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1.
Summary A rigorous analysis of the effect of various concentrations (0.02–1.60M) of ammonium acetate on the distribution coefficients (K) of a number of metal ions using cation exchanger Dowex 50W-X8 (100–200 mesh NH4 +-form) has been made. On account of the low affinity of U(VI) for resin in 0.20M NH4OAc it can be separated from all other metal ions. HighK values of Sr(II), Ba(II) and Hg(II) at higher 0.50M NH4OAc are responsible for their separation from others. The abnormal column Chromatographic behaviour of Al(III) permits its separation from other metal ions including U(VI), Sr(II), Ba(II), Hg(II). A number of binary and ternary separations have been achieved.  相似文献   

2.
A method for the determination of trace amounts of arsenic in food samples using flow injection analysis and atomic absorption spectrometry with hydride generation (FI-HG AAS) was developed. The parameters of the flow injection system and the hydride generation were optimized with respect to reagent concentrations, atomization temperature, injection volume, reaction coil length and carrier flow rate. The limits of detection and quantification were 0.34µgL–1 and 1.2µgL–:1, respectively, and the analytical curve is linear up to 30.0µgL–1 arsenic. The relative standard deviation for 12 replicates varies between 5% for 4.0µgL–1 As and 1.8% for 30.0µgL–1 As, with an injection frequency of up to 135h–1. Interferences from Ni(II), Cu(II), Fe(III), Cr(III), Mo(II), Bi(III), Se(IV), Se(VI), Sb(III) and Sb(V) could be masked with a mixture of ascorbic acid-KI in a 5.0molL–1 HCl solution. The accuracy of the proposed method was evaluated by using certified reference materials of biological samples, and the method was used to determine the content of arsenic in fish and coffee beans.  相似文献   

3.
The reagent bis(isovalerylacetone)ethylenediimine(H2IVA2en) has been examined for HPLC separation and UV determination of cobalt, copper, iron and platinum using off-line precolumn derivatization and extraction in chloroform. The complexes of cobalt(II), cobalt(III), iron(II), iron(III) and the reagent have been subsequently separated on a Microsorb C-18 column. The complexes were eluted isocratically using ternary mixtures of methanol/water/acetonitrile. Detection was achieved by UV monitoring. Detection limits for Co(II), Co(III), Fe(II) and Fe(III) were 2.5–5.0 ng/injection, based on 0.5–1.0 g/ml with 5 l/injection. The concentration of cobalt(II) and cobalt(III) in aqueous solution have been determined. The presence of oxovanadium(IV), platinum(II), and nickel(II) did not affect the determinations. The HPLC method developed has been applied to the determination of cobalt, copper, iron and platinum in pharmaceutical preparations at the 30 g/g to 15 mg/g level and the obtained results were compared to those of atomic absorption spectrometry.  相似文献   

4.
(Corrin)cobalt(III) is reduced by indium(I) to its Co(II) counterpart (cob(II)alamin, B12r) at pH 1-2 in aqueous chloride. In these solutions the aqua oxidant (B12a) is in mobile anation equilibrium with its chloro derivative. At [Cl] 0.03 M, consumption of Co(III) is exponential and proceeds by parallel paths involving the aqua- and chloro-substituted oxidants. At [Cl] 0.10 M, rates are governed mainly by an preliminary act requiring In(I) and 2 Cl, but no Co(III). This initiation step generates a more reactive In(I) species which is taken to result from a slow heterolysis and loss of ligating water from InCl2 (aq).  相似文献   

5.
Zusammenfassung Die Spektren der Spinellmischkristalle Ni2-x MgxGeO4 (0,0 x 1,25) und Co2-x MgxGeO4 (0,0 x 1,0) im Kristallfeldgebiet zeigen starke Unregelmäßigkeiten, die durch die kristallographisch begründete Annahme gedeutet werden können, daß Ni2+ und Co2+ sich in entlang der trigonalen Achse gestauchten Koordinationsoktaedem befinden. Es wird ein Kristallfeldformalismus entwickelt, der eine quantitative Behandlung dieser Spektren gestattet. Weiter zeigt sich, daß nicht immer, wenn eine trigonale Kristallfeldkomponente zugegen ist, Aufspaltungen der Oktaederbanden zu beobachten sind.
The spectra of the spinel type phases Ni2-x MgxGeO4 (0,0 x 1,25) and Co2-x MgxGeO4 (0,0 x 1,0) in the crystal field region show remarkable band splitting effects. They can be explained by the crystallographically plausible assumption, that the coordination octahedra of Ni2+ and Co2+ are compressed along their trigonal axes. A crystal field formalism is developed which allows a quantitative treatment of the spectra. Finally examples are given showing that band splittings are not always observed in the presence of a trigonal component.

