Determination of nanomolar concentrations of lead and cadmium by anodic-stripping voltammetry at the silver electrode

Lead and cadmium have been determined by subtractive anodic-stripping voltammetry (SASV) in the square-wave mode at a silver electrode without removal of oxygen. The sensitivities and detection limits for the two metals differ considerably. Detection limits of 0.05 nM for lead and 1 nM for cadmium have been achieved following 90 s electrodeposition. The repeatability of consecutive SASV runs is good (for lead 0.5% at 20 nM for 30 s electrolysis, 5% at 0.3 nM for 60 s electrolysis; for cadmium 2.5% at 20 nM for 30 s electrolysis, 5% at 5 nM for 60 s). Hundreds of runs can be carried out without any pretreatment of the electrode. The high stability is attributed to renewal of the electrode surface that takes place during the electrodeposition step in a two-electrode cell: the silver counter/quasi-reference electrode generates silver ions that codeposit with lead and cadmium at the Ag-RDE, thus ensuring a continuity of the latter. Underpotential deposition (UPD) plays a central role in anodic-stripping voltammetry (ASV). During the deposition step, the adatom coverage of trace elements is in the range of 0.01-1% and no bulk deposition is invoked for metals that exhibit UPD. The UPD properties and, as a result, the ASV signals are strongly affected by the type and concentration of the supporting electrolyte. The effects of Cl⁻, Br⁻, SO₄²⁻ and NO₃⁻ are shown. The analysis of lead and cadmium in natural waters has been performed. Surfactants distort the SASV signal. In order to ensure surfactant-free solutions, the samples were pretreated by wet ashing.     

Silver Electrodeposition from Cyanide Solutions: Effect of Lead Ions

Effect of lead hydroxy compounds on the process of electrodeposition of silver from cyanide electrolytes is studied on an electrode whose surface is renewed in solution by cutting off a thin layer of metal. This permitted to perform the study on both the freshly renewed electrode and at controlled values of the time of the electrode contact with solution t. Shown is that on the freshly renewed electrode (t<1 s) the presence in the solution of lead ions in concentrations c ₁ on the order of 10^–5 M leads to the process depolarization only in the initial portion of a polarization curve. With c ₁ increased to 10^–4 M the effect of depolarization extends on the entire polarization curve. Keeping the electrode in solution after the renewal of the metal surface magnifies depolarization, and the greater the concentration c ₁, the shorter the time period t required to achieve the same effect. These regularities are attributed to catalytic influence of lead adatoms, whose surface concentration depends on c ₁ and t, as well as on the intensity of their incorporation in the silver deposit.     

Coulometric Determination of Trace Silver in Surfactant-Containing Solutions

The voltammetric behavior of silver in redox reactions [Ag(I) Ag(0)] on a platinum-gauze electrode was studied to select the optimum conditions for the potentiostatic coulometric determination of silver in 10^–6–10^–5 M solutions in the presence of surfactants using the oxidation of silver electrochemically predeposited on the electrode. The determination error and the relative standard deviation varied from 0.5 to 6%, depending on the concentration of silver. The inhibiting effect of surfactants on the rates of silver deposition and dissolution decreased as their concentration was decreased by the repeated dilution of the initial solution and by their removal at the sample preparation stage and as the potentials and times of silver electrodeposition and electrodissolution were changed. The mode of alternating cathodic and anodic polarization of the electrode provided the complete deposition and dissolution of silver; in this mode, silver(I) could be determined from a single portion of the solution many times. The procedure was applied to the determination of silver in drugs and cosmetic and photographic materials.     

Determination of traces of heavy metals in positively charged inorganic colloids in fresh waters

Summary Determination of Traces of Heavy Metals in Positively Charged Inorganic Colloids in Fresh Waters After removal of suspended particulate matter by centrifugation followed by filtration through 0.4-m membrane filters, humic substances and other negatively charged species are sorbed on a small column of macroreticular weak-base anion exchanger DEAE-Sephadex A-25 at fast flow rates. Positively charged inorganic colloids pass through the column and are collected on a 0.015-m membrane filter, which is then ultrasonically treated with 1M nitric acid for the determination of copper, lead and cadmium by differential pulse anodic stripping voltammetry with a static mercury drop electrode. Up to O.2g 1^–1 of the heavy metals are found in positively charged inorganic colloids in river, pond and tap waters.     

