A copper ion-selective electrode with high selectivity prepared by sol-gel and coated wire techniques

A sol-gel electrode and a coated wire ion-selective poly(vinyl chloride) membrane, based on thiosemicarbazone as a neutral carrier, were successfully developed for the detection of Cu (II) in aqueous solutions. The sol-gel electrode and coated electrode exhibited linear response with Nernstian slopes of 29.2 and 28.1 mV per decade respectively, within the copper ion concentration ranges 1.0×10^–5–1.0×10^–1 M and 6.0×10^–6–1.0×10^–1 M for coated and sol-gel sensors. The coated and sol-gel electrodes show detection limits of 3.0×10^–6 and 6.0×10^–6 M respectively. The electrodes exhibited good selectivities for a number of alkali, alkaline earth, transition and heavy metal ions. The proposed electrodes have response times ranging from 10–50 s to achieve a 95% steady potential for Cu²⁺ concentration. The electrodes are suitable for use in aqueous solutions over a wide pH range (4–7.5). Applications of these electrodes for the determination of copper in real samples, and as an indicator electrode for potentiometric titration of Cu²⁺ ion using EDTA, are reported. The lifetimes of the electrodes were tested over a period of six months to investigate their stability. No significant change in the performance of the sol-gel electrode was observed over this period, but after two months the coated wire copper-selective electrode exhibited a gradual decrease in the slope. The selectivity of the sol-gel electrode was found to be better than that of the coated wire copper-selective electrode. Based on these results, a novel sol-gel copper-selective electrode is proposed for the determination of copper, and applied to real sample assays.     

Thermodynamics of solid-state connected ion-sensitive membrane electrodes: The silver-silver chloride system: Part I. Standard potential EM0 at 25, 50, and 75°C

Standard potentials E_M⁰ at 25, 50 and 75°C of all-solid-state silver-silver chloride ring membrane electrodes (Schott) with pressed-in silver foil have been measured with respect to the Pt, H₂ electrode by means of a cell without transference (see also [1]) applied earlier by Bates and Bower who measured standard potentials E⁰ of corresponding electrodes of the 2nd kind. The data evaluated by the extended Debye-Hückel theory can directly be compared with the reported 2nd kind electrode data. Identical thermodynamic behavior of both electrode types is observed; small differences (<1.5 mV) of standard potentials and their temperature dependence are discussed on the basis of different states of electrode materials orignating from different electrode preparation and are applied to calculate thermodynamic data of membrane electrodes referred to those of electrodes of the 2nd kind. The results and contradictory literature data are discussed. A brief characterization of membrane and 2nd kind electrodes is given.     

Determination of hydrogen peroxide in pickling baths for copper alloys by linear sweep voltammetry

Hydrogen peroxide in pickling baths for copper and copper alloys can be determined by linear sweep voltammetry with a glassy carbon electrode. The oxidation mechanism changes around 0.15 M H₂O₂. Catalytic decomposition was found to be much smaller at glassy carbon electrodes than at platinum electrodes. An almost linear calibration curve was obtained up to 60 mM H₂O₂. Interferences from Cu²⁺, Zn²⁺, Ni²⁺, Al³⁺, Fe³⁺ and Pb²⁺ as well as from the stabilizers were small. All measurements were made in sulphuric acid solutions.     

An electsochemical study of copper(II) nitrate and perchlorate in n,n-dimethylformamide

Polarographic, cyclic voltammetric and controlled-potential coulometric studies of copper(II) nitrate and perchlorate in dimethylformamide are reported. Copper(II) in copper(II) perchlorate solutions is directly reduced in a 2e step to copper metal at platinum electrodes and to a copper amalgam at mercury electrodes. Copper(II) in the presence of nitrate forms a complex of composition Cu(N0₃)₂ in DMF; the dissociation constant, measured polarographically, is 9 × lO^-5. The copper(II) nitrate complex is electrochemically reduced in two steps consisting of a reversible dissociation of the complex followed by direct reduction of copper(II) ion to copper(0). The diffusion coefficients of copper(II) ion and the copper(II) nitrate complex are 4.91 × lO^-6 cm² s^-1 and 4.33 × 10^-6 cm² s^-1, respectively.     

