Kinetic-potentiometric determination of copper in real samples with a new antimony(V) ion-selective electrode

Summary A sensitive and selective kinetic method for the determination of copper is proposed. It is based on the catalytic effect of copper on the reaction between hexachloroantimonate(V) and hydroxylamine at pH 4.4 (acetic-acetate buffer). The rate of the reaction is potentiometrically monitored with a new antimony(V) ion-selective electrode using 1,2,4,6-tetraphenyl-pyridinium hexachloroantimonate(V) as electroactive material in a poly-(vinyl chloride) membrane. The proposed method allows the determination of copper(II) concentrations in the 5–510 ng ml^–1 range, with a variation coefficient of 3.5%. The method has satisfactorily been applied to a variety of real samples.     

Coated-wire silver ion-selective electrode based on silver complex of cyclam.

A coated-wire ion-selective electrode (ISE) based on cyclam (1,4,8,11-tetraazacyclotetradecane) as a neutral carrier in a polyvinyl chloride (PVC) matrix was fabricated for the determination of Ag(I) ions. The coated-wire ISE exhibited a linear Nernstian response over the range 1 x 10(-1) to 1 x 10(-7) M with a slope of 59 +/- 2 mV per decade change and a detection limit of 5 x 10(-8) M. The ISE shows a greater preference for Ag over other cations with good precision. The electrode was selective towards Ag(I) ions in the presence of 13 different metal ions tested. The selectivity coefficients (K(ij)) were determined for Na(I), K(I), Mg(II), Ca(II), Ba(II), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pb(II) and Hg(II). The selectivity coefficients of these cations are in the range of 10(-4) to 10(-2). This ISE was used for the determination of free silver and total silver in electroplating bath solutions, additives and brighteners.     

Potentiometric determination of silver(I) by selective membrane electrode based on derivative of porphyrin.

The performance of silver metal complexes with meso-tetraphenylporphyrin ([H2T(4-CH3)]PP) as ionophores for ion-selective electrodes was studied. The electrode exhibited linear response with Nernstian slope of 59.2 +/- 1.0 mV per decade within the concentration range of 1.0 x 10(-7)-1.0 x 10(-1) M silver ions. The limit of detection as determined from the intersection of the extrapolated linear segments of the calibration plot, was 1.0 x 10(-7) M. The response time of the electrode was < 10 s over the entire concentration range. The silver-selective electrode exhibited good selectivity for Ag(I) with respect to alkali, alkaline earth and heavy metal ions. The electrodes could be used at least three months without a considerable divergence in their potential. The electrodes are suitable for use in aqueous solutions in a wide pH range of 3.0-9.0. They were used as indicator electrodes in titration of Ag(I) with sodium iodide solution and were successfully applied to direct determination of silver in real samples.     

A hydrogen ion-selective poly(aniline) solid contact electrode based on dibenzylpyrenemethylamine ionophore for highly acidic solutions.

Hydrogen-ion selective solid contact electrodes based on tribenzylamine, dibenzylnaphthalenemethylamine, and dibenzylpyrenemethylamine ionophores were prepared. With these electrodes, we showed that the response ranges were influenced by the number of phenyl rings in the ionophores. The lower limits for a linear pH response in acidic solutions were pH 2.50, 0.65, and 0.50, respectively. As the number of phenyl rings in the ionophores increased, the slopes of the EMF responses of these electrodes did not change significantly, but their response extended toward an acidic range (shifted to pH 0.50). Thus, their dynamic response range became wider. A solid contact electrode with dibenzylpyrenemethylamine ionophore, in particular, showed the best selectivity, from the interference of cations and anions, and the best reproducibility of the EMF. This electrode was stored in Tris buffer solutions, artificial serum, and hydrofluoric acid solutions for one month without any loss of performance. Their response time was 8 s. Satisfactory results were obtained when it was tested directly with artificial serum (in pH range 6.0 - 8.5) and hydrofluoric acid.     

Application of a renewable silver based mercury film electrode to the determination of Cr(VI) in soil samples

The design and experimental results of the application of a renewable mercury film silver based electrode to the determination of Cr(VI) in soil samples are presented. The main feature of this procedure is that it can be used in field measurements. The procedure is based on the extraction of total Cr(VI) exploiting the complexation property of diethylenetriaminepentaacetic acid (DTPA) followed by electrochemical reduction of Cr(VI) to Cr(III) with the formation of Cr(III)-H₂DTPA complex adsorbed on mercury film electrode. The voltammetric signal is caused by reduction of this complex. The validation of the proposed procedure was made by Cr(VI) determination in the certified reference material “Chromium VI in soil”. The protocol for Cr(VI) determination has also been applied to the analysis of Rendoll soil samples with satisfying precision.