Résumé Le spectre des phases de type spinelle Ni2-x MgxGeO4 (0,0 x 1,25) et Co2-x MgxGeO4 (0,0 x 1,0) dans la région du champ cristallin montre des effets remarquables de séparation de bandes. Ils peuvent être expliqués par l'hypothèse cristallographiquement plausible selon laquelle l'octaèdre de coordination de N2+ et de Co2+ est comprimé selon l'axe trigonal. Un formalisme de champ cristallin développé ici permet un traitement quantitatif des spectres. Enfin on donne des exemples qui montrent que les séparations de bandes ne sont pas toujours observées en présence d'une composante trigonale.


Aus der Habilitationsschrift D. Reinen, Bonn 1965.

Herrn Dr. H. H. Schmidtke habe ich für die kritische Durchsicht des Manuskripts und der Deutschen Forschungsgemeinschaft für die Bereitstellung von Sachbeihilfen zu danken.  相似文献   

6.
The kinetics of electroreduction of ethylenediamine and hydroxyethylenediamine complexes of zinc(II) on a dropping-mercury electrode (DME) in 1 M NaClO4 solutions of pH 9–11.5 is studied at different ethylenediamine concentrations at 25, 35, and 50°C. One wave with a diffusion limiting current is observed at an overall concentration of zinc(II) complexes of 2 × 10–5 M and current recording times t 1 = 0.3–4 s. The polarographic peak that distorts the wave at t 1 0.5 s, pH 11.5, and 25°C is due to the accumulation of insoluble reduction products on the electrode surface. The slow electrochemical step on DME involves complexes Znen2+, which form in preceding reversible chemical steps from complexes present in solution.__________Translated from Elektrokhimiya, Vol. 41, No. 4, 2005, pp. 397–405.Original Russian Text Copyright © 2005 by Kurtova, Kravtsov, Tsventarnyi.  相似文献   

7.
Speciation of arsenic in environmental samples gains increasingly importance, as the toxic effects of arsenic are related to its oxidation state. A method was developed for the determination of trace amounts of arsenic(III) and total arsenic by flow injection hydride generation coupled with an in-house made non-dispersive AAS device. The total arsenic is determined after prereduction of arsenic(V) to arsenic(III) with L-cysteine in a low concentration of hydrochloric, acetic or nitric acid. The conditions for the prereduction, hydride generation and atomization were systematically investigated. A quartz tube temperature of 800°C was found to be optimum in view of peak shape and baseline stability. Pb(II), Ni(II), Fe(III), Cu(II), Ag(I), Al(III), Ga(II), Se(IV), Bi(III) were checked for interfering with the 2g/L As(V) signal. A serious signal depression was only observed for Se(IV) and Bi(III) at a 150-fold excess. With the above system, arsenic was determined at a sampling frequency of about 1/min with a detection limit (3) of 0.01g/L using a 0.5mL sample. The reagent blank was 0.001±0.0003 absorbance units and the standard deviation of 10 measurements of the 2 g/l As signal was found to be 1.2%. Results obtained for standard reference materials and water samples are in good agreement with the certified values and those obtained by ICP-MS  相似文献   

8.
Synergic solvent extraction of Pr(III), Ho(III) and Er(III) was carried out at pH3.5 with a mixture of 2-thenoyltrifluoroacetone (HTTA) and tribenzylamine (TBA) from perchlorate media, having ionic strength 0.1M(H+, ClO 4 ). The stoichiometmric composition of all three synergic adducts was established to be Pr(TTA)3·3TBA, Ho(TTA)3·3TBA and Er(TTA)3·3TBA. The formation constants KTTA and Ksyn and stability constant ±syn were also computed and found to be in the order ErHo>Pr. The effect of various anions on the extraction has also been studied.  相似文献   

9.
A flow-injection procedure for the determination of copper in waste water is described. The procedure is based on the formation of an ion-pair between tetrabutylammonium and the tetrathiocyanatocuprate(II) anion. This ion-pair is extracted with chloroform, and the absorbance of the organic phase is measured at 485nm. Concentrations of copper 0.4mg L–1 can be detected with a linear application range of between 0.5 and 25mg L–1, a relative standard deviation of 2.3% (0.8mg L–1, n=10) and a sampling frequency of 30h–1. Under the proposed working conditions, only Ni(II) and Pd(II) interfere at molar ratios Ni(II)/Cu(II) 50 and Pd(II)/Cu(II) 100.  相似文献   

