络合吸附伏安法同时测定多种重金属离子

在络合剂亚硝基苯胲 乙醇 乙酸铵体系中,Cr(Ⅵ)、Cd2 、Cu2 、Pb2 、Ni2 等离子都能在汞电极上产生灵敏的阴极络合吸附波,其二次导数伏安峰电流均与离子质量浓度有良好的线性关系,可用于这些离子的定量检测,测定线性范围为Cr(Ⅵ)0.0017～0.67μg mL、Cd2 0.0017～0.117μg mL、Cu2 0.0083～5 8μg mL、Pb2 0.083～1.25μg mL、Ni2 0.17～150μg mL,RSD分别为5.7%、1 3%、1.4%、2 5%和1.6%。方法为工业废水、地表水及生活用水等样品中重金属离子的同时测定提供了可靠、灵敏的检测方法。     

Determination of trace metal ions in common salt by stripping voltammetry

Sensitive voltammetric methods using cathodic and anodic differential pulse stripping techniques were applied for determination of trace ions cadmium(II), cobalt(II), copper(II), lead(II), manganese(II), nickel(II), and zinc(II), which are usually found in different grades of common salt as contaminants. The optimal conditions, i.e., deposition time, preconcentration potential, supporting electrolyte, and ionic strength, were investigated for each metal ion. Concentration of the metal ion was determined by the standard addition method. Metal content varied according to the quality of the table salt.     

Selective method for the determination of gold by anodic stripping voltammetry

A highly selective method for the deter- mination of gold by anodic stripping voltammetry is described. For preconcentration a glassy carbon electrode, activated by deposition of small amounts of gold before the measurement, is proposed. The Au³⁺ reduction process at such an electrode is effective starting with the potential +0.4 V vs. Ag/AgCl electrode. A linear dependence of the current of the gold stripping peak on the gold concentration was obtained in the range from 5×10⁻⁸ to 1×10⁻⁶ mol/l. The relative standard deviation for 2×10^-7 mol/l HAuCl₄ was 4.2% (n=5). The detection limit was 4×10^-9 mol/l. The accuracy of the method was verified by the determination of gold in reference materials.     

Selective method for the determination of gold by anodic stripping voltammetry

A highly selective method for the deter- mination of gold by anodic stripping voltammetry is described. For preconcentration a glassy carbon electrode, activated by deposition of small amounts of gold before the measurement, is proposed. The Au³⁺ reduction process at such an electrode is effective starting with the potential +0.4 V vs. Ag/AgCl electrode. A linear dependence of the current of the gold stripping peak on the gold concentration was obtained in the range from 5×10^–8 to 1×10^–6 mol/l. The relative standard deviation for 2×10^-7 mol/l HAuCl₄ was 4.2% (n=5). The detection limit was 4×10^-9 mol/l. The accuracy of the method was verified by the determination of gold in reference materials.     

Trace determination of yttrium and some heavy rare-earths by adsorptive stripping voltammetry

The interfacial and redox behaviour of rare-earth chelates with Solochrome Violet RS are exploited for developing a sensitive adsorptive stripping procedure. Yttrium and heavy rare earths such as dysprosium, holmium and ytterbrium can thus be measured at ng ml levels and below, by controlled adsorptive accumulation of the metal chelate at the hanging mercury drop electrode, followed by voltammetric measurement of the surface species. With a 3-min preconcentration time, the detection limit ranges from 5 x 10(-10) to 1.4 x 10(-9)M. The relative standard deviation at the 7 ng ml level ranges from 4 to 7%. A separation method is required to differentiate between the individual rare-earth metals.     

Regularities in concentrating during anodic stripping voltammetry of metal complex solutions

Summary Analysis of equation of convective non-stationary diffusion for mean metal concentration in amalgams and limits of their applicability for cases of reversible electrode processes adjusted by homogeneous preceding chemical reactions with participation of metal complexes in anodic stripping voltammetry using stationary mercury electrodes of limited bulk is presented. Quantitative evaluation of the influence of chemical reaction parameters, the rate of mixing of the solution, characteristic electrode dimensions and other factors on the rate of electrochemical concentration is shown.

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Gesetzmäßigkeiten bei der Konzentrierung in der Anodic-Stripping-Voltammetrie von Metallkomplexlösungen

     

Sensitive and fast determination of papaverine by adsorptive stripping voltammetry on renewable mercury film electrode

The renewable mercury film electrode, applied for the determination of papaverine traces using differential pulse adsorptive stripping voltammetry (DP AdSV) is presented. The calibration graph obtained for papaverine is linear from 1.25 nM (0.42 µg L^?1) to 95 nM (32.2 µg L^?1) for a preconcentration time of 60 s, with correlation coefficient of 0.998. For the renewable mercury electrode (Hg(Ag)FE) with a surface area of 9.1 mm² the detection limit for a preconcentration time of 60 s is 0.7 nM (0.24 µg L^?1). The repeatability of the method at a concentration level of the analyte as low as 17 µg L^?1, expressed as RSD is 3.3% (n=5). The proposed method was successfully applied and validated by studying the recovery of papaverine from drugs, urine and synthetic solution.      

