Lower limits of the potentiometric titration of perchlorate using a perchlorate ion-selective electrode

Three titrants (tetraphenylarsonium chloride, tetraphenylphosphonium chloride, and tetra-n-pentylammonium bromide) were evaluated for the potentiometric determination of perchlorate. The emf levels were monitored with a perchlorate ion-selective indicator electrode and a double-junction reference electrode. The tetraphenylonium salts were equivalent, yielding the same precision and magnitude of potentiometric breaks. Considerably smaller breaks were obtained with tetra-n-pentylammonium bromide, which, therefore, is not recommended as titrant.The lower limits for the potentiometric titration of perchlorate at ambient temperature were extended to ~0.09 mmol per 50 ml (1.7 × 10^?3N) from the previous 0.25 mmol per 50 ml. If Gran plots are used, they can be further extended to ~0.01 mmol per 50 ml (2.1 × 10^?4N).     

Novel Liquid Membrane Electrode for Selective Determination of Monohydrogenphosphate

A highly selective and sensitive membrane electrode based on vanadyl salen complex (VS), which responds to monohydrogenphosphate (MHP) ions is described. The response of the sensor is Nernstian over the wide concentration range (1.0×10^?1 ? 5.0×10^?6 M) of MHP. The sensitivity of the electrode is high enough to permit the detection of as little as 0.6 μg/mL of MHP without any significant interference from high levels of other anions. The potentiometric selectivity coefficient data revealed negligible interference from 11 common anions. The electrode has a fast response time (<25 s), good slope stability at pH 8.2 for a period of at least eight weeks. It was successfully applied for the direct determination of monohydrogenphosphate in fertilizer and, as indicator electrode, in potentiometric titration of HPO₄^2? ion with barium chloride.     

Novel Bromide PVC‐Based Membrane Sensor Based on Iron(III)‐Salen

A novel bromide PVC‐based membrane sensor, based on iron(III)‐salen (IS) as an electroactive material, is successfully developed. The sensor possesses the advantages of low detection limit (6.0×10^?6), wide working concentration range (7.0×10^?6–1.0×10^?1 M), Nernstian behavior (slope of 59.0±0.5 mV per decade), low response time (<15 s), wide working pH range (3–9), and specially, high bromide selectivity over a wide variety of organic and inorganic anions, specially iodide, chloride, and hydroxide ions. The electrode was used in the direct potentiometric determination of hyoscine butylbromide, and as an indicator electrode in potentiometric titration of bromide ions with silver ions.     

Linear-sweep polarographic determination of active chlorine in aqueous solutions containing phenylthiourea

The linear-sweep polarographic determination of active chlorine is based on its reaction with phenylthiourea in acidic phosphate buffer (pH 2.5) containing potassium chloride. The product, C,C-diphenyldithiodiformamidine, is strongly adsorbed and then reduced at a mercury electrode with two peaks at about ?0.35 V and ?0.87 V (vs. SCE). In the presence of 0.05 M potassium chloride, the potential of the first peak shifts positively to ?0.31 V. This peak provides high sensitivity and selectivity for the determination of traces of active chlorine. The linear range is 1×10^?7?2.5×10^?5 M and the detection limit is 5×10^?8 M (3.6 μg l^?1). The method is used for the direct determination of active chlorine in tap water. The mechanism of the reaction was studied by cyclic voltammetry, electrolysis and potentiometric titration. The first peak (?0.35 V) is ascribed to the reduction of a mercury (II) sulfide film produced by reaction of the adsorbed dithio product with mercury. In the presence of 0.05 M chloride, the formation of a mixed HgS·xHg₂Cl2 film shifts the peak to ?0.31 V.     

Iodide‐Selective Electrode Based on Copper Phthalocyanine

Copper phthalocyanine was used as ion carrier for preparing polymeric membrane selective sensor for detection of iodide. The electrode was prepared by incorporating the ionophore into plasticized poly(vinyl chloride) (PVC) membrane, coated on the surface of graphite electrode. This novel electrode shows high selectivity for iodide with respect to many common inorganic and organic anions. The effects of membrane composition, pH and the influence of lipophilic cationic and anionic additives and also nature of plasticizer on the response characteristics of the electrode were investigated. A calibration plot with near‐Nernestian slope for iodide was observed over a wide linear range of five decades of concentration (5×10^?6?1×10^?1 M). The electrode has a fast response time, and micro‐molar detection limit (ca. 1×10^?6 M iodide) and could be used over a wide pH range of 3.0–8.0. Application of the electrode to the potentiometric titration of iodide ion with silver nitrate is reported. This sensor is used for determination of the minute amounts of iodide in lake water samples.     