10.
A flow-injection system with electrochemical hydride generation and atomic absorption detection for As(III)/As(V) determination is described. A simple electrolytic flow-through cell has been developed and optimized. Several cathode materials like Pt, Ag, Cu, C and Pb have been tested. The influence of the electrolysis current, concentration of sulfuric acid, carrier stream, flow rate, sample volume and interferences by other metals on the arsenichydride generation have been studied. For the determination of total inorganic arsenic, As(V) is reduced to As(III) on-line by postassium iodide or L-cysteine at 95° C. The influence of the temperature and the reduction medium on this pre-reduction step has been tested. The calibration curve is linear in the range of 5 to 50 g/L for As(III) and total inorganic arsenic and shows a higher sensitivity than in case of reduction with sodium tetrahydroborate. The detection limit is 0.4 g/L for As(III) and 0.5 g/L for total inorganic arsenic at a sample volume of 1 mL.  相似文献   

11.
Zusammenfassung Untersuchungen an metallischen Werkstoffen und Schlacken aus der Bronzezeit von Ugarit (Ras Shamra) haben gezeigt, daß die dort gefundenen Kupferwerkstoffe aus zumindest teilweise sulfidischen Erzen hergestellt wurden. Die untersuchten Schlackenstücke weisen unterschiedliche Silikate auf, die jedoch durch ungleichmäßige Temperaturen in den Verhüttungsöfen entstanden sein können. Vielleicht handelt es sich um Votivgaben, da kein Verhüttungsofen in der Nähe gefunden wurde und Kupfer-Erze erst mehrere hundert Kilometer entfernt bei Ergani-Maden bzw. in Zypern vorhanden sind. Neben reinen Arsenbronzen werden auch zinnhaltige Arsenbronzen gefunden. Maßgebend in der damaligen Zeit dürfte die Härte, die durch Kalthämmern erzielt wurde und die Farbe der Werkstoffe gewesen sein. Bei einer reinen Arsenbronze, einem Beilbruchstück (121± 16 10 HV1) vermutlich aus Zypern wurde eine Festigkeit Rm von 254 N/mm2, bei einer Bruchdehnung von 5% und bei einem Beilbruchstück aus Ugarit mit geringem Gehalt an Arsen und hohem Gehalt an Zinn eine Festigkeit von Rm=360 N/mm2 bei einer Bruchdehnung von 24% bei einer Härte von 130±3HV1 gemessen. Die Herstellung von messingähnlichen Legierungen mit Gehalten von 12% Zink, wahrscheinlich aus bleihaltigem Galmei wurde an einem Fingerring, der 1400 v. Chr. datiert wurde, ferner an einem Fabeltier mit einem Ankhzeichen auf einer Sonnenscheibe zwischen Hörnern bestätigt. Einlagen bestehen aus goldarmem Elektron.
Investigations of metallic materials and copper slag from the area of Ugarit (Ras Shamra, syria)
Summary Investigations on bronze age metallic materials and on slags from Ugarit (Ras Shamra) have shown, that the copper investigated was produced from at least in part sulfidic ores. The slag pieces contain different silicates, which may have been produced at different temperatures within the smelting furnaces. Perhaps the slag pieces were votive gifts, as there were no smelting furnaces in the surroundings. Copper ores are to be found only in several hundred kilometers distance near Ergani-Maden and in Cyprus. Besides pure arsenic bronzes there are also bronzes which contain besides arsenic a high addition of tin. During Bronze Age the hardness which was increased by cold deformation to more than 200HV1 and the corresponding strength and also the colour of the metallic materials may have been the fundamental aspect for the smith. The tensile strength of an arsenic bronze axe, probably from Cyprus was 276 N/mm2, elongation 5% and hardness 121± 16 10 HV1; the tensile strength of a bronze axe from Ugarit containing less arsenic and much more tin was 360 N/mm2, elongation 24% and hardness 130±3HV1. The production of brass type alloys containing 12% Zn, probably from Galmei containing lead was prooved in a fingerring dated 1400 B. C. and on a fable-animal with the sign of Ankh on a sundisk between the horns. Round light spots on the body were found to have been fabricated from electron with a low content of gold.
  相似文献   

12.
In this study, a syringe-connected minicolumn resin was used for the separation and enrichment of cadmium, copper, nickel and zinc prior to their determination by flame atomic absorption spectrometry. The proposed technique was compared with classical batch and column techniques in terms of rapidness, simplicity, enrichment and risk of contamination. The minicolumn was filled with Chromosorb-103 resin and connected to a syringe. If the samples were treated with ammonium pyrrolidine dithiocarbamate or 8-hydroxyquinoline, the analytes were quantitatively retained at pH2 and pH5 on the resin, respectively. On the other hand, if no chelating agent was added, the analytes were quantitatively retained at pH10. The analytes retained by the resin were quantitatively eluted by drawing and discharging nitric acid in acetone. The analytes in spiked river-water samples and in certified standard reference Bovine-Liver (NIST SRM 1577 b) were quantitatively (94%) recovered. The relative standard deviations for the determinations were found to be 1.0–10%.  相似文献   