     

Application of 2-mercaptobenzothiazole self-assembled monolayer on polycrystalline gold electrode as a nanosensor for determination of Ag(I)

Fabrication and application of a voltammetric sensor based on gold 2-mercaptobenzothiazole self-assembled monolayer (Au-MBT SAM) for determination of silver ion is described. Preliminary experiments were performed to characterize the monolayer. The surface pK_a determined for the MBT monolayer is 7.0. This value was obtained by impedimetric titration of the monolayer in the presence of Fe(CN)₆^3−/4− as a redox probe. The extent of surface coverage was evaluated as 1.52 × 10⁻⁹ mol cm⁻² based on charged consumed for reductive desorption of the monolayer in the 0.50 M NaOH solution. Then the sensor was used for determination of Ag(I) by square wave voltammetry. The parameters affecting the sensor response, such as pH and supporting electrolyte, were optimized. A dynamic calibration curve with two linear parts was obtained in the concentration ranges of 5 × 10⁻⁸-8 × 10⁻⁷ and 1 × 10⁻⁶-1 × 10⁻⁵ M of Ag(I). The detection limit adopted from cathodic striping square wave voltammetry was as 1 × 10⁻⁸ M for n = 7. Furthermore, the effect of potential interfering ions on the determination of Ag(I) was studied, and an appropriate method was used for the elimination of this effect.     

Magnetic silver(I) ion-imprinted polymeric nanoparticles on a carbon paste electrode for voltammetric determination of silver(I)

Magnetic silver ion imprinted polymer nanoparticles (mag-IIP-NPs) were prepared and used as a recognition element in electrochemical detection of silver(I). The procedure involves two steps: (a) the extraction of the Ag(I) by the mag-IIP-NPs, and (b) determination of the preconcentrated Ag(I) ions on the surface of the magneto carbon paste electrode (MCPE) using differential pulse voltammetry. The amount of sorbent, pH value of the sample solution, extraction time, supporting electrolyte, reduction potential and reduction time were optimized. Under optimal conditions and at a working voltage of +0.02 V (vs. Ag/AgCl), the method displays a linear response in the 0.05 to 150 μg?L^?1 Ag(I) concentration range. Other features include a low detection limit (15 ng?L^?1), a remarkable selectivity and good reproducibility (with an RSD of 4.7%). The results obtained with this analytical assay when analyzing different water samples were compared with the data obtained by GF-AAS, and the results agreed satisfactorily. In our perception, this approach also may be extended to electrochemical detection for other ions, and this makes it a widely applicable strategy for heavy metal ion analysis.

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Graphical abstract Schematic illustration of the procedure for the extraction and voltammetric detection of silver(I) ions.

     

Coated-wire ion-selective electrode for the determination of gold(III)

A coated-wire gold(III)-selective electrode based on the 1,2,4,6-tetraphenyl-pyridinium tetrachloroaurate(III) ion-pair is described. The response is Nernstian in the gold concentration range 10^?2–3 × 10^?6 (slope 59.0 mV/pAu). Of the 22 ions tested, only the interference of thallium(III) is important. The electrode is applied to the determination of gold in an Ag-Pd-Au alloy with satisfactory results.     

Copper(I) activity of the copper(II) ion-selective electrode

The Orion copper(II) ion-selective electrode responds well to copper(II) ions in aqueous medium. However, in the presence of acetonitrile and copper(I) ions, it can behave as a copper(I) ion-selective electrode with Nernstian behaviour.     

Chromium(III) ion-selective electrode based on 4-dimethylaminoazobenzene

A PVC-based membrane of 4-dimethylaminoazobenzene reveals a Nernstian potentiometric response (with slope of 19.5+/-0.6 mV/decade and a correlation coefficient of 0.999) for Cr(III) over a wide concentration range (1.66 x 10(-6)-1.0 x10(-2) mol dm(-3)). The potential of this electrode is independent of pH in the range of 3.0-5.5. It has a fast response time of about 10 s and was used for a period of 3 months with good reproducibility. The detection limits of this membrane electrode was 8 x 10(-7) M. the proposed electrode has been used as an indicator electrode in the potentiometric titration of Cr(III) with EDTA. This sensor exhibits a very good selectivities for Cr(III) over a wide variety of metal ions.     

