Potentiometric carbon paste sensors for lead(II) based on dithiodibenzoic and mercaptobenzoic acids.

Dithiodibenzoic (DTB) acid and mercaptobenzoic (MB) acid were studied to characterize their abilities as modifier agents for lead(II) sensors. For both sensors, the best results were obtained with modified carbon paste electrodes with 24.1% of ligand. The pH influence on the potentiometric response was studied. The selectivity coefficients for both modified electrodes were tabulated. A potentiometric sensor based on DTB acid exhibited a more sensitive and selective response to lead ions than an MB electrode. The limits of detection for the DTB and MB electrodes were very similar, 5.01 x 10(-8) M and 3.98 x 10(-8) M, respectively, for lead(II) activity. The DTB sensor was applied to lead(II) ion determination in real samples and as an indicator electrode in potentiometric titrations. Natural and commercial humic acids were titrated using the DTB electrode to estimate the stability constant between these organic compounds and the lead(II) ions with successful results.     

Determination of two metals from a single potentiometric titration curve The application of two indicator electrodes

The advantages of applying two indicator electrodes in complexometric potentiometric multicomponent titration are shown by means of simulated titration curves. Two measurement arrangements have been considered, one in which the indicator electrodes are directly connected to a voltmeter and the other in which the electrodes are connected to the voltmeter through a summing operational amplifier. They have been compared with the conventional arrangement of a single indicator electrode and a reference electrode. The influence of the stability constants of the complexes in solution and of the electrode parameters on the shape of titration curves has been examined. It is shown that the use of two indicator electrodes may significantly increase the applicability of multicomponent potentiometric titrations.     

Titrations using an apparatus for recording the antilogarithm of pH or pM

A titration apparatus plotting either the concentration of sample ion or the concentration of titrant ion has been tested. An antilog apparatus, converting measured e.m.f. values into concentrations is connected to ordinary titration equipment. The instrument has been tested by means of acid—base titrations (titrations of mixtures of weak acids and of a weak and a strong acid), precipitation titrations (determination of the chloride concentration in tap-water, titration of mixtures of halides), titrations with ion-selective electrodes (determination of the fluoride content of toothpaste) and complexometric titrations (determination of copper with EDTA, using mercuric ion as indicator ion and amalgamated silver rod as indicator electrode, or using a copper-selective indicator electrode). The method considerably simplifies the evaluation of the results as compared to conventional potentiometric titrations.     

The platinum-20% rhodium electrode in potentiometry

The performance of a platinum-20% rhodium alloy indicator electrode is studied in a number of potentiometric redox and acid-base titrations and compared with that of the conventional platinum electrode. The potential breaks obtained with the alloy electrode are always smaller than those obtained with the platinum electrode. The end-points are also usually indicated later than the true end-points. The bimetallic electrode system comprising platinum and platinum-rhodium electrodes gives a peak at the correct end-point even with 0.001N concentration titrations, where the ordinary potentiometric systems do not always give good results.     

Signal processing with a summing operational amplifier in multicomponent potentiometric titrations

It has been proved that application of two indicator electrodes connected to the ordinary titration apparatus through an auxiliary electronic device (a summing operational amplifier) significantly extends the scope of multicomponent potentiometric titrations in which the analytes are determined simultaneously from a single titration curve. For each analyte there is a corresponding potential jump on the titration curve. By application of the proposed auxiliary device, the sum of the electrode potentials is measured. The device also enables the relative sizes of the potential jumps at the end-points on the titration curve to be varied. The advantages of the proposed signal processing are exemplified by complexometric potentiometric titrations of Fe(III) and Cu(II) in mixtures, with a platinum electrode and a copper ion-selective electrode as the indicator electrodes.     

Potentiometric Determination of Acids and Bases using Silicone Rubber Based Graphite Electrode

Abstract

A silicone rubber based graphite electrode has been used as an indicator electrode for potentiometric acid-base titrations. The electrode potential changes an average of 30 mV per pH-unit. If the electrodes are pretreated with a solution of an oxidant before use, the pH-sensitivity is increased. The electrode can be used in both aqueous and non-aqueous solutions. A measuring cell, composed of a silicone rubber based graphite electrode of small surface area and a chloride-selective reference electrode, can be used for acid-base titrations in the micro range.     

