Studies of copper(II) sulphide ion-selective electrodes

Changes in liquid junction potentials in copper(II) solutions were measured when different reference electrodes were used. The slope and intercept of a calibration curve for a copper-selective electrode will depend on the selection of reference electrode. The condition of the electrode surface of an Orion copper-selective electrode was studied microscopically and the influence of redox potential on stability of the electrode against corrosion is discussed. Oxidizing solutions will produce pits at dislocations in the material and there will be a mixed electrode potential. The slope, stability, and speed of response are much lower when the surface contains pits. Diamond-polishing was shown to improve the electrode significantly.     

Lead(II) and copper(II) ion-selective electrodes based on two heterocyclic compounds

In this paper, two nitrogen, sulphur or oxygen containing heterocyclic compounds were used as ionophores in ion-selective electrodes. In these two ion-selective electrodes, 2,6-di(5-methyl-1,3,4-oxadiazol-5-yl)pyridine (DMOP) gives the best Pb²⁺ sensitivity and 2,5-di(2′-methylpyridinethio)thiadiazole (DPTD) gives the best sensitivity for Cu²⁺. These electrodes are composed of KTpClPB as anion excluder and DOS as plasticizer. The two membrane electrodes show Nernstian or near-Nernstian response towards Pb²⁺ or Cu²⁺ (29.3 and 27.3 mV/decade, respectively) over the concentration range 10⁻⁵∼10⁻² and 10⁻⁶∼10⁻³ M, respectively. The response time was less than 20 sec and a good reproducibility over a period of 2 months was observed. The electrodes exhibited good selectivities over a number of alkali, alkaline earth and transition metal ions. The proposed electrodes have also been used for the direct determination of Pb²⁺ and Cu²⁺ ions in real samples.     

The behaviour of two types of copper ion-selective electrodes in different copper(II)-ligand systems

The behaviour of two types of solid-state homogeneous sensors for copper(II), one based on pressed pellets of ternary CuAgSe and the other on thin-layer electroplated Cu(2-x)Se, in 12 different copper(II)-ligand systems, has been thoroughly investigated. Both electrodes exhibit anomalous behaviour when the ligands are of complexone type, the effect of the complexones on the deviations increasing in the order IDA < NTA < EDTA approximately DTPA, and being practically the same for the two types of sensors, thus disproving a previous suggestion that the anomaly is due to the silver in the silver-containing sensors. The experimental data do not support the specific ligand-adsorption hypothesis either. The observed deviations are tentatively explained on the basis that, as suggested by the selectivity coefficients, both sensors act as primary copper(I) ion-selective electrodes rather than copper(II)-electrodes. Thus, at very low copper(II) concentrations, according to the extended Nikolskii equation, the [Cu(I)]/[Cu(II)] ratio at the electrode surface determines the electrode sensitivity towards Cu(II). The lower detection limit could be improved by pH-control and selective complexation of Cu(I). This hypothesis has been proved experimentally. If the copper(I) activity on the electrode surface is decreased, the anomaly observed for the Cu(II)-NTA system disappears and decreases considerably for the Cu(II)-EDTA and Cu(II)-DTPA systems.     

Screen-printed copper ion-selective electrodes

A simple, low-cost and reproducible method for the mass production of potentiometric ion-selective electrodes for copper ions is presented. These planar, strip sensors were obtained by screen-printing. The application of pastes cured at low temperature allows printing of the sensors on low-cost, plastic substrates. The pastes for printing of ion-sensitive thick-film membranes were based on copper (I) and copper (II) sulfides. The analytical characteristics of the thick-film electrodes were compared. The analytical properties (range of determination, sensitivity, selectivity, response time) of the copper (I) sulfide-based sensors were comparable with those for conventional ion-selective electrodes. Received: 12 January 2000 / Revised: 13 March 2000 / Accepted: 16 March 2000     

Screen-printed copper ion-selective electrodes

A simple, low-cost and reproducible method for the mass production of potentiometric ion-selective electrodes for copper ions is presented. These planar, strip sensors were obtained by screen-printing. The application of pastes cured at low temperature allows printing of the sensors on low-cost, plastic substrates. The pastes for printing of ion-sensitive thick-film membranes were based on copper (1) and copper (II) sulfides. The analytical characteristics of the thick-film electrodes were compared. The analytical properties (range of determination, sensitivity, selectivity, response time) of the copper (I) sulfide-based sensors were comparable with those for conventional ion-selective electrodes.     