Ruthenium(III) Schiff's Base Complex as Novel Chloride Selective Membrane Sensor

A novel chloride PVC‐based membrane sensor based on a ruthenium(III) Schiff's base complex, as an excellent neutral carrier, has been developed. The ruthenium complex, in combination with a ketonic plasticizer and a cationic additive led to ISEs with fundamental characteristics, such as slope sensitivity, short response times and selectivity coefficients, which were sufficient for practical applications. The sensor with composition of 30% PVC, 62% benzyl acetate, 5% ruthenium(III) Schiff's base complex and 3% hexadecyltrimethyl ammonium bromide displays near‐Nernstian behavior in a wide concentration range (1.0×10^?1–3.0×10^?6 M with slope of ?54.5±0.5) with a detection limit of 2.0×10^?6 M (71.0 ng per mL). The response of the electrode is independent on pH in the range of 4.0–10.0 and can it be used for at least ten weeks. The proposed electrode shows a very short response time (<20 s) in whole concentration range. The sensor displays high selectivity toward chloride ions over several organic and inorganic anions. It was successfully applied for the determination of chloride in serum samples. It was also used as an indicator electrode in the potentiometric titration of chloride ions with silver nitrate solution.     

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.     

Construction of a new Ho<Superscript>3+</Superscript> PVC-membrane electrochemical sensor based on <Emphasis Type="Italic">N,N</Emphasis>′-dipyridoxyl(1,4-butanediamine)

N,N′-dipyridoxyl(1, 4-butanediamine) (PYBA) (2 wt % ), nitrobenzene (66 wt %), sodium tetra phenyl borate (2 wt ), and poly vinyl chloride (30 wt %) were applied to create a PVC membrane in Ho³⁺ selective electrode (Ho-SE). Over the concentration range of 1.0 × 10^?5 to 1.0 × 10^?2 M in holmium(III) solution a linear response with lower detection of limit equal 4.0 × 10^?6 M was exhibited by new holmium(III) sensor. Ho-SE possessed a Nernstian slope of 20.1 ± 0.8 mV decade^?1 in very short time spans (~9 s). The potential response of electrode remains without any changes over a pH range of 2.77–8.71. The selectivity coefficient data which was considered by matched potential method for variety of common cations indicated no significant interference. An acceptable recovery for Ho³⁺ in the blend of several cations has been achieved. The utility of Ho-SE in potentiometric titration as an end point indicator electrode gave successfully results.     

PVC matrix membrane sensor for potentiometric determination of dodecylsulfate

The construction and performance characteristics of a new potentiometric PVC membrane sensor for the determination of sodium dodecyl sulfate (SDS) are described. The sensor was based on the use of an N-cetyl-N,N,N trimethyl ammonium (CTA) dodecyl sulfate (DS) ion pair as ion exchange sites in PVC matrix in the presence of o-nitrophenyl octylether as plasticiser. The sensor exhibited a fast, stable, and near-Nernstian response for SDS over the concentration range of 1 × 10^?3 to 10^?6 M at 25°C and the pH range 4–8.5 with anionic slope of 52.5 ± 0.5 mV decade^?1. The lower detection limit was 3 × 10^?6 M, and the response time was 25 s. Selectivity coefficients of SDS with respect to a number of different species were investigated. There were negligible interferences caused by most of the investigated anions. The determination of 1.0–280.0 µg mL^?1 of SDS in aqueous solutions showed an average recovery of 99.1%, and the mean relative standard deviation was 1.4 at 100 µg mL^?1. The results obtained in the determination of SDS in liquid soap, water and in some pharmaceutical preparations compared favourably with those obtained by the Methylene Blue active substance method (MBAS). In the present investigation, the DS sensor has been used as an end-point indicator electrode for some precipitation titration reactions, e.g. titration of SDS with CTMABr and cetylpyridinium chloride with SDS.     

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.     

Electrocatalytic oxidation of captopril using a carbon-paste electrode modified with copper-cobalt hexacyanoferrate

A carbon-paste electrode was modified with copper-cobalt hexacyanoferrate by consecutive potential cycling. The kinetic parameters were calculated for the electroactive species. The resulting electrode exhibited electrocatalytic activity towards the oxidation of captopril. The kinetics of the electrocatalytic reaction was studied. A linear relationship was observed between anodic current and the concentration of captopril in the range of 5.0 × 10^?6–3.1 × 10^?5 μM with a detection limit of 4.2 μM (S/N = 3). The modified electrode was used in the analysis of captopril tablets successfully.     

Zinc-Selective Membrane Electrode Based On 5, 6, 14, 15-Dibenzo-l, 4-Dioxa-8, 12-Diazacyclopentadecane-5, 14-Diene

ABSTRACT

A new PVC membrane for zinc ions based on DBDA15C4 as membrane carrier was prepared. The electrode shows a linear stable response over a wide concentration range (5.0 × 10^?5-1.0 × 10^?1 M) with a slope of 22 mV/decade and a limit of detection of 3.0 × 10^?5 M (2.0 μg/ml). It has a very short response time of less than 5 s and can be use for at least 11 months without any divergence in potential. The zinc ion-selective electrode exhibited very good selectivities with respect to alkali, alkaline earth and some transition and heavy metal ions and could be used in a pH range 1.5-7.0. It was successfully applied for the direct determination of zinc in a pharmaceutical sample and, as an indicator electrode, in potentiometric titration of Zn²⁺ ions.     

