Simultaneous determination of Zn(II) and Ni(II) in the presence of crown ether by dc polarography

Summary The simultaneous determination of Zn(II) and Ni(II) was studied in the presence of a crown ether by dc polarography. Addition of this reagent caused the difference in the halfwave potentials between the two ions to increase from 0.01 to 0.34 V. The relationship between the concentration of the ion and the wave current was linear for both ions, which suggests the feasibility of a simultaneous determination of Zn(II) and Ni(II) in the presence of a crown ether.     

Simultaneous determination of In(III) and Cd(III) in the presence of polyethylene glycol monostearate by direct current polarography

In the presence of polyethylene glycol monostearate (PEGMS), the reduction potentials for In(III) and Cd(II) become well separated in 0.1 mol dm^?3 potassium chloride medium. The relationships between the currents for the ions and their concentrations are linear in the presence of PEGMS, which makes the simultaneous determination of In(III) and Cd(II) possible.     

Simultaneous determination of In(III) and Cd(II) by differential pulse polarography in the presence of poly β-cyclodextrin

The difference in the peak potentials of In(III) and Cd(II), whose reduction potentials are very close to each other, becomes large in the presence of poly beta-cyclodextrin in sodium perchlorate medium. The relationships between the peak currents for these two ions and their concentrations are linear, suggesting that the simultaneous determination of the ions is possible in the presence of this reagent.     

Simultaneous determination of chromium(III) and cadmium(II) by differential pulse anodic stripping voltammetry on a stannum film electrode

A stannum film electrode has been developed for the simultaneous determination of trace levels of chromium(III) and cadmium(II) by differential pulse anodic stripping voltammetry (DPASV). The stannum film electrode was generated in situ by depositing simultaneously the stannum film and the metals obtained by reduction of Cd(II) and Cr(III) at −1.4 V on a glassy carbon electrode. Then, the reduced products were oxidized by scanning the potential of the electrode from −1.4 to −0.4 V using DPASV. The electrode exhibited well-defined and separated stripping signals for both metals accompanied with a low background contribution. The possible mechanism of this design was proposed. Under the optimized working conditions, the detection limit was 2.0 and 1.1 μg l⁻¹ for Cr(III) and Cd(II) at a deposition time of 3 min. Finally, the stannum film electrode was successfully applied to the determination of Cd(II) in tap water with satisfactory results.     

Electrochemical reduction of the lanthanide ions: Part II. Second reduction step of europium(III), ytterbium(III) and samarium(III) in acidic tetramethylammonium perchlorate solution

The second reduction step of Eu(III), Yb(III) and Sm(III) in 0.04 M tetramethylammonium perchlorate in the pH range 1.8–7 was investigated by cyclic voltammetry and d.c. polarography. The proposed reaction scheme at large hydrogen ion/lanthanide ion concentration ratios involves the reduction of the lanthanide(II) ion to the metallic state accompanied by a surface catalytic reaction in which the reactant is regenerated and also hydroxyl ions are formed which induces the precipitation of lanthanide(II) hydrous oxide on the electrode surface. This lanthanide(II) hydroxide is reduced at more negative potentials than the hydrated lanthanide(II) species. At lower hydrogen ion/lanthanide ion concentration ratios a preceding chemical reaction, probably involving hydrolyzed lanthanide(II) species, becomes rate determining.     

Simultaneous determination of In(III) and Cd(II) by differential pulse polarography in the presence of poly ?-cyclodextrin

The difference in the peak potentials of In(III) and Cd(II), whose reduction potentials are very close to each other, becomes large in the presence of poly -cyclodextrin in sodium perchlorate medium. The relationships between the peak currents for these two ions and their concentrations are linear, suggesting that the simultaneous determination of the ions is possible in the presence of this reagent.     

