Automated potentiometric analysis with selective electrodes

An automated potentiometric analyzer based on a residual-chlorine electrode has been developed that can determine chlorine concentrations of a 4–75 ppb (±2 ppb, standard deviation 0.6–1.9 ppb). A microcomputer-controlled digital buret delivers a predetermined number of aliquots of standard, and the electrode measures the potential of the test solution after each addition. An arithmetic processing unit transforms the acquired potentiometric data to the Gran (antilog) domain; the microcomputer then calculates a set of equivalence-point estimates and, using an error function criterion, selects the best estimate. The instrument includes a digital buret, 8080 microcomputer, arithmetic processing unit, real-time clock, video display, and 16-character key pad; it uses a modified version of the computer language BASIC compiled and programmed into Programmable Read-Only Memory (PROM). Although this system was designed to assay residual chlorine in water, the analyzer can also function as a digital pH (or millivolt) meter or, with minor software modifications, serve as a general-purpose instrument using any appropriate electrode system.     

Determination of total chlorine in waste oil

Summary A simple method has been developed to determine the concentration of organic chlorine in waste oil. The determination is based on the conversion of organic chlorine to inorganic chloride by reaction with sodium biphenyl followed by extraction with nitric acid and a mixture of nitric acid and water. The concentration of chloride is determined by direct potentiometry with an ion-selective electrode. The limit of determination amounts to 3·10^–5 mol·l^–1 chloride ions with a standard deviation of 3.5%. Different samples of waste oil have been analyzed and the results have been compared to those obtained by combustion in a H₂/O₂ flame followed by potentiometric titration with silver nitrate.     

Electrochemical Determination of Copper(II) in Water Samples Using a Novel Ion-Selective Electrode Based on a Graphite Oxide–Imprinted Polymer Composite

A novel copper(II)-selective electrode based on graphite oxide/imprinted polymer composite was developed for the electrochemical monitoring of copper(II) (Cu²⁺) ions. The electrode exhibited highly selective potentiometric response to Cu²⁺ with respect to common alkaline, alkaline earth and heavy metal cations. The composite composition studies indicated that the most suitable composite composition performing the most promising potentiometric properties was 20.0% ionophore (Cu²⁺-ion imprinted polymer), 10.0% paraffin oil, 5.0% multiwalled carbon nanotubes, and 65.0% graphite oxide. The fabricated electrode exhibited a linear response to Cu²⁺ over the concentration range of 1.0?×?10^??6–1.0?×?10^??1?M (correlation coefficient of 0.9998) with a sensitivity of 26.1?±?0.9?mV decade^??1. The detection limit of the fabricated electrode was determined to be 4.0?×?10^??7?M. The electrode worked well in the pH range of 4.0–8.0. The electrode had stable, reversible and fast potentiometric response (3?s). In addition, the electrode had a lifetime of more than 1 year. The analytical applications of the proposed electrode were performed using as an indicator electrode for the potentiometric titration of Cu²⁺ with ethylene diamine tetraacetic acid solution and for the determination of Cu²⁺ of spiked river, dam, and tap water samples. The obtained results for potentiometric titration and water samples were satisfactory.     

Potentiometric flow-injection determination of trace chlorine based on its redox reaction with an iron(III)/iron(II) buffer

A very sensitive and rapid potentiometric determination of trace chlorine in water is described. The method is based on the transient potential changes which appears during the reduction of dissolved chlorin with an iron(III)/iron(II) potential buffer containing chloride and sulfuric acid. The sample is injected into a water carrier stream and merged with a stream of this potential buffer solution; chlorine is reduced during passage through a short reaction coil. The potential change from the baseline is measured with a flow-through ORP (oxidation-reduction potential) electrode. Potential changes (peak heights) are proportional to chlorine concentrations from 10^?7 M to 10^?5 M. The detection limit is 5 × 10^?8 M (3.5 μgl^?1 as Cl₂). The sample throughput is 45 h^?1. Reproducibility is in the range 2.5–1.1%. Results for potable water agree with those obtained by the o-tolidine method.     

A bromide-selective electrode-redox electrode cell for the potentiometric determination of bromine and free residual chlorine

A potentiometric cell consisting of a bromide-selective electrode and a platinum redox electrode is sensitive to free residual chlorine (FRC) when the sample solution is treated before measurement with reagents to give pH 5 and a bromide content of 0.1M. The calibration graph of e.m.f. vs. log [FRC] is linear over the [FRC] range from about 0.05 to 50 mg l . (the highest level tested). Not all forms of bromide-selective electrode prove suitable, but one with a silver bromide single-crystal membrane has been found to give a theoretical calibration slope, whereas one with an Ag(3)SBr compressed pellet membrane gave a sub-Nernstian response. The response to combined residual chlorine (CRC) is negligible but if both FRC and CRC are present, the sample treatment is likely to cause a reduction in FRC concentration. Tests have shown that a similar bias can be found with the commonly used DPD colorimetric method.     