Electrometric titrations with two polarized second-order electrodes

Electrometric titrations at constant resistance with two polarized second-order electrodes are shown to be possible. The polarization curve of the silver/silver chloride electrode is investigated theoretically and experimentally in order to find the best conditions for chloride titrations.Directions are given for the preparation and manipulation, of electrodes which enable quick titrations with rather dilute standard solutions (up to 0.001N AgNO₃). The titration apparatus used and some practical applications of the amperometric titration are described.     

Poly(Vinyl Chloride) Containing Dibenzo-18-crown-6 as an Ion-Selective Membrane for Hyamine 1622

Abstract

A poly(vinyl chloride) membrane ion-selective electrode for the Hyamine 1622 cation is proposed. The active substance of the electrode was the neutral carrier dibenzo-18-crown-6 and di-iso-octylphthalate was used as plasticizer. The electrode had a Nernstian behaviour between 6.0 × 10^?6 and 1.6 × 10^?3 mol/dm³, a pH working range of 2 – 12 and high selectivity towards inorganic cations. Among the organic cations tested, only those having surfactant properties did interface. The electrode was suitable for determining the critical micelle concentration and as end-point detector in the potentiometric titration of the cationic surfactants.     

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.     

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.     

Determination of fluoxetine in pharmaceutical preparations and biological samples using potentiometric sensors based on polymeric membranes

The construction and general performance of four novel potentiometric membrane sensors for the determination of fluoxetine have been described. The sensors are based on the formation of the ion association complex of fluoxetine with sodium tetraphenylborate and phosphotungstic acid as electroactive materialles, dispersed in a PVC matrix with dibuthyl sebacate (or diethyl sebacate) as a plasticizer. These sensors exhibit fast, stable and near-Nernstian response for the monocharged fluoxetine cation over wide concentration range from 3.0 × 10^?6 to 1.2 × 10^?2 M and pH 4.0–7.5. No interferences are caused by many inorganic and organic species. Direct potentiometric determinations of 5–100 μg/mL of fluoxetine in drug and urine samples show good recovery of fluoxetine. The developed membrane electrodes have been used as an end point indicator electrode; the potentiometric titration of fluoxetine with sodium tetraphenylborate as a titrant has been monitored.     

Determination of caprolactam by adsorptive voltammetry after separation by thin-layer chromatography

Caprolactam (2-oxohexamethyleneimine) can be determined in wastewaters and natural waters by adsorptive stripping voltammetry after separation of the product of the reaction between caprolactam and p-(N,N-dimethylamino)benzene-p′-azobenzoyl chloride. When a hanging mercury drop electrode is used with an accumulation time of 60 s in stirred solution, caprolactam can be determined from a lower limit of 0.2 μg ml^?1. With a 360-s accumulation time, linear calibration plots are obtained for 8 × 10^?10?8 × 10^?9 mol l^?1 caprolactam. The effect of interfering sample components is eliminated by the TLC separation.     

Mixed Aza‐Thioether Crowns Containing a 1,10‐Phenanthroline Sub‐Unit as Neutral Ionophores for Silver Ion

Three different recently synthesized aza‐thioether crowns containing a 1,10‐phenanthroline sub‐unit (L1–L3) and a corresponding acyclic ligand (L4) were studied to characterize their abilities as silver ion ionophores in PVC‐membrane electrodes. Novel conventional silver‐selective electrodes with internal reference solution (CONISE) and coated graphite‐solid contact electrodes (SCISE) were prepared based on one of the 15‐membered crowns containing two donating S atoms and two phenanthroline‐N atoms (L1). The electrodes reveal a Nernstian behavior over wide Ag⁺ ion concentration ranges (1.0×10^?5?1.0×10^?1 M for CONISE and 5.0×10^?8?4.0×10^?2 M for SCISE) and very low limits of detection (8.0×10^?6 M for CONISE and 3.0×10^?8 M for SCISE). The potentiometric response is independent from pH of the solution in the pH range 3.0–8.0. The electrodes manifest advantages of low resistance, very fast response and, most importantly, good selectivities relative to a wide variety of other cations. The electrodes can be used for at least 2 months (for CONISE) and 4 months for (SCISE) without any appreciable divergence in potentials. The electrodes were used as an indicator electrode in the potentiometric titration of Ag⁺ ion and in the determination of silver in photographic emulsions and in radiographic and photographic films.     

Novel Dy(III) Sensor Based on a New Bis‐Pyrrolidene Schiff's Base

In this work a dysprosium [Dy(III)]‐selective solvent polymeric membrane sensor based on N,N‐bis(pyrrolidene) benzne‐1,2‐diamine, poly(vinyl chloride)(PVC), the plasticizer benzylacetate (BA), and anionic site is described. This sensor responds to Dy(III) activity in a linear range from 1.0×10^?5 to 1.0×10^?1 M, with a slope of 20.6±0.2 mV per decade and a detection limit of 6.0×10^?6 M at the pH range of 3.5–8.0. It has a fast response time of<20 s in the entire concentration range, and can be used for at least 2 months without any considerable divergence in the electrode potentials. The proposed sensor revealed comparatively good selectivity with respect to common alkali, alkaline earth, transition and heavy metal ions. It was used as an indicator electrode in the potentiometric titration of fluoride ions and in determination of concentration of F ^– ions in some mouth washing solutions.