Voltammetric behavior of the iron(II)-(III) and cerium(III)-(IV) couples in potentiometric titrations at constant current and amperometric titrations with two indicator electrodes

The voltammetric behavior at the rotated platinum electrode of the iron(II)-(lII) and cerium (III)-(IV) couples in sulfuric and hydrochloric acids has been investigated The iron and cerium couples are not reversible at a platinum electrode when current flows in the system, and the current-potential curves deviate considerably from those predicted on the basis of reversibility Titration curves for potentiometric titrations at constant current using one and two indicator electrodes are predicted from the current-potential curves and compared with the experimental curves.The degree of reversibility of the iron couple depends greatly on the pretreatment of the electrode The current-potential curves of the iron couple at a platinum electrode coated with a monomolecular film of platinum oxide approach reversibility while those at a clean electrode are highly irreversible Experimental and calculated titration lines for amperometric titrations using two indicator electrodes are compared, and the effects of medium and applied e.m.f. upon the characteristics of the titration curves are considered.     

A Samarium (III) Selective Electrode Based on Zirconium (IV) Boratophosphate

A samarium(III) selective potentiometric sensor has been prepared on the basis of polyvinyl chloride (PVC) membranes containing an ion exchanger (zirconium boratophosphate) as an electro-active material. The best performance was exhibited by a membrane having the following composition: zirconium boratophosphate (10%) and poly vinylchloride (90%). This membrane works well over a wide concentration range (from 1 × 10^?5 to 1 ? 10^?1 M) of Sm(III) ions with a Nernstian slope of 20.2 mV/decade. The response time of the sensor is 15 s, and the membrane can be used for more than six months with good reproducibility. Selectivity coefficients determined by the fixed interference method for a number of mono-, di-, and trivalent cations are reported. The sensor has also been used as an indicator electrode in the potentiometric titrations of samarium (III) ions with EDTA solution.     

Galvanic cell without liquid junction for potentiometric determination of copper

This paper describes potentiometric measurements in an integrated galvanic cell with both indicator and reference electrodes. Both electrodes are conducting polymer-based. The copper-sensitive indicator electrode is made by using poly(3,4-ethylenedioxythiophene) (PEDOT) doped with 2-(o-arsenophenylazo)-1,8-dihydroxynaphthalene-3,6-disulphonic sodium salt (Arsenazo-I) as the electroactive substance in the film, while the reference electrode is based on PEDOT doped by 2-morpholineoethanesulfonic acid (MES). It is shown that the galvanic cell can be used for determination of copper both in non-aqueous media (where all PVC-based membranes failed) and in the presence of chloride ions, which disturb the signal of conventional copper ion-selective electrodes with solid-state membranes. It is further shown that the titration of copper ions can be successfully monitored using the described electrochemical cell.     

Construction of a permanganate ion-selective electrode and its application to potentiometric titrations

The construction of a liquid-membrane type permanganate ion-selective electrode and its application to potentiometric titrations are described. The benzylcetyldimethylammonium-permanganate ion-pair in the aqueous phase is easily extracted into nitrobenzene and the extract is employed as the liquid ion-exchange membrane of the ion-selective electrode. The electrode gives Nernstian response to permanganate in the concentration range from 10(-6) to 10(-1)M, and the potential is almost independent of pH over the range from 3.0 to 10.5. The electrode can be used as indicator electrode in potentiometric titrations with permanganate.     

Ketoconazol‐Triiodide Ion Pair Complex as a Suitable Carrier in an Iodide Selective Membrane Electrode

A novel membrane sensor for selective monitoring of iodide, consisting of a triiodide‐ketoconazole ion pair complex dispersed in a PVC matrix, plasticized with a mixture of 2‐nitrophenyl octyl ether and dioctylphtalate with unique selectivity toward iodide ions, is described. The influence of membrane composition, pH of test solution and foreign ions on the electrode performance were investigated. The optimized membrane demonstrates a near‐Nernstian response for iodide ions over a wide linear range from 1.0 × 10^?2 to 1.0 × 10^?5 M, at 25 ± 1 °C. The electrode could be used over a wide pH range 3–10 and has the advantages of high selectivity, fast response time and good lifetime (over 4 months). It was successfully used as indicator electrode in potentiometric titrations and direct potentiometric assay of iodide ions.     