Simultaneous Voltammetric Determination of Heavy Metals by Use of Crown Ether‐modified Electrodes and Chemometrics

A three‐sensor array consisting of a graphite‐epoxy composite electrode (GEC), 4‐carboxybenzo‐18‐crown‐6‐GEC and 4‐carboxybenzo‐15‐crown‐5‐GEC was employed for the simultaneous determination of Cd(II), Pb(II) and Hg(II) by differential pulse anodic stripping voltammetry (DPASV). Sensors were firstly studied for the determination of Hg(II); secondly, peak current responses confirmed that all sensors showed differentiated response for the three considered metals. A response model was developed to resolve mixtures of Cd(II), Pb(II) and Hg(II) at the µg L^?1 level; Discrete Wavelet Transform was selected as preprocessing tool and artificial neural network used for the modelling of the obtained responses.     

Detection of lead(II) using an glassy carbon electrode modified with Nafion, carbon nanotubes and benzo-18-crown-6

A glassy carbon electrode was modified with Nafion, carbon nanotubes and benzo-18-crown-6 to give an electrode for the selective determination of lead(II) via square wave anodic stripping voltammetry. The use of carbon nanotubes with their extraordinary electrical conductivity and strong adsorption ability warrants high sensitivity. Benzo-18-crown-6 is employed as a “molecular scavenger” because of its excellent selectivity for lead(II). The modified electrode shows enhanced sensitivity, reproducibility and selectivity for lead(II) even without applying an electrical potential during the accumulation time. It responds linearly to lead(II) in the 1 to 30 nM concentration range (with a correlation coefficient of 0.9992) after a 10-min accumulation time. The detection limit is 1 nM. The sensor exhibits excellent selectivity over other heavy metal ions such as Cd(II), Cu(II), Zn(II), and Hg(II).

Polarographic analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III)

The analytical determination of Hg(II), Cu(II), Cd(II), As(III), Sb(III), Ti(IV) and U(VI) in the presence of Fe(III) and 1 M H₂SO₄ are investigated using the polarographic technique. The wave corresponding to the reduction of Fe(III) to Fe(II) was found to be completely suppressed by the addition of 1% pyrogallol. Thus, different mixtures of these elements, viz. Hg(II), Cu(II), Cd(II), As(III) and Fe(III)-mixture (A), Cu(II), Cd(II), Sb(III), As(III) and Fe(III)-mixture (B), and Cu(II), Cd(II), Ti(IV), U(VI) and Fe(III)-mixture (C), were quantitatively determined using 1% pyrogallol and 1 M H₂SO₄ as supporting electrolyte. The i₁/c results give excellent correlations in each case, as indicated from the results of leastsquares regression analysis.     

Simultaneous kinetic determination of Fe(III) and Fe(II) by H-point standard addition method

The H-point standard addition method (HPSAM) was applied to kinetic data for simultaneous determination of Fe(III) and Fe(II) or selective determination of Fe(III) in the presence of Fe(II). The method is based on the difference in the rate of two processes; reduction of Fe(III) with Co(II) and subsequent complex formation of resulted Fe(II) with 1,10-phenanthroline, and direct complex formation between Fe(II) and 1,10-phenanthroline in pH 3 and cetyl trimethyl ammonium bromide, CTAB, micellar media. Fe(III) can be determined in the range of 0.75-5.13 mug ml(-1)with satisfactory accuracy and precision in the presence of excess Fe(II) under working conditions. The proposed method was successfully applied to the simultaneous determination of Fe(III) and Fe(II) and also to the selective determination of Fe(III) in the presence of Fe(II) in several synthetic mixtures containing different concentration ratios of Fe(III) to Fe(II).     

Application of modified normal pulse polarography and its differential mode to alkaline-earth metal ions in acid solutions

The simultaneous determination of alkaline-earth metal ions in acid solution was studied by modified normal pulse polarography. Well-defined waves were recorded for calcium, strontium and barium, but no limiting current was found for magnesium, because of its very negative reduction potential. The differential mode of this method gives peak-type polarograms and is useful for the simultaneous determination of species for which the half-wave potentials lie close together. The interference of dissolved oxygen was eliminated by the use of tetramethylammonium chloride as a supporting electrolyte.     

Polarographic determination of Zn(II), Ni(II) and Co(II) in the presence of polyethylene glycol

Summary The difference in the half-wave potentials of Zn(II) and Ni(II), whose reduction potentials are close to each other, becomes larger in the presence of polyethylene glycol. The relationship between the concentration of the ions and their wave currents was linear for both ions in the presence of this polymer, suggesting that the simultaneous determination of Zn(II) and Ni(II) is possible.     