Electroreduction of Anions and Silver Kryptate on a Mercury Electrode in Conditions of Adsorption of Kryptate Complexes

Electroreduction of persulfate, hexacyanoferrate, and perbromate anions on a mercury electrode is studied in conditions of individual adsorption of kryptate complexes of cations and in the case of their co-adsorption with surface-active substances that form two-dimensional condensed layers on the electrode/solution interface. The electroreduction dramatically accelerates during both individual adsorption of kryptate complexes and their co-adsorption with 1-adamantanol, due to an electrostatic effect. The behavior of electrochemically active kryptate complexes is investigated by studying the Ag⁺ kryptate. In the system studied the [Ag⁺ 222] complex undergoes diffusion-controlled reduction.     

Application of a bismuth film electrode to the voltammetric determination of trace iron using a Fe(III)–TEA–BrO<Stack><Subscript>3</Subscript><Superscript>−</Superscript></Stack> catalytic system

A sensitive catalytic voltammetric method for determining trace iron at a bismuth film electrode (BiFE) is described. The method is based on the cathodic reduction of the Fe(III)–triethanolamine (TEA) complex to Fe(II). It has been proved that the addition of KBrO₃ causes rapid oxidation of Fe(II) and TEA, and therefore results in a large increase in the analytical signal from Fe(III) when TEA is placed in alkaline solution. When TEA was present in the solution, operating the BiFE under optimized conditions yielded a stable catalytic voltammetric response for iron, with high sensitivity (0.88 A M^–1), good precision (RSD=3.9%) and a low detection limit (7.7×10^–9 M), obtained without any preconcentration procedure. Possible interferences from the coexisting ions and surface-active substances were investigated. Finally, the method was applied with satisfactory results to the determination of iron in certified reference river water samples.     

Empfindliche Silberbestimmung in Blei

Zusammenfassung Eine empfindliche spektrophotometrische Methode zur Bestimmung von Silber wurde beschrieben (Molarextinktion =1,8×10⁶). Das Lambert-Beersche Gesetz wird zwischen 43×10^–4 und 38,8×10^–3 g/ml gut befolgt. Salicylsäure wird in Gegenwart von Ammoniumpersulfat, 2,2'-Dipyridyl und Silber als Katalysator oxydiert, wobei sich ein gelbbrauner Farbstoff bildet, der bei 410 nm ein Maximum der Absorption zeigt.Die Methode eignet sich zur Bestimmung von Silberspuren in Blei, da sich dieses in großen Mengen mit ÄDTA maskieren läßt.

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A sensitive determination of silver in lead

Summary A sensitive method of spectrophotometric determination of silver is described (molar extinction =1.8×10⁶). Lambert-Beer's Law is valid between 43×10^–4 g/ml and 38.8×10^–3 g/ml. Silver as catalyst oxidizes salicylic acid in the presence of ammonium persulfate and 2,2'-dipyridyl as activator producing a yellow-brown color that shows a maximum of absorption at 410 nm.This method seems to be adequate for the determination of traces of silver in lead because lead can be masked in great quantities with EDTA.

     

A New Neutral Carrier for Silver Ions Based on a Bis(Thiothiazole) Derivative and its Evaluation in Membrane Electrodes