13.
A method for the determination of Fe(III), Co(II) and Cr(III) by flame atomic absorption spectrophotometry (FAAS) after preconcentrating on a column containing S. carlsbergensis immobilized on Amberlite XAD-4 has been developed. The optimum values of pH, amount of adsorbent, elution solution and flow rate of the sample solution were determined for the quantitative recovery of the analytes. The effect of interfering ions on the recovery of the analytes was also investigated. Under the optimum conditions, recoveries of Fe(III), Co(II) and Cr(III) by S. carlsbergensis immobilized on Amberlite XAD-4 were 99±2, 100±2 and 98±2% at 95% confidence level, respectively. The limit of detections for Fe(III), Co(II) and Cr(III) were 2.8, 3.9 and 7.4ngmL–1, respectively. The proposed method was applied to the determination of the analytes in various water samples. The validity of the method was checked with spiked water samples. Fe(III), Co(II) and Cr(III) was determined with a relative error of less than 5%.  相似文献   

14.
Two new 1:2 polymeric complexes of copper(II) azide with ethyl isonicotinate (1) and methyl isonicotinate (2) have been synthesized and characterized by spectroscopic and crystallographic methods. The polymeric structure of complex (1) features six coordinated copper centers, a pair of trans-coordinated ligand molecules, and asymmetric 2-1,1 and 2-1,3-azido bridges resulting in a 1D chain structure. In complex (2), each copper atom which is located at an inversion center, is coordinated to a pair of trans ligand molecules, to the nitrogen atom of two -1,1-azido ligand and to an oxygen atom of a bridging (-O,O) nitrogen group. The i.r., electronic and e.s.r. spectra of the complexes are reported.  相似文献   

15.
In the system CdO·xFe2O3 formed from co-precipitated and boiled hydroxides of Cadmium(II) and Iron(III) the following can be identified by X-ray study: atx0.8-besides the Cd(OH)2 phase--Fe2O3, at 1.5x0.8 fine crystalline -Fe2O3 and traces of -Fe2O3, at 4>x>1.5 both modifications, i.e. -Fe2O3 and -Fe2O3, and atx>4 only -Fe2O3.The course of specific magnetisation as a function of composition confirms the X-ray findings.

Mit 3 Abbildungen  相似文献   

16.
A new dinuclear ligand L, ethylene[OO-bis-salicylidene--diketone] bearing two symmetrical coordination sites was synthesized by the condensation of salicylaldehyde and acetylacetone, L, with 1,2-dibromoethane under reflux. The ligand L in a 1:1 ratio was treated with CuCl2 and NiCl2 to yield the complexes, tetrachloro bis[OO-bis- salicylidene--diketone copper(II)] and bis[OO-bis-salicylidene--diketone nickel(II)] chloride. The complexes were subsequently characterized by spectroscopic techniques, elemental analysis, i.r., 1H-n.m.r., 13C-n.m.r., u.v.–vis., e.p.r. spectroscopy, and conductance measurements. The conductance measurements in DMF reveal that the CuII complex is covalent while the NiII complex is ionic and the spectral data support the CuII complex to be distorted octahedral whereas the NiII complex has square-planar geometry. The dioxygen binding was studied spectrophotometrically by the oxidation of tetrachloro bis[OO-bis-salicylidene--diketone copper(II)] with pyrocatechol in the presence of oxygen. The kinetic experiments were performed with the copper complex in DMF by monitoring the increase in absorbance over time at pH 8.0 in the presence of pyrocatechol at 25 °C. The kinetic parameters Vmax and KM were determined on the Michaelis–Menten Approach. Redox behavior of the dinuclear copper(II) complex was investigated by cyclic voltammetry in the presence of O2 with the pyrocatechol (substrate) and also without the substrate. The large difference in potentials E0 is indicative of reversible oxygen binding of the complex and distinct catalytic activity.  相似文献   