Voltammetric measurement of copper(II)/organic interactions in estuarine waters

The voltammetry of copper in organic ligand/chloride media is dominated by the formation of CuCl^?₂ species and by induced adsorption of Cu(I) in organic coatings on the electrodes. These phenomena are utilised in a novel method for evaluating Cu(II)/organic ligand interactions, based on the principle of ligand exchange. The Cu(II)/organic species competes with glycine which forms copper glycinate. These two complexes can be distinguished voltammetrically: copper glycinate gives a higher surface excess of copper at a gelatin-coated hanging mercury drop electrode, partly because of the increased production of CuCl^?₂ from copper glycinate at the electrode surface. The method proved satisfactory for pure ligand/surfactant/chloride media and for estuarine waters. It is shown that there are two type of Cu(II)-binding ligand in estuarine waters: humic material (> 10^?6 mol l^?1, assuming 1:1 site binding) with polyelectrolyte-type binding, and discrete ligands (? 10^?6 M) with stability constants around 10⁹. The extent of Cu(II) binding by the humic material decreases down the estuary because of dilution and increased salinity.     

Calcium‐Selective Electrodes for Measurements in the Presence of Anionic Surfactants

Calcium selective electrodes with various membrane formulations were studied in solutions containing CaCl₂ and sodium dodecylsulfate (NaDS). It is shown that electrodes based on neutral ionophores ETH 1001 and ETH 129 cannot be used as Ca²⁺ ion sensors in these solutions because of strong anion interference from DS^? anion. Among other formulations, that based on calcium bis(tetramethylbutylphenyl)phosphate in tri(2‐ethylhexyl)phosphate appear the most promising. The interpretation of the ISE response in solutions under study relied on a novel approach which considers three forms of calcium: Ca²⁺ free ions, Ca in Ca(DS)₂ precipitate, and Ca²⁺ bound by the DS^? micelles. Data needed for the respective calculations were obtained by DS^? selective electrode based on tetradecylammonium, and Na⁺ selective glass electrode.     

The reactivity of photogenerated NO32− on polycrystalline gold electrodes with different surface structures

We considered the role of the superficial atomic structure of polycrystalline gold electrodes on the electrochemical oxidation and the reduction of NO₃^2? photogenerated by trapping of electrons emitted from the electrode. The perturbation of the superficial structure of the electrode by mechanical polishing slows down the oxidation of NO₃^2?. We observed only an activated process in this case. The superficial atomic reorganization of the surface by cyclic polarization makes this reaction faster without perturbation of the short-range diffusion process of reactive species. The production of highly dispersed surfaces (black gold) gives slightly more active electrodes than the preceding one, but influences the short-distance diffusion mode in solution. The last two electrode types exhibit barrier-less and activated processes for the charge-transfer step.     

Calcium ion selective membrane electrode

The calcium salts of the mono- and diesters of [4-(1,1,3,3-tetramethylbutyl)phenyl phosphoric acid] have been prepared, and the individual esters as well as mixtures of the esters have been used with several varieties of polyvinyl chloride to construct macro membrane electrodes selective to calcium ions. These electrodes have been calibrated by using solutions of CaCl₂ and Ca ion buffers. The mixed ester electrodes showed Nernstian response in the concentration range 10^-1 to 10^-7M; the diester electrodes showed Nernstian response down to 7.9 x 10^-8M. The detection limit of the mixed ester electrode was 10^-8M, whereas that of the diester electrode was 7.9 x 10^-9M. Contrary to these results, the monoester electrodes showed unsatisfactory behavior. The responses of both the mixed ester and diester electrodes to calcium ions were not affected by the presence of sodium, potassium, or other divalent ions. Only ferric and lanthanum ions showed interferences with the electrode response to calcium ions. p]The electrode response was independent of pH in the approximate range 5–8 at a CaCl₂ concentration of 10^-4M. As the Ca ion concentration was increased, the range of pH independence widened to approximately 4–8. The dynamic response time constant of the mixed ester electrode was in the range 0.7–1.5 sec, whereas that of the diester electrode was in the range 0.5–0.75 sec.     