A novel method for fast determination of vitamin B6 by fast continuous cyclic voltammetry

In this work a novel method for the determination of Vitamin B6 in flow-injection systems has been developed. The fast Fourier transform continuous cyclic voltammetry (FFTCV) at gold microelectrode in flowing solution system was used for determination of Vitamin B6. This method is rapid, simple and highly sensitive procedures allowing the determination of Vitamin B6 in pharmaceutical analysis. The effects of various parameters on the sensitivity of the method were investigated. The best performance was obtained with the pH value of 2, scan rate value of 30 V/s, accumulation potential of 200 mV and accumulation time of 0.3 s. The proposed method has some advantages over other reported methods such as, no need for the removal of oxygen from the test solution, a sub-nanomolar detection limit, and finally the method is fast enough for the determination of any such compound, in a wide variety of chromatographic methods. To obtain a sensitive determination, the integration range of currents was set for all the potential scan ranges, including oxidation and reduction of the Au surface electrode, while performing the measurements. The potential waveform, consisting of the potential steps for cleaning, accumulation and potential ramp of analyte, was applied on an Au disk microelectrode (12.5 μm in radius) in a continuous way. The detection limit of the method for Vitamin B6 was 2.8 pg/ml. The relative standard deviation of the method at 2.1% was 8 runs. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 2, pp. 173–181. The text was submitted by the authors in English.     

Indirect determination of surfactants by adsorptive stripping voltammetry

The effect of some anionic, cationic and nonionic surface-active substances on the suppression of adsorptive accumulation of the bis(dimethylglyoximato)nickel(II) complex, Ni(DMG)₂, is described. Competitive adsorption of surfactants can be used to determine surfactants commonly used in commercial detergents. Triton X-100 shows the most pronounced effect on the peak height. The shape of the calibration curve depends on the concentration and on the adsorption potential. Highest sensitivity is obtained when equilibrium between Ni(DMG)² in solution and on the electrode surface is attained rapidly. Under these conditins, the detection limit is 1 μ 1^?1 Triton X-100. Calibrations are linear over 1–2 orders of magnitude.     

The determination of gold by anodic stripping voltammetry

A method is described for the routine determination of gold as its chloride or cyanide complex by anodic stripping voltammetry at a glassy carbon electrode coupled to a microprocessor-controlled voltammeter. The preferred supporting electrolyte is 0.1 M HCl/0.32 M HNO₃, with plating at ?200 mV or ?1200 mV (vs. Ag/AgCl). The stripping peak potentials range from 830 to 1150 mV (vs. Ag/AgCl) depending on concentration and plating time. Precision (percent relative standard deviation) is better than 5 % for a range of concentrations between 5 μg l^?1 and 1000 μg l^?1. The detection limit is about 5 μg l^?1 for a 5-min plating period. Interferences from Cu, Hg, Ag and other electroactive species are overcome by preliminary extraction with diethyl ether.     

Removal of heavy metal ions from aqueous solutions by alkaline-earth metal phosphates

The possibility of utilization of calcium or magnesium phosphates of various composition for heavy and non-ferrous metal extraction from aqueous solutions has been studied. The efficiency of the phosphates in removal of Pb(II), Cr(III) and Fe(III) ions has been shown to decrease in the following sequence: Mg₃(PO₄)₂>MgNH₄PO₄>Ca₃(PO₄)₂>CaHPO₄>Ca₁₀(PO₄)₆(OH)₂ which is inverse to their hydrolytic stability series. It has been established that phosphates of non-apatite structure are capable of binding up to 12 mmol g⁻¹ of the named heavy metals by a chemical interaction. Hydroxyapatite interacts with the polyvalent metal ions via either the above mentioned or ion-exchange mechanism, depending on preparation method used for the apatite and the nature of metal.     

The determination of traces of thiocyanate and copper(II) ions by cathodic stripping voltammetry

Cathodic stripping methods are described for the determination of traces of thiocyanate ions down to 2 × 10^-8 mol l^-1 and Cu(II) ions down to 1 × 10^-8 mol l^-1. The method involves electrolytic accumulation of copper(I) thiocyanate on the surface of a hanging mercury drop electrode followed by stripping of the deposit during the cathodic scan. For the determination of thiocyanate, a copper amalgam electrode can be used. Examples of application of the method for the determination of traces of thiocyanate in common salts, in saliva and urine as well as for the determination of copper(II) ions in tap water are described.     