A Novel Al(III)‐Selective Electrochemical Sensor Based on N,N′‐Bis(salicylidene)‐1,2‐phenylenediamine Complexes

A polyvinylchloride membrane sensor based on N,N′‐bis(salecylidene)‐1,2‐phenylenediamine (salophen) as membrane carrier was prepared and investigated as a Al³⁺‐selective electrode. The sensor exhibits a Nernstian response toward Al(III) over a wide concentration range (8.0×10^?7–3.0×10^?2 M), with a detection limit of 6.0×10^?7 M. The potentiometric response of the sensor is independent of the pH of the test solution in the pH range 3.2–4.5. The electrode possesses advantages of very fast response and high selectivity for Al³⁺ in comparison with alkali, alkaline earth and some heavy metal ions. The sensor was used as an indicator electrode, in the potentiometric titration of aluminum ion and in determination of Al³⁺ contents in drug, water and waste water samples.     

Chromium(III) Ion Selective Electrode Based on Oxalic Acid Bis(Cyclohexylidene Hydrazide)

A poly(vinyl chloride) membrane sensor based on oxalic acid bis (cyclohexylidene hydrazide) as membrane carrier was prepared and investigated as a Cr(III)‐selective electrode. The electrode reveals a Nernstian behavior (slope 19.8±0.4 mV decade^?1) over a wide Cr(III) ion concentration range 1.0×10^?7–1.0×10^?2 mol dm^?3 with a very low limit of detection (i.e., down to 6.3×10^?8 mol dm^?3). The potentiometric response of the sensor is independent of the pH of the test solution in the pH range 1.7–6.5. The electrode possesses advantage of very fast response, relatively long lifetime and especially good selectivity to wide variety of other cations. The sensor was used as an indicator electrode, in the potentiometric titration of chromium ion and in the determination of Cr(III) in waste water and alloy samples.     

Plant tissue-based bioselective membrane electrode for glutamate

A novel potentiometric membrane electrode with selective response to L-glutamate over the 2 × 10^-4–1.3 × 10^-2 M concentration range is constructed by immobilizing slices of yellow squash tissue at a CO₂ gas sensor. This system represents the first successful use of intact plant materials as biocatalysts in the construction of bioselective potentiometric membrane electrodes; as a result, the range of future possibilities may be greatly extended. The glutamate-sensing electrode combines excellent selectivity characteristics over some 25 possible interferences tested, good reproducibility, and a useful lifetime of 7 days in aqueous samples.     

A miniaturized FIA system for the determination of residual chlorine in environmental water samples.

The present study was aimed at developing a portable miniaturized FIA system with a two-electrode based amperometric detector for on-site monitoring of residual chlorine in environmental samples. The electrode potential control and current data collection were conducted with a home-designed potentiostat with a size of 150 x 100 x 40 mm and the weight of 350 g. It was confirmed that the amperometric response increased in proportion to the chlorine concentration up to 5 microg/ml, and the detection limit for chlorine was 0.05 microg/ml. Besides a drastic reduction in the size of the analytical system, such miniaturization achieved the advantages of increased speed, minimal mobile-phase consumption, and high sensitivity. The proposed method was successfully applied to the determination of residual chlorine in samples of pool water and tap water. The results were well agreed with those obtained by the N,N-diethyl-p-phenylenediamine (DPD) photometric method.     

Chromium(III) Potentiometric Sensor Based on Para‐Tertiary‐Butyl Calix[4]arene

A new chromium(III) PVC membrane sensor incorporating p‐tertiary‐butyl calix[4]arene as ionophore, potassium tetrakis as additive and dibutyl phthalate (DBP) as plasticizer was constructed. The electrode exhibited an excellent potentiometric response over a wide concentration range of 1.0×10^?7–1.0×10^?1 M with a Nernstian slope of 20±0.5 mV per decade. The detection limit was 5.0×10^?8 M. The electrode showed a better performance over a pH range of 3.0–8.0, and had a short response time of about <15 s.The electrode was successfully applied to potentiometric titration of Cr (III) with EDTA and for direct determination of chromium(III) in waste water.     