Membrane electrodes based on 2,2-dithiobis(benzothiazole), DTBBT, as a neutral carrier for silver ions are described. Silver-selective membrane electrodes formulated with 2wt% DTBBT ionophore and 50mol% TFPB in an FPNPE plasticized poly (vinyl chloride) exhibited near-Nernstian responses towards silver ions (60.3±0.5mVdecade^–1) over a wide silver ion activity range of 0.83µM to 94mM. Increasing the amount of anionic sites, TFPB, to 100 or 150mol% (relative to the DTBBT weight) resulted in super-Nernstian responses toward silver ions. Membrane electrodes prepared using a low dielectric constant plasticizer, however, exhibited sub-Nernstian responses. Polymer membrane electrodes with optimal composition (i.e., 2wt% DTBBT, 50mol% TFPB in FPNPE plasticized poly(vinyl chloride)) exhibited high potentiometric selectivity towards silver ions over alkali, alkaline earth, transition metal ions, as well as heavy metal ions such as Hg²⁺ and Pb²⁺. A good correlation was found between the potentiometric selectivity coefficients and the change in the UV-visible spectra of the ionophore upon exposure to different metal ions. The overall performance of the silver-selective membrane electrodes based on DTBBT ionophore, which is available at low cost, was found to be comparable to the performance of silver electrodes prepared with Fluka silver ionophore-IV. A DTBBT-based silver electrode was used as an indicator electrode for titrations of silver ions using standard sodium chloride solutions. Sharp inflections occur at the end point, and the data obtained showed 99.4% recovery with a standard deviation of 0.7% (n=3). In addition, the applicability of the DTBBT-based silver-selective electrode is illustrated by measuring the silver concentrations in natural water spiked with silver nitrate and by analyzing the silver in electroplating wastewater samples. The results obtained utilizing a DTBBT-based silver electrode showed very good agreement with the standard methods of analysis.     

Evaluations of solid electrodes for use in voltammetric monitoring of heavy metals in samples from metallurgical nickel industry

Evaluation of different solid electrode systems for detection of zinc, lead, cobalt, and nickel in process water from metallurgical nickel industry with use of differential pulse stripping voltammetry has been performed. Zinc was detected by differential pulse anodic stripping voltammetry (DPASV) on a dental amalgam electrode as intermetallic Ni–Zn compound after dilution in ammonium buffer solution. The intermetallic compound was observed at –375 mV, and a linear response was found in the range 0.2–1.2 mg L^–1 (r²=0.98) for 60 s deposition time. Simultaneous detection of nickel and cobalt in the low g L^–1 range was successfully performed by use of adsorptive cathodic stripping voltammetry (AdCSV) of dimethylglyoxime complexes on a silver–bismuth alloy electrode, and a good correlation was found with corresponding AAS results (r²=0.999 for nickel and 0.965 for cobalt). Analyses of lead in the g L^–1 range in nickel-plating solution were performed with good sensitivity and stability by DPASV, using a working electrode of silver together with a glassy carbon counter electrode in samples diluted 1:3 with distilled water and acidified with H₂SO₄ to pH 2. A new commercial automatic at-line system was tested, and the results were found to be in agreement with an older mercury drop system. The stability of the solid electrode systems was found to be from one to several days without any maintenance needed.     

Overlapping voltammetric peaks—an analytical procedure for simultaneous determination of trace metals. Application to food and environmental matrices

Voltammetric methods are very suitable, versatile and rapid techniques for simultaneous determination of metals in complex matrices. The present work, determination of Cu(II), Sn(II), Sb(III), Tl(I), and Pb(II) by square-wave anodic-stripping voltammetry and Cr(VI) by square-wave adsorptive-stripping voltammetry, is an interesting example of the possibility of simultaneous determination of each single element in food and environmental samples, even in the presence of reciprocal interference. Dibasic ammonium citrate, pH 6.3 or 8.2, was employed as supporting electrolyte. The voltammetric measurements were carried out using a stationary hanging mercury drop electrode as working electrode and a platinum electrode and an Ag|AgCl|KCl_sat electrode as auxiliary and reference electrodes, respectively. The analytical procedure was verified by analysis of standard reference materials—wholemeal BCR-CRM 189, wheat flour NIST-SRM 1567a, rice flour NIST-SRM 1568a, estuarine sediment BCR-CRM 277, river sediment BCR-CRM 320, and Montana soil with moderately elevated traces NIST-SRM 2711. Precision and accuracy, expressed as relative standard deviation and relative error, respectively, were generally below 6% whereas limits of detection for each element were below 0.069 g g^–1. In the presence of reciprocal interference the standard addition method considerably improved the resolution of the voltammetric technique, even for very high element concentration ratios. After being set up on the standard reference materials the analytical procedure was transferred and applied to commercial samples of meal and soil samples taken from sites devoted to agricultural practice. A critical comparison with graphite furnace atomic-absorption spectroscopy is also discussed. Work partially presented at Euroanalysis XIII, Salamanca, Spain, 5–10 September 2004     