Effects of surface-active substances in square-wave voltammetry and potentiometric stripping analysis of amalgam-forming metal ions

The influence of surface active substances (SAS) (Triton X-100, sodium dodecyl sulfate and dodecyl pyridinium chloride (DPC)) on the potentiometric stripping analysis (PSA), square-wave voltammetry (SWV) and anodic stripping square-wave voltammetry (ASSWV) of Cd²⁺, Cu²⁺, Zn²⁺ and Bi(III) are measured for various contact times and detergent concentrations. Diagnostic criteria for the presence of SAS in electrolytes are reported. Zinc ions accumulate in the adsorbed layer of DPC, probably as a ZnCl⁺ complex. An anomalous dependence of zinc SWV peak currents on the delay time is observed.     

Cathodic adsorptive stripping voltammetry of 6-thiopurine in absence and presence of some metal ions

Summary Cathodic stripping voltammetry of an adsorbed 6-thiopurine at HMDE was investigated in solutions of varying pH. A rapid and sensitive differential pulse voltammetric method was selected for its trace determination. A method has also been developed for the determination of 6-thiopurine in presence of Cu(II), due to the strong adsorption of the Cu-6-thiopurine complex at the surface of the HMDE and subsequent reduction of the surface-bound complex. A detection limit of 9.9×10^–9 mol/l was achieved in presence of Cu(II) and the slope of the straight line was seven times the slope in absence of Cu(II). Cathodic adsorptive stripping (CAS) voltammetry of 6-thiopurine in presence of Ni(II), Pb(II), Cd(II), and Fe(III) was also investigated. The influence of several operational parameters has been considered. Statistical analysis of the calibration curve data is included.     

Flow-through coulometric stripping analysis and the determination of manganese by cathodic stripping voltammetry

A simple flow-through system is described for collection of liquid samples into a closed loop. This arrangement can be used for coulometric determinations by the stripping method without previous calibration. The usefulness of the system is demonstrated on the determination of manganese (ca. 10^-6 M) in acetate buffer by cathodic stripping voltammetry.     

The determination of molybdenum in selected mushrooms by stripping voltammetry

The highly sensitive method of adsorptive stripping voltammetry (AdSV), with differential pulse steps, was performed at a mercury film electrode and has been applied here for the determination of trace molybdenum content in selected wild mushrooms. Fruiting body caps of 12 selected macrofungi species from Basidiomycetes have been investigated. Molybdenum content of investigated samples was determined in the range of 0.006 to 0.38 mg kg⁻¹ of dry matter. The highest value of molybdenum content was found in Leccinum rufum and the lowest in Lactarius deliciosus.     

The determination of silver in ores by anodic stripping voltammetry

Stripping voltammetry at a rotating glassy carbon electrode is proposed for the determination of silver in ores. The ores or concentrates are dissolved in suitable acid mixtures, and silver is separated either by extraction with dithizone in carbon tetrachloride, or by adsorption on silica from ammoniacal buffered solution and subsequent elution with 0.1 M nitric acid. The results obtained with stationary and rotating glassy carbon electrodes are discussed. Stripping voltammetry and fire assay give results in reasonably good agreement.     

Simultaneous determination of mercury and arsenic by anodic stripping voltammetry

An electrochemical method for the simultaneous determinations of Hg^II concentration and total As^III and As^V concentration has been developed. The method does not require the additional preliminary step of the chemical reduction of As^V to As^III, or oxidation of As^III to As^V before stripping analysis takes place. Also, the method for the simultaneous determination of Hg^II concentration and As^III concentration is described. Measurements were performed in 0.1 M HCl using a gold-plated graphite electrode as sensor. Detection limits for both methods are below 0.4 ppb. Relative standard deviation did not exceed 15%. The possible interference by other trace metals was investigated. Analyses of natural water and industrial solutions were made using proposed methods and AAS. The t-test demonstrates that there was no significant difference between the results obtained with these methods. Proposed methods decrease the time of analysis because concentrations of the Hg^II and arsenic ions were measured simultaneously. Also, the removal of the additional step of chemical reduction of As^V to As^III or oxidation of As^III to As^V decreases analysis time, and also reduces the chance of contamination due to the use of additional reagents.     

Trace determination of molybdenum by adsorptive cathodic stripping voltammetry

Molybdenum is determined by adsorptive cathodic stripping voltammetry in 0.15 M nitric acid solution containing 15 μM 2′,3,4′,5,7-pentahydroxyflavone (morin) as a ligand. In this medium, molybdenum is preconcentrated on a hanging mercury drop electrode and stripped cathodically in square-wave voltammetry mode, with a peak potential of -350 mV vs. Ag/AgCl (saturated KCl). The effect of various parameters (ligand concentration, supporting electrolyte composition, accumulation potential and collection time) on the sensitivity and linear range of the calibration curve are discussed. With controlled accumulation for 1 min, the detection limit (3σ) was 0.45 ng ml^?1 molybdenum and the calibration curve is linear up to 70 ng ml^?1. The procedure is applied to the determination of molybdenum in real samples with satisfactory results.