used to determine copper concentrations in the range 10–39 ppM, in some Austrian waters.     

Isolation and ultramicro determination of hydrogen sulphide in air or water by use of ion-exchange resin

Summary A method is described for the ultramicro determination of hydrogen sulphide in gaseous mixtures or water, based on the sorption of hydrogen sulphide on columns of Amberlite IRA 400, followed by elution with 4M sodium hydroxide and colorimetric estimation as Methylene Blue. The method permits the rapid determination of 1–20g of hydrogen sulphide present at dilutions of 0.07–20 ppm in air or down to 0.1 ppM in water. The resin retains the sulphide for about 10 days without loss.

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Zusammenfassung Ein Verfahren zur Ultramikrobestimmung von Schwefelwasserstoff in Gasgemischen oder in Wasser wurde beschrieben. Es beruht auf der Adsorption an Amberlit IRA 400 und nachfolgender Eluierung mit 4-m Natronlauge. Schließlich wird als Methylenblau kolorimetrisch gemessen. 1 bis 20g H₂S können in Verdünnungen von 0,07 bis 20 ppm in Luft bzw. bis zu 0,1 ppM in Wasser bestimmt werden. Der Austauscher hält das Sulfid für 10 Tage ohne Verlust.

     

The O–H···O, O–H···N and C–H···O hydrogen bonds in 1,4-dimethylpiperazine mono-betaine monohydrate

1,4-Dimethylpiperazine mono-betaine (1-carboxymethyl-1,4-dimethylpiperazinium inner salt, MBPZ) crystallizes as monohydrate. The crystals are orthorhombic, space group Pccn. Two MBPZ molecules and two water molecules form a cyclic oligomer, (MBPZ·H₂O)₂. The O–H···O and O–H···N hydrogen bonds are of 2.769(1) and 2.902(1) Å, respectively. The dimers interact with the neighboring molecules through the C–H···O hydrogen bonds of 3.234(1) Å. The piperazine ring assumes a chair conformation with the N(4)–CH₃ and N⁺(1)–CH₂COO⁻ groups in the equatorial position and the N⁺(1)–CH₃ group in the axial one. The FTIR spectrum is compared with that calculated by the B3LYP/6-31G(d,p) level of theory.     

Anwendung von ionenaustauschverfahren zur bestimmung von spurenelementen in natürlichen wässern—VI: Zink

A method is described for the separation of ppM levels of zinc in natural waters and final determination by atomic absorption. The sample is acidified, filtered, treated with potassium thiocyanate, and passed through Dowex 1 × 8 (thiocyanate form). The anionic zinc thiocyanate complex is sorbed and separated from most of the accompanying elements. The column is washed with an aqueous-organic hydrochloric acid solution and with 1M hydrochloric acid, and the zinc is then eluted with 0.15M hydrobromic acid and determined directly in the eluate by atomic-absorption. The method was used for determining zinc in some Austrian waters, zinc contents in the range 18–685 ppM being found.     

New insight in the structure–luminescence relationships of Ca9Eu(PO4)7

The double phosphate Ca₉Eu(PO₄)₇, obtained by solid state reaction, was found to be isotypic with Ca₃(PO₄)₂, with space group R3c and unit cell parameters a=10.4546(1) Å, c=37.4050(3) Å, V=3540.67(9) Å³, Z=6. The structure parameters refined using the Rietveld method showed that europium shares positions M1, M2 and M3 with calcium, contradicting previously published Mössbauer results. Low temperature luminescence under selective excitation of Eu³⁺ in Ca₉Y_1−xEu_x(PO₄)₇ and in Ca₉Eu(PO₄)₇ samples was studied, confirming the Eu³⁺ distribution into these sites. At 10 K, ⁵D₀→⁷F₀ emission lines of Eu³⁺ were observed at 578.5, 579.5, 580.1 nm for the M3, M1 and M2 sites, respectively. High temperature X-ray powder diffraction evidenced a second-order phase transition around 573 °C.     