New polyacrylate-based lead(II) ion-selective electrodes

A novel polyacrylate-based matrix for potentiometric ion-selective electrodes has been developed. Isododecyl acrylate, acrylonitrile and hexanedioldiacrylate co-monomers along with the thermo-initiator 2,2-dimethoxy-2-phenylacetophenone were used as polymeric matrix components. A lead(II)-selective electrode (Pb-ISE) was constructed using the above matrix. The electrode showed comparable analytical performance in the micromolar range to Pb-ISEs with conventional poly(vinyl chloride)-based membranes containing neutral ionophore and with solid-state membranes containing a mixture of lead sulphide and silver sulphide. Electrochemical impedance spectroscopy studies revealed much lower ion mobility in the polyacrylate membrane than in plasticized poly(vinyl chloride) membranes. This result additionally indicates the possibility of obtaining a lower detection limit for ISEs using the new acrylate matrix.     

Calixazacrown ethers for copper(II) ion-selective electrode

Five novel 1,3-alternate calix[4]azacrown ethers having 2-picolyl, 3-picolyl, and benzyl unit on the nitrogen atom were synthesized and used as ionophores for transition metal-selective polymeric membrane electrodes. The electrode based on 2-picolyl armed 1,3-alternate calix [4] azacrown ether exhibited Nernstian response toward copper (II) ion over a concentration range (10(-4.5) M-10(-2.5) M). The detection limit was determined as 10(-5) M in pH 7 and the selectivity coefficients for possible interfering cations were evaluated. Anions in the sample solution strongly affected the electrode response.     

Solid-state ion-selective electrodes for the potentiometric determination of hexacyanoferrate (II)

Hexacyanoferrate(II)-sensing electrodes were prepared by mixing Ag₂S and Ag₄Fe (CN)₆. The 6:1 Ag₂S/Ag₄Fe (CN)₆ provided the best potentiometric response and speed of response. The log concentration vs. potential curves were linear with Nernstian slope (14.8 mV/decade) over the range 10^?1-10^?6 M hexacyanoferrate (II) at pH 7.00 with constant ionic strength. Interferences included iodide, sulfide and bromide. This electrode was used as indicator in potentiometric titrations of hexacyanoferrate (II).     

Mercury(II) ion-selective electrodes based on heterocyclic systems

Mercury ion-selective electrodes (ISEs) were prepared with a polymeric membrane based on heterocyclic systems: 2-methylsulfanyl-4-(4-nitro-phenyl)-l-p-tolyl-1H-imidazole (I) and 2,4-diphenyl-l-p-tolyl-1H-imidazole (II) as the ionophores. Several ISEs were conditioned and tested for the selection of common ions. The electrodes based on these ionophores showed a good potentiometric response for Hg2+ ions over a wide concentration range of 5.0 x 10(5-) - 1.0 x 10(-1)M with near-Nernstian slopes. Stable potentiometric signals were obtained within a short time period of 20 s. The detection limits, the working pH range of the electrodes were 1.0 x 10(-5) M and 1.6-4.4 respectively. The electrodes showed better selectivity for Hg2+ ions over many of the alkali, alkaline-earth and heavy metal ions. Also sharp end points were obtained when these sensors were used as indicator electrodes for the potentiometric titration of Hg2+ ions with iodide ions.     

Solubilities of the molybdates and tungstates of silver and copper(II) in water by ion-selective electrodes

The solubilities of silver molybdate, silver tungstate, copper molybdate and copper tungstate in water have been determined over the temperature range 20–40°C using ion-selective electrodes. The molar heats of solution for these salts have been calculated at 25°C. The discrepancies between our data and the existing literature values have been discussed.     