Ti/TiO2 indicator electrodes formed by plasma electrolytic oxidation for potentiometric analysis

Ti/TiO₂ indicator electrodes were prepared by plasma electrolytic oxidation (PEO) method in the tetraborate electrolyte and were used for potentiometric indication of chemical reactions of different types and for analysis of surface and industrial wastewaters on the example of potentiometric determination of alkalinity and chloride. The electrodes formed at current densities of 0.05, 0.1, 0.15 and 0.2 A/cm² are different in composition, surface morphology and electroanalytical properties. The electrodes formed at a current density of 0.05 A/cm² exhibit the highest pH-sensitivity and generate the highest analytical signal at the equivalence point in the acid–base and precipitation titrations. The maximum analytical signal at the equivalence point, exceeding in magnitude the analytical signal, obtained by classical Pt electrode in oxidation–reduction and complexometric titrations generates PEO layers formed at a current density of 0.05 A/cm² and a platinum-modified nanoparticles. The results of the potentiometric titration of the surface and technogenic waters using as indicator Ti/TiO₂ electrodes are comparable with the conventionally used glass electrode (to determine alkalinity) and Ag electrode (to the determine chloride) and the results of visual titration. The advantage of the obtained metal oxide systems is the ability to determine two hydrochemical parameters due to their multifunctionality and opportunity to work with a single electrode. In addition, these sensors offer some analytical characteristics such as sensitivity, good reproducibility, high mechanical stability and a simple preparation procedure.     

Simple PVC–PPy electrode for pH measurement and titrations

Cobaltabis(dicarbollide) [3,3'-Co(1,2-C2B9H11)](-)-doped polypyrrole (PPy) films have been prepared galvanostatically on glassy carbon electrodes in acetonitrile solution. The potential response behavior of the film of this new material has been investigated in some common pH buffers and in acid-base titrations. The potentiometric characteristics of the resulting films are indicative of a quasi-Nernstian response (approximately 50 mV/pH unit), a linearity range from pH 12 to 3 and correlation coefficients (r2) of approximately 0.98. The electrode is suitable for pH measurements and for monoprotic titrations of strong alkalis with strong acids, and weak bases with strong acids, but the long response time hinders the use of this electrode for multiprotic titrations. The time response has been dramatically improved by reducing the film thickness by using the template effect of a non-conducting polymer (PVC) cast over the graphite surface before PPy deposition. PPy polymerization occurs in the free channels of PVC leading to the formation of PPy wires. The morphological change of PPy does not affect the slope or linearity range. The response of the PVC-PPy electrochemical sensor is rapid and the sensor is easy to prepare, at low cost, and its performance is comparable with that of commercial glass electrodes.     

Determination of Cr(VI) with Selective Sensing of Cr(VI) Anions by a PVC‐Membrane Electrode Based on Quinaldine Red

A dichromate‐selective PVC‐membrane electrode based on Quinaldine Red (an acridinium derivative) is described. The electrode exhibits rapid (< 30 s) and linear response to the activity of Cr(VI) anions in the range of 5.2 × 10^?6 ?1.0 × 10^?1 M dichromate with the limit of detection 2.5 × 10^?6 Mof Cr₂O₇^2?. The sensor is used as an indicator electrode in potentiometric determination of Cr(VI) anions and is also suitable for end‐point indication in the titrations of proper metal ions with dichromate under laboratory conditions. The proposed electrode has been applied to the direct potentiometric determination of Cr(VI) anions in water samples with satisfactory results.     