Column chromatographic separation of Ce(III) from U(VI) and other elements in hippuric acid medium as an analytical application of poly[dibenzo-18-crown-6]

A simple and efficient column chromatographic method has been developed for the separation of Ce(III) from U(VI) and Ni(II)/Zn(II)/Cd(II)/Co(II)/Ba(II) etc. using poly[dibenzo-18-crown-6] as stationary phase and hippuric acid as a counter ion. HCl and H₂SO₄ were most efficient eluting agents for Ce(III). The capacity of crown polymer for Ce(III) was found to be 0.285 ± 0.01 mmol/g. The tolerance limits of various cations and anions for Ce(III) were determined. Ce(III) was quantitatively separated from U(VI) and Ni(II)/Zn(II)/Cd(II)/Co(II)/Ba(II) in binary as well as multicomponent mixtures. The good separation yields were obtained and had good reproducibility (±2 %). The method incorporated the determination of Ce(III) in real sample. The method was simple, rapid and selective.     

Analytical applications of triethylenetetraminehexa-acetic acid: Part 4. amperometric titrations of metal ions

The behaviour of metal ions during titration with triethylenetetraminehexaacetic acid (TTHA) in several supporting electrolytes was investigated by d.c. and square-wave polarography. The composition of the complexes (M₂L or ML) formed during titration is reported as well as the [M] : [L] ratio corresponding to the end-point of amperometric titration. The optimal conditions (by d.c. and s.w. detection) are given for titrations of Cu(II), Ni(II), Cd(II), Pb(II) and Zn(II) based on the reduction current of metal ions, as well as for titrations of Cu(II), Cd(II), Pb(II), Zn(II), Al(III), Ca(II) and Mg(II) based on the anodic current of TTHA. Application of the anodic current of TTHA permits determinations of polarographically inactive metals and is valuable in analysis of mixtures.     

Synthese und Kristallstruktur von [Ba(18-Krone-6)(DMF)4][Cd(Se4)2]

Synthesis and Crystal Structure of [Ba(18-Crown-6)(DMF)₄][Cd(Se₄)₂] The title compound has been prepared by the reaction of a DMF-solution of lithium polyselenide with BaSe₂ and cadmium acetate in the presence of 18-crown-6, forming black crystals. The compound was characterized by IR spectroscopy and by an X-ray structure determination. Space group P2/a, Z = 4, 5392 observed unique reflections, R = 0.048. Lattice dimensions at ?90°C: a = 2021.9(12); b = 1019.8(6); c= 2270.8(14)pm, ß = 106.98(4)°. The structure consists of [Ba(18-crown-6)(DMF)₄]²⁺ ions, in which the barium ions are coordinated by the six oxygen atoms of the crown ether molecule and by four oxygen atoms of the DMF molecules, and of [Cd(Se₄)₂]^2? ions. The cadmium atoms are coordinated by two tetraselenide ions in a chelating fashion.     

正交回归多元标准加入法同时测定干扰组分

提供了同时测定混合物中彼此严重干扰的多种组分的新方法。该方法采用多元标准加入法的正交回归设计,因此,由微机上的正交回归分析,得到一组准确的回归方程,该方法用于光度法中,同时测定了工业污水中的铜,镍,镉,锌,并用于差分脉冲极谱法中,同时测定了河水中的铅,铊,镉,测定结果的误差均不大于4％,这个结果说明该方法具有良好的准确性和可靠性。     

[Sb(12-Krone-4)2(CH3CN)][SbCl6]3 und [Bi(12-Krone-4)2(CH3CN)][SbCl6]3, die ersten Trikationen von Antimon(III) und Bismut(III)