Differential Pulse Voltammetric Determination of Free Chlorine for Water Disinfection Process

The electrochemical detection of free chlorine based on the reduction at a gold electrode has been studied. The differential pulse voltammetric curves exhibited well‐defined cathodic peaks. Investigations with this system suggested that the active species in the cathodic reaction is HClO. Excellent reproducibility was demonstrated at pH 5. The peak height could be used for accurate and rapid determination of free chlorine in a sample water. A linear relationship (r²=0.99) was found for the concentration range of 1–5 mg Cl dm^?3 and the detection limit was estimated to be 0.04 mg Cl dm^?3.     

Voltammetric Method for Determining Ferric Ions with Quercetin

A novel, simple, rapid, inexpensive, highly sensitive voltammetric method developed for determining ferric ions with quercetin in water samples and iron supplements using a disposable bare pencil graphite electrode is described. The limit of detection and analytical ranges for the ferric ions were 3.6 nM and 17.9–716.0 nM, respectively. The results with the water samples were compared with those obtained from a potentiometric auto-titration system, and the method's accuracy was tested using certified reference material. The complex stoichiometry and electrode reaction were also systematically investigated with UV-visible spectrophotometry, ¹H-NMR spectroscopy and voltammetry.     

Flow injection analysis for residual chlorine using Pb(II) ion-selective electrode detector

A simple flow injection analysis (FIA) system for residual chlorine in tap water has been developed by using a Pb(II) ion-selective electrode (ISE) detector. The method is based on a specific response of the Pb(II)-ISE to residual chlorine. The FIA system consists of a millivolt meter, a peristaltic pump, a Pb(II)-ISE detector and a recorder. A linear working curve between peak height and concentration of residual chlorine was obtained from 0.1 to 1 mg l(-1) for the developed FIA system. The relative standard deviation for repeated injections of a 0.2 mg l(-1) residual chlorine sample was 2%. The regression line and its correlation factor between the conventional o-tolidine colorimetric method and the present method were Y=0.75X+0.17 and 0.967, respectively, for this determination.     

Self‐Assembled Mercapto‐Compound‐Gold‐Nanoparticle‐Modified Carbon Paste Electrode for Potentiometric Determination of Cadmium(II)

A new modified carbon paste electrode (CPE) based on a recently synthesized ligand [2‐mercapto‐5‐(3‐nitrophenyl)‐1,3,4‐thiadiazole] (MNT), self‐assembled to gold nanoparticles (GNP) as suitable carrier for Cd(II) ion with potentiometric method are described. The proposed electrode exhibits a Nernstian slope of 29.4±1.0 mV per decade for Cd(II) ion over a wide concentration range from 3.1×10^?8 to 3.1×10^?4 mol L^?1. The detection limit of electrode was 2.0×10^?8 mol L^?1 of cadmium ion. The potentiometric responses of electrode based on MNT is independent of the pH of test solution in the pH range 2.0–4.0. It has quick response with response time of about 6 s. The proposed electrode show fairly good selectivity over some alkali, alkaline earth, transition and heavy metal ions. Finally, the proposed electrode was successfully employed to detect Cd(II) ion in hair and water samples.     

A coated-metal enzyme electrode for urea determinations

A potentiometric enzyme electrode is reported in which an enzyme immobilized in polyvinyl chloride is used to coat an antimony metal electrode to detect changes in pH when the electrode is immersed in a solution of the enzyme substrat. As an example, urea is determined in solution by using immobilized urease on an antimony electrode, giving a linear concentration range of 5.0 × 10^-4–1.0 × 10^-2 M urea with a slope of 44 mV per decade change in urea concentration. The response slope is stable for about 1 week, with response times in the range 1–2 min, but with absolute potential changes occurring from day to day.     

Chemically Modified Carbon Paste Electrode for Determination of Sulfate Ion by Potentiometric Method

Four Schiff base complexes of different metal ions, M=Cr(III), Mn(III), Fe(III), and Co(III), were studied to characterize their ability as sulfate ion carriers in carbon paste electrode (CPE). The modified CPE electrode with Schiff base complex of Cr(III), N,N′‐ethylenebis(5‐hydroxysalicylideneiminato) chromium(III) Chloride, showed good response characteristics to SO₄^2? ion. The proposed electrode exhibits a Nernstian slope of 28.9±0.4 mV per decade for SO₄^2? ion over a wide concentration range from 1.5×10^?6?4.8×10^?2 M, with a detection limit of 9.0×10^?7 M. The CPE electrode manifested advantages of relatively fast response time, suitable reproducibility and life time and, most important, good potentiometric selectivity relative to a wide variety of other common inorganic anions. The potentiometric response of the electrode is independent of the pH of the test solution in the pH range 4.0–9.0. The proposed electrode was used as an indicator electrode in potentiometric titration of sulfate with Ba²⁺ ion, the determination of zinc in zinc sulfate tablet and also determination of sulfate content of a mineral water sample.     