Surface modification of amine-functionalised graphite for preparation of cobalt hexacyanoferrate (CoHCF)-modified electrode: an amperometric sensor for determination of butylated hydroxyanisole (BHA)

A cobalt hexacyanoferrate (CoHCF)-modified graphite paraffin wax composite electrode was prepared by a new approach. An amine-functionalised graphite powder was used for the fabrication of the electrode. A functionalised graphite paraffin wax composite electrode was prepared and the surface of the electrode was modified with a thin film of CoHCF. Various parameters that influence the electrochemical behaviour of the modified electrode were studied by varying the background electrolytes, scan rates and pH. The modified electrode showed good electrocatalytic activity towards the oxidation of butylated hydroxyanisole (BHA) under optimal conditions and showed a linear response over the range from 7.9 × 10⁻⁷ to 1.9 × 10⁻⁴ M of BHA with a correlation coefficient of 0.9988. The limit of detection was 1.9 × 10⁻⁷ M. Electrocatalytic oxidation of BHA was effective at the modified electrode at a significantly reduced potential and at a broader pH range. The utility of the modified electrode as an amperometric sensor for the determination of BHA in flow systems was evaluated by carrying out hydrodynamic and chronoamperometric experiments. The modified electrode showed very good stability and a longer shelf life. The modified electrode was applied for the determination of BHA in spiked samples of chewing gum and edible sunflower oil. The advantage of this method is the ease of electrode fabrication, good stability, longer shelf life, low cost and its diverse application for BHA determination. Figure Cyclic Voltammogram of () CoHCF modified electrode, () in presence of 1.9 x 10⁻⁵ M of BHA and () bare electrode, () in the presence of 1.9 x 10⁻⁵ M of BHA in 1.0 M NaCl, pH 7.0     

Preconcentration and voltammetric behaviour of Ag+ at carbon paste electrodes modified by N-benzoyl-N′,N′-di-i-butyl-thiourea

The preconcentration of silver at carbon paste electrodes (CPE) modified with N-benzoyl-N,N-di-i-butyl-thiourea and its subsequent voltammetric determination is studied with test solutions. The preconcentration of silver at the surface of the modified CPE succeeds as well with open circuits as with applied potentials. The amount preconcentrated depends on the electrode potential with a maximum at +0.1 V vs. Ag/AgCl, thus enabling the preconcentration of silver without cathodic treatment. The detection limit is in the order of 10^–4 mmol/l Ag⁺. The surface reactions during the preconcentration are discussed. It is assumed that silver complexes of the modifier are formed in a fast reaction followed by a slow reaction with participation of silver and of carbon surface groups.     

Structure of indolylphenylmethyl cations

The charge distribution in 1-methyl-2-carboxy-3-indolylphenylmethyl cation (II), which is formed by dissociation of the C-X bond in 1-methyl-2-carboxy-3-(-X-benzyl)indoles (I) in H₂SO₄ solution, was studied by PMR and¹³C NMR spectroscopy. Cation II may have a structure with a positive charge on the benzyl carbon atom (IIa), the nitrogen atom (IIc), or on the-carbon atom of the indole ring (IIc). Structures IIc and IIa make the major contributions to the II structure; this is confirmed by calculations by the Pariser-Parr-Pople (PPP) method within the- approximation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 60–62, January, 1978.     

Potentiometric determination of tetraphenylborate ions with silver nitrate. Determination of silver, potassium and thallium(I)

Summary The potentiometric determination of tetraphenylborate with silver nitrate solution was investigated a) at i=0 in the presence of calomel reference electrode and silver resp. silicone rubber based halide-selective indicator electrodes and b) at i0 in the presence of silver (cathode)-calomel, silver-silver, silver-platinum, platinum-silver and graphite-silver electrode couples. An indirect method is described for the determination of potassium ions with potentiometric end-point indication. Experiments were also carried out in order to develop methods for the titration of silver, potassium and thallium(I) ions with sodium tetraphenylborate solution in the presence of anodic polarized graphite and calomel reference electrodes. The relative standard deviations were 0.38–0.49% for tetraphenylborate, 1.96% for potassium and 1.07% for thallium(I).