17.
Summary In this paper the authors report on several methods for the direct determination of EDTA and indirect determination of iron(III), based on the inhibition effect of EDTA on the catalytic action of copper (II) on the oxidation of 2,2-dipyridyl ketone hydrazone by hydrogen peroxide and on the decrease of this inhibition effect in the presence of Fe(III), respectively. These methods allow the determination of EDTA in the ranges of 0.4–2.0 g · ml–1 and 0.2–1.0 g · ml–1 for the normal and reversed FIA modes, respectively, and of 40–240 ng · ml–1 for Fe(III) by reversed FIA.
Katalytisch-fluorimetrische Bestimmung von EDTA und Eisen(III) durch FließinjektionsanalyseInhibitionsmethoden
Zusammenfassung Verfahren zur direkten Bestimmung von EDTA sowie zur indirekten Bestimmung von Eisen(III) werden beschrieben. Sie beruhen auf der Inhibitorwirkung von EDTA auf den katalytischen Effekt von Kupfer(II) bei der Oxidation von 2,2-Dipyridylketonhydrazon mit Wasserstoffperoxid bzw. auf der Schwächung dieser Inhibitorwirkung in Gegenwart von Eisen(III). Es ist mit diesen Methoden möglich, EDTA im Bereich von 0,4–2,0 g/ml (normale FIA) bzw. 0,2–1,0 g/ml (umgekehrte FIA) und Eisen im Bereich von 40–240 ng/ml (umgekehrte FIA) zu bestimmen.
  相似文献   

18.
1-(2-Thenoyl)-4-trifluoro-2-[2-hydroxy-3-sulfo-5-nitrophenylazo]butadione-1,3 (H2L) was synthesized from 2-thenoyltrifluoroacetone. The formation of a copper(II) complex of the synthesized reagent was studied in the presence and absence of 8-hydroxyquinoline (HR). Monoligand [Cu(HL)2] and mixed-ligand [Cu(HL)2HR] compounds were obtained at pH 4 and 3, respectively. The ratio of components in the monoligand and mixed-ligand compounds were 1 : 2 and 1 : 2 : 1, respectively. Beers law was obeyed in the ranges of copper concentrations from 0.20 to 2.56 and from 0.25 to 2.56 µg/mL, respectively. The dissociation constants of the reagent were .K1 = 4.25µ0.01 and .K2 = 8.20µ0.01 . The stability constants of [Cu(HL)2] and [Cu(HL)2HR] complexes were K1 = 4.96µ0.03 and 4.92µ0.01, respectively. A procedure was developed for the photometric determination of copper(II) in rocks.Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 2, 2005, pp. 157–161.Original Russian Text Copyright © 2005 by Alieva, Chyragov, Makhmudov.This revised version was published online in April 2005 with corrections to the author names and book review format.  相似文献   

19.
The kinetics of the reaction of oximate ions with 2,4-dinitrophenyl p-toluenesulfonate, 4-nitrophenyl p-toluenesulfonate, diethyl 4-nitrophenyl phosphate, and ethyl 4-nitrophenyl ethylphosphonate in H2O-DMSO mixtures (0 to 95 vol % of DMSO) cannot be described in terms of a single Bro/nsted equation. Regardless of the nature of the reaction center and leaving group, both in water and in 80% DMSO fast leveling of the reactivity of oximate ions is observed, the -effect decreases at pK a 9.0 and disappears at pK a 12.0 owing to difference in the solvation of weakly (pK a 9.0) and strongly basic (pK a 9.0) oximate ions rather than to change of the transition state. Just unfavorable solvation effects are responsible for the fact that the limiting nucleophilic reactivity of oximate ions (as typical -nucleophiles) is not higher than the reactivity of strongly basic alkoxide ions.  相似文献   

20.
The complexation behavior of zinc (II) tetraphenylporphyrin-viologen covalently linkedcompounds by a polymethylene chain (ZnPCnV2+; n = 4–9) withtri-O-methyl--cyclodextrin (TM--CD) was investigated by meansof 1H NMR and UV/Vis absorption spectrometry in acetonitrile-water (1:1, v/v).The 1H NMR spectra indicated that ZnPCnV2+ existed as a mixture ofa dimer and a monomer at high concentration (>1 × 10-3 M). The dimerwas degraded to the monomer upon complexation with TM--CD involving theformation of 1:1 and 1:2 (ZnPCnV2+: TM--CD) complexes, whichwas observed by UV/Vis spectrometry. Furthermore, 1H NMR spectra exhibitedthat there are at least two types of structures for these complexes, one is a fastexchanging complex, and another is a slow exchanging one. A slow exchanging complexcould be assigned as a rotaxane type structure in which the methylene chain moiety ofZnPCnV2+ penetrated into the cavity of TM--CD. Discrete formationconstants for these complexes were evaluated. The values were little affected by the spacermethylene chain length (n 7).  相似文献   

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