Octaethylporphyrin as an ionophore for aluminum potentiometric sensor based on carbon paste electrode

A new sensor to quantitatively sense aluminum in real sample conditions is presented that uses the potentiometric ion selective electrodes. Aluminum is a cation that plays an important role in the environmental process. This approach is proposed to determine aluminum levels in real samples in the required range (10^?6–10^?2 M). Carbon paste electrode (CPE) is introduced here as a potentiometric sensor to measure free concentration of aluminum ion. Octaethylporphyrin (OEP) acts as a selective aluminum recognition agent in the CPE. The suitable selectivity coefficient is obtained for the CPEs compare to interfering cation. The Nernstian slope and detection limit are achieved 18.4 mV/decade and 2.5 × 10^?6 M Al³⁺, respectively. Finally, the proposed method is applied to determine aluminum concentration in real water samples and the result of this method is in agreement with the result of atomic absorption spectroscopy (AAS).     

Sequential injection with lab-at-valve (LAV) approach for potentiometric determination of chloride

Sequential injection with “Lab-at-Valve (LAV)” approach is demonstrated for potentiometric determination of chloride. The LAV flow-through electrode system consists of two Ag/AgCl electrodes: one as a reference electrode, silver chloride activated surface-silver wire soaked in a constant-concentration chloride ion solution in a small tube covered with a polymer-membrane, another as a working electrode (a similar silver chloride activated surface-silver wire) placed in a flow channel. The electrode system is attached at one port of a 10 port multiposition valve. A modified autoburette was used as a propelling device. Using SI operation via a program written in-house, based on LabVIEW^®, a standard/sample is inserted, via the selection valve, in potassium nitrate as an electrolyte and water is used as a carrier. The zones are transported from the holding coil to the flow cell to monitor the difference in potential due to concentration cell behavior. The potential difference is then recorded as a peak. Peak height is proportional to logarithm of chloride concentration. The SI-LAV for chloride determination is very simple, fast, precise, accurate, automatic and economical. Applications to mineral drinking water and surface water have been made. The results agree with those of IC and titrimetric methods.     

Preparation of a solid-state ion-selective electrode based on polypyrrole conducting polymer for magnesium ion

In this study, a potentiometric sensor based on a pencil graphite electrode (PGE) coated with polypyrrole doped with Titan yellow dye (PPy/TY) was prepared for potentiometric determination of magnesium ion in aqueous solutions. The structural characteristics of magnesium sensor electrode (PGE/PPy/TYMg) were studied using scanning electron microscopy and Fourier transform infrared along with energy-dispersive spectroscopy. Under the optimal conditions, the electrode reveals a good Nernstian behavior with slope of 28.27 ± 0.40 mV per decade over the concentration range of 1.0 × 10^?5–5.0 × 10^?2 M and a detection limit of 6.28 × 10^?6 M. The potentiometric response of fabricated electrode toward magnesium ion was found to be independent of the pH of the test solution in the pH range of 4.5–8.0. The electrode showed fast response time (<10 s) and good shelf lifetime (>2 months). The prepared magnesium sensor electrode can also be used as an indicator electrode in potentiometric titration of Mg²⁺ with EDTA with distinguished end point. The electrode revealed good selectivity with respect to many cations including alkali, alkaline earth, transition and heavy metal ions. The introduced magnesium electrode was used for measurement of Mg²⁺ ion in real samples without any serious interferences from other ions.     

Électrochimie dans l'oxydipropionitrile: Comportement électrochimique du solvant. Stabilité des complexes argent(I) halogénures. Solvatation des anions

Electrochemical possibilities of oxydipropionitrile have been shown. The system Ag(s)/Ag⁺ has been used to make a reference electrode in this medium. The electroactivity range which depends on the electrolyte and the kind of electrode used has been specified. At a platinum electrode, in LiClO₄ medium, the electroactivity range is very large. At a mercury electrode, water does not interfere but at a platinum electrode it is oxidizable; the electroactivity range depends on its concentration. The second part treats the complexes with silver ion and halides. Stability constants of complexes and solubility products have been obtained from potentiometric titration curves. The determination of the transfer parameters for ionic species is based on the Strehlow assumption that the potential of the ferrocene/ferricinium couple is constant in all solvents. The results show that the silver ion is more strongly solvated in oxydipropionitrile than in water; on the other hand halide ions are little solvated in this solvent.