Solid Membranes of Copper Hriacyanoferrats (III) as Thallium (I) Sensitive Electrode

Abstract

Solid membranes of copper hexacyanoferrate (III) in Areldite are evaluated as thallium (I) sensitive electrode. The membrane electrode gave a linear near Normstian response to thallium (I) ions in the concentration range 10^?1 - 5 × 10^?4 M and can be used to estimate T1 (I) down to 10^?4 M. The responses of the electrode is fast and steady potentials are obtained in less than a minute. The same membrane has been used over a period of six months without any appreciable drift in potential. The electrode can also be used satisfactory in partially non-aqueous media and in presence of a number of interfering ions. It is superior to the existing T1(I) solid membrane electrodes as it can function in alkaline range also.     

Influence of copper hexacyanoferrate film thickness on the electrochemical properties of self-assembled 3-mercaptopropyl gold electrode and application as a hydrazine sensor

A copper hexacyanoferrate film was obtained on a modified electrode prepared by self-assembly of 3-mercaptopropyltrimethoxysilane on a gold surface. The film thickness was controlled using a layer-by-layer technique to tune the electrocatalytic properties of the electrode. Two electrodes with different hexacyanoferrate film thicknesses were prepared via three immersions (AuS/CuHCF3) and six immersions (AuS/CuHCF6) of the film in the precursor solutions. Cyclic voltammetry data were obtained to determine the adequate film thickness. Scanning electron microscopy images showed a roughness increase due to the growth of the film thickness at the electrode surface. Electrochemical impedance spectroscopy showed distinct behavior for the two electrodes prepared; while diffusion and charge transfer processes can be observed in both electrodes, an additional capacitive process at intermediary frequencies was observed for the AuS/CuHCF6 electrode. The charge transfer resistance (R _ct) for the AuS/CuHCF3 electrode (19.6 Ω cm²) was lower than for AuS/CuHCF6 (27.9 Ω cm²) due to the hexacyanoferrate film thickness, since the charge transfer process demands the simultaneous diffusion of K⁺ into the surface. Cyclic voltammetry was used to evaluate the application of the AuS/CuHCF3 electrode as an electrochemical sensor, revealing a linear correlation for hydrazine concentrations.     

Construction of novel simple phosphate screen-printed and carbon paste ion-selective electrodes

The construction and performance characteristics of different phosphate ion-selective electrodes are described. Three types of electrodes are demonstrated, namely screen-printed, carbon paste and the conventional PVC membrane electrodes. The cited electrodes are based on bisthiourea ionophores and show a considerable selectivity towards hydrogenphosphate with Nernstian slopes depending on the type of the electrode and the ionophore used. Matrix compositions of each electrode are optimised on the basis of effects of type and concentration of the ionophore as well as influence of the selected plasticizers. The screen-printed electrodes work satisfactorily in the concentration range 10⁻⁵ to 10⁻² mol L⁻¹ with anionic Nernstian compliance (32.8 mV/decade activity) and detection limit 4.0 × 10⁻⁶ mol L⁻¹. The screen-printed electrodes show fast response time of about 2.2 s and exhibit adequate shelf-life (4 months). The fabricated electrodes can be also successfully used in the potentiometric titration of HPO₄²⁻ with Ba²⁺.     

Electrodeposition of rare earth metals Y,Gd, Yb in ionic liquids

The possibility of yttrium, gadolinium, and ytterbium electrodeposition from solutions of their triflates in different ionic liquids at 100°C was investigated. It was shown that these metals could be deposited on the cathode from electrolytes based on ionic liquids with quaternary ammonium cations, and these metals do not deposit from 1-butyl-2,3-dimethylimidazolium triflate. It was established that, in the case of butyltrimethylamonium triflate usage, metal deposition occurs on a copper electrode, and it does not occur on a platinum electrode, and in 1-butyl-1-methylpirrolidinium triflate, the reduction process is possible on both electrodes. Yb³⁺ reduction occurs step by step via Yb²⁺ formation. It was shown that the limiting stage of the cathode process is adsorption of a metal cation on the electrode.     