Potassium ion-selective electrode based on a cobalt(II)-hexacyanoferrate film-modified electrode

A potassium ion-selective electrode based on a cobalt(II)-hexacyanoferrate(III) (CHCF) film-modified glassy carbon electrode is proposed. The electroactive film is introduced onto the glassy carbon electrode surface by electrodeposition of cobalt, which forms a thin CHCF film on subsequent anodic scanning in KClHCl solution (pH 5.0–5.5) containing K₃Fe(CN)₆. The thickness of the film on the electrode surface can be controlled by changing the electrodeposition time and the concentrations of cobalt(II) and Fe(CN)^3?₆ ions. The modified electrode exhibits a linear response in the concentration range 1 × 10^?1 ?3 × 10^?5 M potassium ion activity, with a near-Nernstian slope (48–54 mV per decade) at 25 ± 1°C. The detection limit is 1 × 10^?5 M. The stability, response time and selectivity were investigated. The electrode exhibits good selectivity for potassium ion with the twelve cations investigated. The relative standard deviation is 1.5% (n=10). The effects of the thickness of the electroactive film and the pH of the solution on the electrode response were also investigated.     

A highly selective thallium(I) electrode based on a thia substituted macrocyclic ionophore

A new highly Tl(I)-selective PVC membrane electrode based on tetrathia macrocycle 6,7: 14,15-dibenzo-5,8,13,16-tetraoxo-1,4,9,12-tetrathiacyclohexadecane [Bz₂O₄(16)aneS₄] (I) as membrane carrier, o-nitrophenyloctyl ether (o-NPOE) as solvent mediator and potassium tetrakis(p-chlorophenyl)borate (KTpClPB) as lipophilic additive has been developed. The best performance was given by the membrane of macrocycle (I) with composition 3:120:1.5:50 (I:o-NPOE:KTpClPB:PVC). This electrode exhibits a Nernstian response to Tl(I) ions in the concentration range 1.0 × 10⁻¹-2.23 × 10⁻⁶ M with a slope of 58.2 mV/decade of concentration and a detection limit of 1.58 × 10⁻⁶ M. The response time of the sensor is 12 s and can be used over a period of 4 months with good reproducibility. The proposed electrode revealed good selectivity over a wide variety of other cations including alkali, alkaline earth, heavy and transition metals. The electrode works well over a pH range of 3.2-11.5 and in partially non-aqueous medium with up to 30% organic content. The sensor was also used as an indicator electrode in potentiometric titration of Tl(I) ions with KI solution.     

Unmodified silver nanoparticles based multisensor for Ni (II) ions in real samples

This article report microwave assisted green method for the synthesis of silver nanoparticle from Brassica oleracea var. Italica (BI) extract. The synthesized silver nanoparticle (AgNP-BI) was characterized by various analytical techniques. Here we are reporting three methods for the sensing of Ni (II) from the synthesized AgNP-BI. First one is the detection of Ni (II) ion based on changes in the absorbance resulting from the complex formation of the Ni (II) ion with AgNP-BI. The second one is the fluorescent sensing of Ni (II) ion using AgNP-BI by the changes in the fluorescence intensity. The third one is the electrochemical sensing of Ni (II) ion in which silver nanoparticle attached to the platinum electrode surface. The above-mentioned methods exhibit outstanding selectivity towards Ni (II) ion. The practical application of the AgNP-BI was also carried out for the trace determination of Ni (II) ions. The limit of detection was found to be 0.932 µM using differential pulse voltammetry (DPV).     

Ion imprinted polymer based ion-selective electrode for the trace determination of dysprosium(III) ions

Ion-selective electrode (ISE) was designed by dispersing the dysprosium(III) IIP particles in 2-nitrophenyloctyl ether plasticizer and then embedded in polyvinyl chloride matrix. The ISE shows a Nernstian response for dysprosium(III) over a wide concentration range (8.0 × 10⁻⁶ to 1.0 × 10⁻¹ M) with a slope of 21.7 mV per decade. The limit of detection was 2 × 10⁻⁶ M. This sensor has a very fast response time (∼10 s) and offers high selectivity compared to conventional chemical sensors towards dysprosium(III) with respect to several alkali, alkaline earth and transition metal ions as the selectivity is 10-100-fold better. The sensor was used for determination of dysprosium(III) ions by potentiometric (EDTA) titration and has been successfully demonstrated for the determination of fluoride in mouth wash solution.     