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Potentiometrische Bestimmung von Tetraphenylborationen mit Silbernitrat. Bestimmung von Silber, Kalium und Thallium(I)

Zusammenfassung Die Möglichkeit der potentiometrischen Bestimmung von Tetraphenylborat mit Silbernitrat wurde untersucht a) in Anwesenheit von Kalomel-Bezugselektrode und Silber- bzw. haloidselektiven Silicongummi-Indicatorelektroden bei i=0 und b) in Anwesenheit von Silber (Kathode)-Kalomel-, Silber-Silber, Silber-Platin-, Platin-Silber- und Graphit-Silber-Elektrodenpaaren bei i0. Eine Methode zur indirekten potentiometrischen Bestimmung von Kalium sowie Verfahren zur Bestimmung von Silber-, Kalium- und Thallium(I)-ionen mit Natriumtetraphenylboratlösung in Anwesenheit einer anodisch polarisierten Graphitelektrode und einer Kalomel-Referenzelektrode wurden ausgearbeitet. Die relativen Standardabweichungen betragen für Tetraphenylborat 0,38–0,49%, für Kalium und Thallium 1,96 bzw. 1,07%.

     

Studies on the voltammetric behaviour of a 2-mercaptoimidazole containing carbon paste electrode: determination of traces of silver

The voltammetric behaviour of a 2-mercaptoimidazole (2-MI) containing carbon paste electrode was studied. When mixed to carbon paste as an electrode modifier, 2-MI can be reduced at negative potentials (–1 V vs. SCE), but it does not give a response in the potential range where Ag(0) is oxidized to Ag(I). Silver could be accumulated from 0.1 mol l^–1 acetate buffer onto a 2-MI modified carbon paste electrode without a potential applied; after medium exchange, it was reduced at –1 V vs. SCE in 0.1 mol l^–1 acetate buffer solution and determined by differential pulse anodic stripping voltammetry. With suitable preconcentration times, the detection limit was 0.1 g l^–1; a linear relation between current and concentration was found to exist within a range of 0.5 to 1000 g l^–1. In the presence of EDTA, common metal ions have no or only little effect on the voltammetric determination of silver.     

Determination of dopamine in synthetic cerebrospinal fluid by SWV with a graphite–polyurethane composite electrode

This work describes an electroanalytical investigation of dopamine using cyclic voltammetry (CV) and the graphite–polyurethane composite electrode (GPU). In CV studies, well-defined redox peaks characterize the oxidation process at the GPU electrode, which is indicative of electrocatalytic effects associated with active sites on the GPU electrode surface. A new analytical methodology was developed using the GPU electrode and square wave voltammetry (SWV) in BR buffer solution (0.1 mol L^–1; pH 7.4). Analytical curves were constructed under optimized conditions (f=60s^–1, E_a=50 mV, E_I=2 mV) and detection and quantification limits of 6.4×10^–8 mol L^–1 (12.1 g L^–1) and 5.2×10^–6 mol L^–1 (0.9 mg L^–1), respectively, were achieved. The precision of the method was checked by performing ten successive measurements for a 9.9×10^–6 mol L^–1 dopamine solution. For intra-assay and inter-assay precisions, the relative standard deviations were 1.9 and 2.3%, respectively. In order to evaluate the developed methodology, the determination of dopamine was performed with good sensitivity and selectivity, without the interference of ascorbic acid in synthetic cerebrospinal fluid, which indicates that the new methodology enables reliable analysis of dopamine.     