Voltammetric determination of sorbite at a mechanically renewed copper electrode

Potentials and currents of D-sorbitol oxidation peaks as a function of polarization conditions for a copper electrode in situ renewed by mechanically cutting a 0.5-μm surface layer are studied by direct-current cyclic voltammetry. Oxidation peaks of sorbite emerge in cyclic voltammograms recorded in alkaline supporting electrolytes (0.05–0.10 M KOH and NaOH solutions) upon scanning the potential to the anodic region (E _p = 0.50–0.58 V) and in the reverse direction (E _p = 0.60–0.62 V). The shape and parameters of these peaks depend on the concentration of KOH, because of the different copper oxides involved in the oxidation of sorbite formed at the electrode surface. The regeneration of the electrode surface is the necessary condition for good reproducibility of the peak parameters. The signals obtained on the surface of the unrenewed electrodes are almost halved and less reproducible. The calibration graph of the current of the sorbite oxidation peak as a function of its concentration is linear in the range from 5 × 10⁻⁴ to 1 × 10⁻² M.     

The Ternary Coppersilver Selenide—A New Homogeneous Solid State Ion-Selective Electrode for Copper (II)

Abstract

The performance characteristics of a copper (II) ion-selective electrode, based on pressed-pellet membrane of ternary CuAgSe, are reported. The sensing material is isostructural with the natural mineral β -eucairite and shows high corrosion resistivity which results in stable and reproducible electrode performance upon ageing. The electrodes exhibit a linear Nernstian response dawn to 5.10^?8 M in non buffered medium and down to 10^?13M in copper-glycine ion buffer. Data on the electrode stability for a period of two and a half years, on the electrode response time, pH-dependence, selectivity etc. are also presented.     

Prussian blue solid-state films and membranes as potassium ion-selective electrodes

The use of thin films of Prussian blue and heterogeneous Prussian blue membranes as potassium ion-selective electrodes was investigated. All of the heavier group I cations and NH⁺₄ interfere strongly but there is relatively good selectivity towards Na⁺ with a selectivity coefficient of ca. 5 × 10^?3. The thin-film measurements, based on Prussian blue deposited on platinum, involve conditioning the electrode to a fixed potential according to the method used by Engel and Grabner for copper hexacyanoferrate(III) films. The membrane electrodes were based on mixing Prussian blue with polymeric supporting films such as polystyrene and epoxy. A particularly simple practical configuration involves Prussian blue membranes deposited directly on copper conductors where one membrane serves as a reference electrode. A reversible cell, without liquid junction, is formed with Prussian blue and Ag/AgCl electrodes and this serves as a means for determining an accurate value for the standard reduction potential of Prussian blue, which is found to be 0.238 V vs. Ag/AgCl at 25 °C.     

Solid-contact Cu(II) ion-selective electrode based on 1,2-di-(<Emphasis Type="Italic">o</Emphasis>-salicylaldiminophenylthio)ethane

The development of Cu(II) solid-contact ion-selective electrodes, based on 1,2-di-(o-salicylaldiminophenylthio)ethane as a neutral carrier, is presented. For the electrodes construction, unmodified carbon ink (type 1 electrode) and polymer membrane-modified carbon ink (type 2 electrode) were used as solid support and transducer layer. Also, carbon ink composite polymer membrane electrode (type 3 electrode) was prepared. The analytical performance of the electrodes was evaluated with potentiometry, while bulk and interfacial electrode features were provided with electrochemical impedance spectroscopy. It is shown that modification of carbon ink with polymer membrane cocktail decreases the bulk contact resistance of the transducer layer and polymer membrane, thus enhancing the analytical performance of the electrode in terms of sensitivity, linear range, and stability of potential. The optimized electrodes of types 2 and 3 exhibit a wide linear range with detection limits of 1.8 × 10⁻⁶ and 1.6 × 10⁻⁶ M, respectively. They are suitable for determination of Cu²⁺ in analytical measurements by direct potentiometry and in potentiometric titrations, within pH between 2.3 and 6.5. The electrodes are selective for Cu²⁺ over a large number of tested transition and heavy metal ions.     