Coated wire chromium(III) ion-selective electrode based on azamacrocycles

Tetraazacyclotetradecane, tetratosyltetraaza 12C4, and tritosyltriaza 9C3 have been explored as electroactive materials for preparing coated wire ion-selective electrodes (CWISEs) for Cr(III) ions. The best performance was observed for the membrane comprising electroactive material (tetratosyltetraaza 12C4), plasticizer (dibutyl phthalate), and poly(vinyl chloride) in the optimum ratio 5:60:35 (w/w). Linear Nernstian response for this electrode was obtained over the total Cr(III) concentration range of 1×10^–1 to 1×10^–7 M in 0.05 M NH₄NO₃ medium, with a slope of 20±1 mV per decade change. The working pH range of the electrode was 1.8–5.5. Selectivity coefficients of some mono, divalent, and trivalent metal ions were determined. Analyses of electroplating bath solutions, chromating, and effluent samples have been carried out using this CWISE and the results are found to be comparable with those obtained by using conventional methods or by AAS.     

New cadmium(II)-selective electrode based on a tetraazacyclohexadeca macrocyclic ionophore.

A poly(vinyl chloride)-based membrane of 3,4:11,12-dibenzo-1,6,9,14-tetraazacyclohexadecane with sodium tetraphenyl borate (NaTPB) as an anion excluder and dibutylphthalate (DBP), dibutyl(butyl)phosphonate (DBBP), tris(2-ethylhexyl)phosphate (TEHP) and tributyl phosphate (TBP) as a plasticizing solvent mediator was prepared and investigated as a Cd2+-selective electrode. The best performance was observed with the membrane having a ligand-PVC-DBP-NaTPB composition of 2:25:60:1, which worked well over a wide concentration range (1.6 x 10(-6) - 1.0 x 10(-1) M) with a Nernstian slope of 29.5 mV per decade of activity between pH 2.0 - 6.0. This electrode showed a fast response time of 13 s and was used over a period of 4 months with good reproducibility (S = 0.4 mV). The selectivity coefficient for mono-, di- and trivalent cations indicated excellent selectivity for Cd2+ ions over a large number of cations. Anions such as NO3- and SO4(2-) , did not interfere. The membrane sensor has been successfully used to determine Cd2+ in real samples.     

The determination of lead in water and sediment samples using a lead ion-selective electrode

Lead concentrations in water and sediment samples near a stationary metal emission source were determined using the lead ion-selective electrode. These results were then verified by use of atomic absorption spectrophotometric methods. Samples were collected at three strategic sites near a local lead company in Southeast Houston, Texas. Accumulated rain water and sediment (soil deep down core) were analyzed in order to estimate lead concentration as a function of depth. Data indicate that the level of lead concentrations in both surface water and water extracted from the sediments exceed the limits for drinking water as established by the Environmental Protection Agency. The lead concentrations of the soil samples were higher in most cases when compared with various soils in the United States. The highest concentrations of lead were found in surface water samples.     

Mercury ion selective poly(aniline) solid contact electrode based on 2-mercaptobenzimidazol ionophore

A mercury(II) ion selective poly(aniline) solid contact electrode based on 2-mercaptobenzimidazol (2MBI) ionophore as a sulfur containing sensing material was successfully developed. The electrode exhibits a good linear response of 29.1 mV/decade (at 20 ± 0.2°C, r ² = 0.997) within the concentration range of 1 × 10^?2?1 × 10^?7 M Hg(II). The composition of this electrode was: ionophore 0.100, polyvinylchloride (PVC) 0.330, dibutylphthalate (DBP) 0.470, potassiumtetrakis(4-chlorophenyl)borate (KTpCIPB) 0.090, and oleic acid (OA) 0.010. A poly(aniline) solid contact electrode based on 2MBI with DBP and OA plasticizers exhibited the best response characteristics of the results obtained for similarly coated wire type electrodes and solid contact electrodes based on only one DBP plasticizer. The electrode shows good selectivity for mercury(II) ions in comparison with alkali, alkaline earth, transition and heavy metal ions. This electrode is suitable for use with aqueous solutions of pH 3.3?C8.0 and the standard deviation in the measured EMF difference was ±0.5 mV in a mercury nitrate sample solution of 1.0 × 10^?2 M and ±1.1 mV in a mercury nitrate sample solution of 1.0 × 10^?3 M. The stabilization time was less than 15 min and the response time was less than 33 s. The electrode was applied as a sensor for the determination of Hg(II) content in a sea water sample and some amalgam alloys. The results show good correlation with data obtained by atomic absorption spectrometry.