Ionic liquid-based ultrasound-assisted dispersive liquid–liquid microextraction combined with electrothermal atomic absorption spectrometry for a sensitive determination of cadmium in water samples

A new method was developed for the determination of cadmium in water samples using ionic liquid-based ultrasound-assisted dispersive liquid–liquid microextraction (IL-based USA-DLLME) followed by electrothermal atomic absorption spectrometry (ETAAS). The IL-based USA-DLLME procedure is free of volatile organic solvents, and there is no need for a dispersive solvent, in contrast to conventional DLLME. The ionic liquid, 1-hexyl-3-methylimidazolium hexafluorophosphate (HMIMPF₆), was quickly disrupted by an ultrasonic probe for 1 min and dispersed in water samples like a cloud. At this stage, a hydrophobic cadmium–DDTC complex was formed and extracted into the fine droplets of HMIMPF₆. After centrifugation, the concentration of the enriched cadmium in the sedimented phase was determined by ETAAS. Some effective parameters of the complex formation and microextraction, such as the concentration of the chelating agent, the pH, the volume of the extraction solvent, the extraction time, and the salt effect, have been optimized. Under optimal conditions, a high extraction efficiency and selectivity were reached for the extraction of 1.0 ng of cadmium in 10.0 mL of water solution employing 73 µL of HMIMPF₆ as the extraction solvent. The enrichment factor of the method is 67. The detection limit was 7.4 ng L^− 1, and the characteristic mass (m₀, 0.0044 absorbance) of the proposed method was 0.02 pg for cadmium (Cd). The relative standard deviation (RSD) for 11 replicates of 50 ng L^− 1 Cd was 3.3%. The method was applied to the analysis of tap, well, river, and lake water samples and the Environmental Water Reference Material GSBZ 50009-88 (200921). The recoveries of spiked samples were in the range of 87.2–106%.     

Strontium–copper selenite–chlorides: Synthesis and structural investigation

Two new complex selenite–chlorides of strontium and copper Sr₂Cu(SeO₃)₂Cl₂ (I) and SrCu₂(SeO₃)₂Cl₂ (II) were obtained and characterized by X-ray diffraction technique, DTA and IR spectroscopy. Both compounds crystallize in the monoclinic system I: Sp. gr. P2₁/n, a=5.22996(3) Å, b=6.50528(4) Å, c=12.34518(7) Å, β=91.3643(2)°, Z=2; II: Sp. gr. P2₁, a=7.1630(14) Å, b=7.2070(14) Å, c=8.0430(16) Å, β=95.92(3)°, Z=2. Comparison of the crystal structure of (I) with the structures of Sr₂M(SeO₃)₂Cl₂ (M=Co, Ni) was performed. The substitution of strontium atom in the structure of (I) by Cu²⁺ ion with a 3d⁹ Jahn–Teller distorted surrounding leads to the lowering of the structure symmetry and to the appearance of the noncentrosymmetric structure of (II). The noncentrosymmetric character of the structure of (II) was confirmed by SHG signal (1.2 units relative to an α-quartz powder sample).     

Spectrophotometric determination of molybdenum by extraction of its thiosulphate complex

A simple and rapid spectrophotometric determination of molybdenum is described. The molybdenum thiosulphate complex is extracted into isoamyl alcohol from 1·0–1·5M hydrochloric acid containing 36–40 mg of Na₂S₂O₃·5H₂O per ml. The absorbance at λ_max = 475 nm obeys Beer's law over the range 0–32 μg of Mo per ml of solvent phase. Up to 5 mg/ml of Ti(IV), V(V), Cr(VI), Fe(III), Co(II), Ni(II), U(VI), W(VI), Sb(III), 1 mg/ml of Cu(II), Sn(II), Bi(V) and 10 μg/ml of Pt(IV) and Pd(II) do not interfere. Large amounts of complexing agents interfere. The method has been applied to analysis of synthetic and industrial samples.     