The calibration and response of ion-selective electrodes at low concentrations of primary ions

Electrolytic generation of ions is proposed for the preparation of standard solutions for the calibration of iodide and silver ion-selective electrodes in the concentration range 10^-4–10^-7 M. The responses of these electrodes and also the copper(II) ion-selective electrode were examined in various electrolyte solutions. The current efficiencies of the electrolytic generation of the iodide ions into the various solutions were measured coulometrically. The advantages of this newly proposed calibration technique are discussed.     

Electrochemical carbon dioxide and bicarbonate reduction on copper in weakly alkaline media

The electrochemical reduction of CO₂ on copper is an intensively studied reaction. However, there has not been much attention for CO₂ reduction on copper in alkaline electrolytes, because this creates a carbonate buffer in which CO₂ is converted in HCO₃ ^? and the pH of the electrolyte decreases. Here, we show that electrolytes with phosphate buffers, which start off in the alkaline region and, after saturation with CO₂, end up in the neutral region, behave differently compared to CO₂ reduction in phosphate buffers which starts off in the neutral region. In initially alkaline buffers, a reduction peak is observed, which is not seen in neutral buffer solutions. In contrast with earlier literature reports, we show that this peak is not due to the formation of a CO adlayer on the electrode surface but due to the production of formate via direct bicarbonate reduction. The intensity of the reduction peak is influenced by electrode morphology and the identity of the cations and anions in solution. It is found that a copper nanoparticle-covered electrode gives a rise in intensity in comparison with mechanically polished and electropolished electrodes. The peak is observed in the SO₄ ^2?-, ClO₄ ^?-, and Cl^?- containing electrolytes, but the formate-forming peak is not seen with Br^? and I^?.     

The use of copper solid amalgam electrodes for determination of the pesticide thiram

The complexes formed between copper and thiram and between mercury and thiram have been electrochemically (voltammetrically) investigated in the present work. Their structure was confirmed using electrospray ionization mass spectrometry. Due to formation of the complex between copper (from copper solid amalgam electrode) and thiram, the concentration of this pesticide can be determined. The voltammetric behavior of thiram was investigated at polished (p-CuSAE) and mercury meniscus modified (m-CuSAE) copper solid amalgam electrodes (inner diameter 1.5 mm) by differential pulse voltammetry (DPV) and by direct current voltammetry (DCV). Optimum conditions for DPV determination of thiram were found in Britton–Robinson buffer. The reaction mechanism was investigated using DCV and elimination voltammetry with linear scan. DPV with optimized parameters was applied for determination of thiram in analyzed solutions. The limits of detection were calculated as 16 nmol?L^?1 (t _acc?=?100 s) for m-CuSAE and 23 nmol?L^?1 (t _acc?=?60 s) for p-CuSAE. The proposed method was successfully applied for thiram determination in real sample solutions.     

Electrochemical behaviour of lanthanum fluoride in molten fluorides

The electrochemical behaviour of lanthanum fluoride dissolved in molten lithium fluoride and in eutectic mixture LiF-CaF₂ was investigated by cyclic voltammetry and laboratory electrolysis. The cyclic voltammetry experiments were carried out at 900°C and 800°C, respectively, in a graphite crucible (counter electrode). Several types of working electrodes (Mo, W, Ni and Cu) were used. Ni/Ni(II) was used as a reference electrode. Laboratory electrolysis was carried out in the system LiF-CaF₂-LaF₃ at 800°C in galvanostatic (j _c = −0.21 A cm⁻²) and potentiostatic (E = 0.87 V) regimes. In both cases, nickel served as the cathode and graphite as the anode. It was found that no new separate reduction peak occurred on the molybdenum or tungsten electrodes in the investigated systems. When copper or nickel electrodes were used, new peaks corresponding to the reduction of lanthanum(III) to lanthanum metal appeared. This can be explained by the formation of alloys or intermetallic compounds of lanthanum with copper or nickel. X-ray microanalysis showed that lanthanum was electrodeposited together with calcium under formation of intermetallic compounds with the electrode materials in the galvanostatic regime. In the potentiostatic regime, mainly lanthanum was deposited, which enabled its separation.