The renovated silver ring electrode in determination of lead traces by differential pulse anodic stripping voltammetry

The study of a new type of working electrode - the renovated silver ring electrode (RSRE) - for lead ions detection via differential pulse anodic stripping voltammetry (DP ASV) without removal of oxygen is reported. The only four constituents of the RSRE: a specially constructed silver ring electrode, a silver sheet used as silver counter/quasi-reference electrode and a silicon O-ring, are fastened together in a polypropylene body. The renovation of this electrode is carried out through mechanical removal of solid contaminants and electrochemical activation in the electrolyte which fills the RSRE body. Excellent repeatability and reproducibility - also in organic samples solutions - were reached in a period of a few weeks through the renovation of the electrode surface before each measurement. The reduction and stripping of lead on silver electrode under the DP ASV conditions are underpotential deposition/dissolution phenomena. The RSRE is used for the determination of Pb ions in concentrations ranging from 1 × 10⁻⁹ to 1 × 10⁻⁷ M. The repeatability of DP ASV runs in synthetic solutions covering the entire concentration range is better than 2%. Obtained calibration curves are represented by a correlation coefficient of at least 0.999. The detection limit (LOD) for the time of electrodeposition equal to 60 s is 0.2 × 10⁻⁹ M. LOD for Pb²⁺ detection at the RSRE is similar to this reported for a rotating silver electrode in subtractive anodic stripping voltammetry (E. Kirowa-Eisner, et al., Anal. Chim. Acta, 385 (1999) 325). The analysis of Pb²⁺ in synthetic solutions with and without surfactants, certified reference materials and natural water samples have been performed.     

Electrical Double Layer on Liquid Bi–Ga Alloys in Aqueous Solutions

Double-layer characteristics of a liquid bismuth–gallium electrode are studied in aqueous electrolyte solutions. Based on the results obtained it is shown that Bi in an alloy with Ga is a surface-active component and forced out to the electrode surface layer. For electrode charges q –5 C/cm², the double layer characteristics of Bi–Ga electrodes approach those of a bismuth electrode. Thus, with respect to its electrochemical properties, a Bi–Ga electrode containing 0.25 at. % Bi simulates a liquid bismuth electrode. The corrected electrochemical work function is determined for bismuth. The close values of the difference of zero-charge potentials on mercury and bismuth in water and the difference of corrected electrochemical work functions for these metals points to the very low hydrophilicity of the Bi–Ga electrode, which approaches the value for mercury at negative electrode potentials. Taking into account that the Bi–Ga electrode displays no semimetallic properties, the similarity of the electric double layer (EDL) parameters for the Bi–Ga alloy and solid pure Bi indicates that the semimetallic properties of bismuth make no contribution to the EDL characteristics of the alloy in the studied range of negative charges q –5 C/cm².     

Determination of silver in photographic material by flow-injection analysis with a coated tubular solid-state silver sulphide ion-selective electrode as detector

Summary The incorporation, behaviour and suitability of a simple and cheap home-made coated tubular solid-state silver(I)-selective electrode into the conduits of a flow-injection system is described. With 30 l samples the flow-injection flow-through electrode system covers a working range up to 5000 mg/l. The system is suitable for the determination of silver(I) in diluted plant solutions from photographic material at a sample frequency of about 80 h^–1. This procedure is also characterized by excellent reproducibility (<0.24% for 0.06–76 g/l silver in the original plant solution). The results obtained agree well with results by a standard atomic absorption spectrometric method.

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Bestimmung von Silber in photographischem Material mit Hilfe der Fließinjektionsanalyse mit einer überzogenen Feststoff-Silbersulfid-ionensensitiven Röhren-Elektrode als Detektor

     

Use of a graphite–polyurethane composite electrode for electroanalytical determination of indole-3-acetic acid in soil samples

A new electroanalytical methodology was developed for the quantification of the phytohormone indole-3-acetic acid (IAA), using a graphite–polyurethane composite electrode (GPU) and the square wave voltammetry (SWV), in 0.1 mol L^− 1 phosphoric acid solution (pH 1.6). Analytical curves were constructed under optimized conditions (f = 100 s^− 1, a = 50 mV, E_i = 5 mV) and the reached detection and quantification limits were 26 μg L^− 1 and 0.2 mg L^− 1, respectively. The developed methodology is simple and accurate for the routine determination of IAA. In order to verify the application of the electroanalytical methodology in fortified soil samples without previous treatment, an IAA assay was performed without serious interferences of the soil constituents.