Mild hydrothermal synthesis, crystal structure, spectroscopic and magnetic properties of the [M=Fe, x=2.08, y=1.58; M=Co, Ni, x=2.5, y=2] compounds

The [M=Fe (1), x=2.08, y=1.58; M=Co (2), x=2.5, y=2; Ni (3), x=2.5, y=2] compounds have been synthesized using mild hydrothermal conditions at 170 °C during five days. Single-crystals of (1) and (2), and polycrystalline sample of (3) were obtained. These isostructural compounds crystallize in the orthorhombic system, space group Aba2, with a=9.9598(2), b=18.8149(4) and c=8.5751(2) Å for (1), a=9.9142(7), b=18.570(1) and c=8.4920(5) Å for (2) and a=9.8038(2), b=18.2453(2) and c=8.4106(1) Å for (3), with Z=8 in the three phases. An X-ray diffraction study reveals that the crystal structure is composed of a three-dimensional skeleton formed by [MO₅F] and [MO₄F₂] (M=Fe, Co and Ni) octahedra and [HPO₃] tetrahedra, partially substituted by [PO₄] tetrahedra in phase (1). The IR spectra show the vibrational modes of the water molecules and those of the (HPO₃)²⁻ tetrahedral oxoanions. The thermal study indicates that the limit of thermal stability of these phases is 195 °C for (1) and 315 °C for (2) and (3). The electronic absorption spectroscopy shows the characteristic bands of the Fe(II), Co(II) and Ni(II) high-spin cations in slightly distorted octahedral geometry. Magnetic measurements indicate the existence of global antiferromagnetic interactions between the metallic centers with a ferromagnetic transition in the three compounds at 28, 14 and 21 K for (1), (2) and (3), respectively. Compound (1) exhibits a hysteresis loop with remnant magnetization and coercive field values of 0.72 emu/mol and 880 Oe, respectively.     

Phase Relations at 1500°C in the Ternary System ZrO2–Gd2O3–TiO2

Phase relations at 1500°C in the ternary system ZrO₂–Gd₂O₃–TiO₂ have been determined by the powder X-ray diffraction of samples prepared by standard solid state reaction. A large area of this ternary oxide system centered on the Gd₂Ti₂O₇–Gd₂Zr₂O₇ join was shown to exhibit the pyrochlore and defect fluorite structures. The pyrochlore structure was observed for stoichiometries as far from the ideal M₄O₇ as M₄O_6.7 and M₄O_7.4, although the degree of disorder seemed much higher at these stoichiometries. On further deviation from the ideal M₄O₇ stoichiometry a smooth transition to fluorite average structure was observed for Zr-rich compositions. None of the other binary phases were observed to show significant extent of solid solution into the ternary region.     

Reinvestigation of the Fe-rich part of the pseudo-binary system SrO–Fe2O3

The phase relations in the Fe-rich part of the pseudo-binary system SrO–Fe₂O₃ (>33 mol% Fe₂O₃) were reinvestigated between 800 and 1500 °C in air. A combination of microscopy, electron probe micro-analysis, powder X-ray diffraction and thermal analysis was used to determine phase relations, crystal structure parameters and phase transition temperatures. M-type hexagonal ferrite SrFe₁₂O₁₉ (85.71 mol% Fe₂O₃) is stable up to 1410 °C. No indication of a significant phase width was found; Sr₄Fe₆O_13±δ appears as a second phase in compositions with <85.71±0.2 mol% Fe₂O₃. Sr₄Fe₆O_13±δ itself is stable between 800 and 1250 °C. Two other hexagonal ferrites were found to exist at high temperatures only: W-type SrFe²⁺₂Fe³⁺₁₆O₂₇ is stable between 1350 and 1440 °C and X-type ferrite Sr₂Fe²⁺₂Fe³⁺₂₈O₄₆ between 1350 and 1420 °C, respectively, which is shown here for the first time. These findings in combination with previously published data were used to derive a corrected phase diagram of the Fe-rich part of the pseudo-binary system SrO–Fe₂O₃.     

Système ternaire : H2O–Fe(NO3)3–Co(NO3)2 isotherme : 30 °C

Ternary system: H₂O–Fe(NO₃)₃–Co(NO₃)₂ isotherm: 30 °C. The H₂O–Co(NO₃)₂ binary system has been investigated in the –28 to 50 °C temperature range. The solid–liquid equilibria of the ternary system H₂O–Fe(NO₃)₃–Co(NO₃)₂ were studied by using a synthetic method based on conductivity measurements. One isotherm is established at 30 °C, and the stable solid phases that appear are iron nitrate nonahydrate: Fe(NO₃)₃·9 H₂O, iron nitrate hexahydrate: Fe(NO₃)₃·6 H₂O, cobalt nitrate hexahydrate: Co(NO₃)₂·6 H₂O, and cobalt nitrate trihydrate: Co(NO₃)₂·3 H₂O. To cite this article: B. El Goundali et M. Kaddami, C. R. Chimie 9 (2006).     