Release of copper from commercial solid-state copper ion-selective electrodes

The release of copper from two commercial solid-state cupric ion-selective electrodes [Orion 94-29 Cupric Electrode (I) and Radiometer F1112 Selectrode (II)] was measured by immersion in the following media: 0.1M potassium nitrate (pH = 4.7), 0.5M sodium chloride (pH = 4.7) and 0.1M nitric acid. In the 0.1M potassium nitrate medium, the amount of copper released from both electrodes causes interference when they are used for the determination of cupric ion at the 10⁻⁷M level. In comparison with the 0.1M potassium nitrate medium, the copper release in the 0.5M sodium chloride and 0.1M nitric acid media was increased for electrode II but not for electrode I. The release of copper was not affected by removal of oxygen from the media but can be substantially lowered by coating the electrodes with a thin cation-exchange membrane (Nafion). The mechanism of copper dissolution is investigated.     

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.     

A microcomputer-based system for potentiometric measurements with ion-selective electrodes

A comparison, on completely equal terms, of a microcomputer-based system with manual measurements is described in detail. The main features compared are the precision and accuracy of the results and the number of determinations per time unit. The example used is a standard addition measurement of fluoride in toothpaste. The microcomputer system and its interfacing to the peripheral units are also described. The microcomputer system for control, supervision and evaluation of the measurements results in a significant gain in precision and speed. Accuracy requires the use of a non-theoretical value of the Nernstian slope. The memory effect of the ion-selective electrode is large when the type of sample is changed.     

Inexpensive device for measurements with ion-selective and pH electrodes

The design and construction of a simple device for measuring ionic concentrations (or pH) with ion-selective electrodes are described. The automated system includes a special electronic circuit with an operational amplifier, a signal conditioner and a personalcomputer. A digital multimeter can be used if automation is not required. The results obtained in tests with iodide-, chloride- and nitrate-selective electrodes and glass electrodes show very good agreement with those obtained with sophisticated commercial apparatus.     

Simultaneous semi-automatic catalytic titration of binary mixtures of mercury(II) with copper(II) or cadmium at the micromolar level

Copper(II) and mercury(II) act as catalyst and inhibitor, respectively, for the oxidation of 4,4'-dihydroxybenzophenone thiosemicarbazone by hydrogen peroxide in an ammonium chloride medium. The combination of these two effects and blocking of the catalytic cycle by EDTA are used as the basis for titrimetric methods for individual and simultaneous titrations of mercury and copper or cadmium, with catalytic end-point detection. Mixtures can be resolved in the mole ratio range 20.1–4.1 for Cu/Hg and 27.1–1.1 for Cd/Hg. Titrations are viable for 10^?7?10^?6 M mercury(II) and 10^?6-10^?5 M copper(II) or cadmium(II).     

Kinetic influences on studies of copper(II) hydrolysis by copper ion-selective electrode

The hydrolysis of micromolar solutions of copper(II) is dominated by the formation of a copper—hydroxy colloid, both in the presence and absence of atmospheric carbon dioxide. Presence of the colloid was inferred from the response of the copper ion-selective electrode and confirmed by light scattering measurements. The colloid is only slowly converted to thermodynamically more stable species, with the result that copper—carbonate complexes are not formed to any significant extent in solutions exposed to atmospheric carbon dioxide. However, copper—carbonate complexes are formed in solutions containing a constant amount of total carbonate. Speciation and complexation capacity measurements should be interpreted with caution because thermodynamic equilibrium may not be attained in solution.     

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.     

The calibration of glass electrodes and cadmium and copper ion-selective electrodes

The glass electrode is calibrated on the concentration scale against the hydrogen electrode from measurements of the potentials of the two electrodes immersed in the same buffer. The p[H⁺] of the buffer is changed between 2 and 11 by addition of base. The difference in potential between the electrodes is used to correct the glass electrode potentials. Analogously, cadmium and copper ion-selective electrodes (i.s.e.) can be calibrated against the corresponding metal-amalgam electrodes in p[M²⁺] buffers. The response of the copper i.s.e. (Radiometer Selectrode) was always close to Nernstian, whereas the response of the cadmium i.s.e. was variable and larger than Nernstian. The method is independent of errors in equilibrium constants and composition of the buffers, but it assumes ideal behaviour of the hydrogen and amalgam electrodes.