Development of a Novel Solid‐State pH Sensor Electrode Based on Titanium Oxide Thin Film as an Indicator Electrode in Potentiometric Acid‐Base Titrations in Fused NaNO3 at 350°C

A solid‐state pH sensor was fabricated using a transparent conductive titanium oxide film on a glass substrate. The coating of the glass substrate was achieved by a novel simple chemical vapor deposition (CVD) procedure. The sensor slope was found to increase as the temperature of the solution was increased. The performance of the sensor was investigated in the pH range from 2.2 to 11.19. The E‐pH curve is linear with slope of 0.054 V at 298.15 K. This value is closed to the theoretical value 2.303RT/F (0.059 V at 298.15). The standard potential of this electrode, E°, is computed as 177.58 mV with respect to the SCE as reference electrode. Results obtained by the suggested sensor compares very well with conventional pH electrodes where the square of the correlation coefficient was 0.998. This electrode can be used as an indicator electrode in potentiometric acid‐base titration. This electrode behaves reversibly and responds to the oxide ion concentration in molten NaNO₃. K₂Cr₂O₇ was potentiometrically titrated with Na₂O₂ and K₂CO₃ as titrants in molten NaNO₃ at 350°C, using the above mentioned indicator electrodes. An acidity/basicity scale of the oxyanions was established in molten NaNO₃ at 350°C.     

Co2+-selective membrane electrode based on the Schiff Base NADS

A new PVC membrane electrode for cobalt(II) ions based on a recently synthesized Schiff base of 5-((4-nitrophenyl)azo)- N-(2',4'-dimethoxyphenyl)salicylaldimine is reported. The electrode exhibits a Nernstian response for Co(2+) ions over a wide concentration range (9.0 x 10(-7)-1.0 x 10(-2) M) with a slope of 29(+/-1). The limit of detection is 8.0 x 10(-7) M. The proposed sensor revealed good selectivities over a wide variety of other cations including hard and soft metals. This electrode could be used in a pH range of 3.5-6.0. It was used as an indicator electrode in potentiometric titrations of cobalt(II) ions and can be used in the direct determination of Co(2+) in aqueous solutions.     

Construction and evaluation of ion-selective electrodes for potassium and calcium with a summing operational amplifier. Application to wine analysis

Electrodes selective to potassium and calcium with improved senstivity were constructed like conventional electrode (ISEs), but used an operational amplifier to sum the potentials supplied by the four membranes (ESOAs). The results obtained during the evaluation of their working characteristics were compared to those obtained by conventional ISEs and were found to be similar, but with higher precision. The electrodes were used in the potentiometric determination of potassium, calcium and magnesium in wines. The results given by ESOAs were more precise than those from ISEs. The results obtained by potentiometry were in good agreement with those from AES for potassium and AAS for calcium and magnesium.     

Determination of mercaptopyrimidines with copper(II) in acetonitrile

A non-aqueous oxidimetric method is described for the determination of mercaptopyrimidines with copper(II) perchlorate in acetonitrile, diphenylamine being used as indicator. A bright platinum wire is used as indicator electrode and a modified calomel or an antimony electrode as reference for potentiometric titrations. The method, based on the oxidation of the mercapto group to the disulphide, is simple, accurate and reliable.     

Calixarene-based potentiometric ion-selective electrodes for silver

Four lipophilic sulphur and/or nitrogen containing calixarene derivatives have been tested as ionophores in Ag(I)-selective poly (vinyl chloride) membrane electrodes. All gave acceptable linear responses with one giving a response of 50 mV/dec in the Ag(I) ion activity range 10(-4)-10(-1)M and high selectivity towards other transition metals and sodium and potassium ions. This ionophore was also tested as a membrane coated glassy-carbon electrode where the sensitivity and selectivity of the conventional membrane electrode was found to be repeated. The latter electrode was then used in potentiometric titrations of halide ions with silver nitrate.     

A Simple Sensor for Potentiometric Titrations

Abstract

A sensor for potentiometric titrations was prepared by coating a spectroscopic graphite rod with a solution of poly(vinyl chloride) and dioctylphthalate in tetrahydrofuran. The reference was a Ag/AgCl single-junction electrode. The sensor was used in the following potentiometric titrations:

1. precipitation titrations 2. acid-base titrations, 3. compleximetric titrations, and 4. redox titrations.

A survey of its use in such titrations is presented.

Preparation of the coated-graphite sensor is simple and rapid. Moreover, it is quite inexpensive. A limitation is its applicability in aqueous media only, because organic solvents will dissolve the membrane.