Electrostriction around colloid molecules and interfacial action of inhalation anesthetic: Volume function

Poly( -lysine) exists as a polyelectrolyte in an aqueous solution with charged -NH₃⁺ of the side-chain terminals at pH values below 10.5, while it loses the charges above this pH. Due to the electrostatic repulsion, the conformation of the charged form is random coil while that of the uncharged form is helix. The densities of each form were measured by an oscillation densimeter at several poly( -lysine · HBr) concentrations and the apparent molal volumes were estimated. By extrapolating the apparent molal volumes to infinite dilution, the partial molal volumes of each form at infinite dilution were obtained. When expressed by the partial molal volume per residue at infinite dilution, the values were 125.3 cm³ residue⁻¹ for the uncharged form and 112.8 cm³ residue⁻¹ for the charged form at 298.15°K. From the temperature dependence of the partial molal volume, the partial molal expansibilities were found to be 0.070 cm³ residue⁻¹ deg⁻¹ for the uncharged form and 0.106 cm³ residue⁻¹ deg⁻¹ for the charged form. The smaller partial molal expansibility of the uncharged form compared to the charged form is in agreement with the general pattern that hydrophobic macromolecules show smaller expansibility than hydrophilic macromolecules. An inhalation anesthetic, methoxyflurane, did not alter the volume of the uncharged form and expanded only the charged form. At the anesthetic concentration of 1.7 × 10⁻³ m, the partial molal volume of the charged poly( -lysine · HBr) was expanded by 0.27%. The partial molal volume of methoxyflurane in aqueous solution was 108.5 cm³ mole⁻¹ at 278.15°K while that of the pure liquid state was 113.1 cm³ mole⁻¹. The decrease of the partial molal volume of methoxyflurane in aqueous solution is attributable to the structuring of water molecules around the anesthetic. The partial molal volume of the anesthetic in the 1.0 × 10⁻⁴ m charged poly( -lysine · HBr) solution was 110.9 cm³ mole⁻¹. This increase of the partial molal volume of methoxyflurane in the peptide solution indicates that the anesthetic-water contact is partially destroyed by the binding.     

Spectrofluorometric study of 1,4-diaminoanthraquinone-calcium complex in aqueous sulfuric acid mediums: Spectrofluorometric determination of calcium

The spectrofluorometric study was made of the complex 1,4-diaminoanthraquinone-Ca in aqueous sulfuric mediums [λ_max,ex = 410 nm; λ_max,em = 580 nm; 50% H₂O; stable for at least 4 hr; range temperature OPTIMUM = 20–35 °C; [R]_optimum = 2 × 10⁻⁴M; stoichiometry 2:1 (fluorescent complex) and 1:1 (no fluorescent complex)]. A new method for the spectrofluorometric determination of Ca traces is proposed for concentrations between 150 and 400 ppb. The relative error and the interferences of the method have been investigated.     

Structural and magnetic properties of “one-dimensional” barium vanadium triselenide

BaVSe₃ has been synthesized and its crystal structure determined at 293(2)°K. The structure was solved in the hexagonal space group P6₃/mmc (D⁴_6h), with a = 6.9990(11) and c = 5.8621(13) Å. Scans (2 Θ) of a polycrystalline sample revealed that BaVSe₃ undergoes a transition to an orthorhombic unit cell (b′ 3^1/2 a, a′ a, c′ c) at 303(5)°K. Magnetic susceptibility measurements between 4 and 300°K indicate that BaVSe₃ is paramagnetic down to 41(1)°K, where magnetic ordering occurs, with a magnetic moment in the ordered phase of 0.2 μ_B per vanadium atom. The orthorhombic lattice distortion may be caused by the “freezing in” of “soft” vibrational modes.