[Sb(12-Crown-4)₂(CH₃CN)][SbCl₆]₃ and [Bi(12-Crown-4)₂(CH₃CN)][SbCl₆]₃, first Trications of Antimony(III) and Bismuth(III) The crown ether complexes [M(12-crown-4)₂(CH₃CN)][SbCl₆]₃ with M = Sb and Bi are formed by the reaction of antimony trichloride and bismuth trichloride, respectively, with antimony pentachloride in acetonitrile solution in the presence of 12-crown-4. They form colourless, moisture sensitive crystals, which were characterized by X-ray structure determinations and by IR spectroscopy. The complex with M = Sb was also characterized by ¹²¹Sb Mössbauer spectroscopy. Both complexes crystallize isotypically in the orthorhombic space group Pbcn with four formula units per unit cell. M = Sb: 3 483 observed unique reflections, R = 0.038. M = Bi: 2 958 observed unique reflections, R = 0.036. The compounds consist of SbCl₆^? ions and trications [M(12-crown-4)₂(CH₃CN)]³⁺, in which the M³⁺ ions are ninefold coordinated by the eight oxygen atoms of the crown ether molecules and by the nitrogen atom of the acetonitrile molecule. The lone pair of the M³⁺ ions has no steric effect.     

Separation and determination of trace amounts of beryllium(II), aluminium(III) and chromium(III) with chromotrope 2C chelates by RP-HPLC

A reversed-phase high-performance liquid chromatographic separation and determination of beryllium(II), aluminium(III) and chromium(III) with chromotrope 2C chelates on a C18-bonded stationary phase is reported. Methanol-water (45:55 v/v) containing 6 x 10(-3)M tetra-n-butylammonium bromide (TBAB) and 2 x 10(-2)M acetate buffer solution (pH 6.0) as mobile phase and with spectrophotometric detection at 530 nm was applied. The method has high sensitivity, the detection limits being 0.2 ppb for beryllium(I), 1 ppb for aluminium(III) and 2 ppb for chromium(III). Under the optimum conditions, most other metal ions did not interfere, e.g. up to 2 mg of Hg(II), Sn(II, IV), Pb(II), Bi(III), Ag(I), Zn(II), Cd(II), Cu(II), 1.5 mg of Fe(II), Co(II), Ni(II), 1.2 mg of Ca(II), Mg(II), Sr(II), Ba(II), 1 mg of Ga(III), In(III), 0.5 mg of Fe(III), 1 mg of Ga(III), In(III), 0.5 mg of Fe(III), 0.4 mg of Th(IV), Zr(IV). The method can be applied to the simultaneous determination of trace amounts of beryllium(II), aluminium(III) and chromium(III), in water, rice, flour and human hair samples.     

Stripping polarography and the reduction of copper(II) in sea water at the hanging mercury drop electrode

An approximate but general theoretical treatment for reversible and irreversible stripping polarographic systems is presented. The treatment is based on the development of an average current (i), which at plating times exceeding 15 s. is analogous to the instantaneous current in d.c. polarography. Plots of i vs. (E – E°) are generated for reversible and irreversible waves and are discussed for the reduction of copper(II) in sea water as an example. From stripping polarography and anodic stripping voltammetry, this work indicates that the overall reduction of copper(II) at the natural pH is kinetically hindered and thus is “irreversible”. The reversibility and the determination of copper in sea water by a.s.v. can be improved by acidification and/or by the addition of ethylenediamine.     

Synthesis of chromogenic crown ethers and liquid-liquid extraction of alkali metal ions

New crown ethers carrying a pendent phenolic chromophore were synthesized. These crown ethers, on dissociation of the phenolic proton, provide lipophilic anions which can extract alkali metal cations into 1,2-dichloroethane by forming highly-colored uncharged metal complexes. Structural effects on the extraction were studied for possible use of these crown ethers as extraction—spectrophotometric reagents selective for alkali metals. The following factors are discussed in detail: (i) nature of the crown ether ring (ring size. aza-crown or standard crown ether), (ii) nature of the pendent phenolic group, and (iii) geometry between the crown ether center and pendent phenolic group. 15-Crown-5 or smaller ring-sized reagents favored the extraction of lithium ion when the basicity of the pendent phenolate was relatively high and a six-membered “chelate” ring was possible for the phenolate and the crown ether-bound metal. 15-Crown-5 type reagents were sodium-selective when an eight-membered “chelate” ring was possible between the phenolate and the crown ether-bound metal. 18-Crown-6 type reagents were generally potassium-selective. However, these selectivities were not absolute, and other structural parameters, steric and conformational, must be considered to explain in detail the selectivities of the individual reagents.